WO2003085029A1 - Resin composition for light emitting diode reflectors - Google Patents

Resin composition for light emitting diode reflectors Download PDF

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Publication number
WO2003085029A1
WO2003085029A1 PCT/JP2003/004361 JP0304361W WO03085029A1 WO 2003085029 A1 WO2003085029 A1 WO 2003085029A1 JP 0304361 W JP0304361 W JP 0304361W WO 03085029 A1 WO03085029 A1 WO 03085029A1
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Prior art keywords
derived
mole
dicarboxylic acid
aliphatic
mol
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PCT/JP2003/004361
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French (fr)
Japanese (ja)
Inventor
Kunihiro Ouchi
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Mitsui Chemicals, Inc.
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Application filed by Mitsui Chemicals, Inc. filed Critical Mitsui Chemicals, Inc.
Priority to AU2003236271A priority Critical patent/AU2003236271A1/en
Priority to JP2003582215A priority patent/JPWO2003085029A1/en
Publication of WO2003085029A1 publication Critical patent/WO2003085029A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function

Definitions

  • the present invention relates to a polyimide resin composition suitable for a molded article material of a light-emitting diode reflector, having low water absorption and excellent heat resistance, and a molded article thereof.
  • Light-emitting diodes are broadly divided into two types: a shell type made of epoxy resin and a resin reflector. The latter light-emitting diode is manufactured by installing a light-emitting diode on a reflector formed of resin and sealing it with epoxy.
  • the resin used to mold this light-emitting diode reflector must have performance such as high light reflectance, high light resistance, high adhesion to the epoxy encapsulant, and heat resistance that does not easily discolor at the curing temperature of the epoxy encapsulation process. .
  • LCP liquid crystal polymer
  • heat-resistant polyamide have been used.
  • LCP is excellent in heat resistance and light resistance, but has the drawback that adhesion to an epoxy sealing material is very poor.
  • the heat-resistant polyamide produced by the conventional technology has good adhesion to the epoxy encapsulant, but has problems such as peeling off of the epoxy encapsulant and bubbles during curing of the epoxy encapsulant. .
  • the heat-resistant polyamide according to the conventional technique removes water that was previously naturally contained in the heat-resistant polyamide. If the pre-drying operation is not performed (preliminary drying operation such as heating operation), the pre-drying operation is not necessary in view of the problem of the conventional technology that peeling and bubbles occur during epoxy bonding and epoxy sealing.
  • Another object of the present invention is to provide a light-emitting diode reflector and a heat-resistant polyamide.
  • One of the problems to be solved by the present invention is that peeling and bubbles are generated during epoxy bonding or epoxy sealing without a special drying operation such as a heating operation during manufacturing. It is another object of the present invention to provide a light-emitting diode reflector including the resin composition.
  • the problem to be solved by the present invention is to solve the problems in the conventional technology as described above, and is suitable for a molded article material of a light emitting diode reflector, low water absorption and heat resistance. It is an object of the present invention to provide a polyamide resin composition having excellent properties, a light-emitting diode reflector including the resin, and a light-emitting diode reflector formed by molding the resin.
  • DISCLOSURE OF THE INVENTION In order to overcome the above-mentioned problems, the present inventors have studied the components constituting the polyamide resin in more detail, and as a result, have found a resin having low water absorption and further excellent heat resistance.
  • the present invention 1, 9 - and Diaminononane 5 0-1 0 0 mole 0/0, fats having linear aliphatic Jiamin a carbon number of 6 to 1 2, and Z or the side chain of 6-1 2 carbon atoms family Jiamin 0-5 0 mole% derived from Jiamin derived constituent unit - and (a 1), and terephthalic acid 6 0-1 0 0 mole 0/0, other than terephthalic acid
  • 2 meds were baked (heat treated) before processing.
  • the present inventors have reported that the conventional heat-resistant polyamide, if not baked (heat-treated) before processing, would cause the epoxy encapsulant to peel off or generate bubbles when the epoxy encapsulant is cured. Since the heat-resistant polyamide is water-absorbing, the moisture that the heat-resistant polyamide naturally occupies may cause peeling of the epoxy encapsulant and bubbles during curing of the epoxy encapsulant. We made a working hypothesis that it might As a result, when the “water absorption” described later in the “Examples” section of the present application specification was adopted as the evaluation scale, the water absorption of the heat-resistant polyamide according to the conventional technology was approximately 3.9%. That was all.
  • the heat-resistant polyamide has a moisture content in a range of 0 to 3.9% of moisture content that does not cause peeling of the epoxy sealing material or generation of bubbles when the epoxy sealing material is cured.
  • the critical value threshold value
  • the epoxy absorption was found to be 3.5% or less, preferably 3.0% or less, more preferably 2.5% or less, and even more preferably 2.0% or less. It has been found that neither exfoliation nor bubbles occur.
  • a heat-resistant polyamide having a water absorption of 3.5% or less preferably a heat-resistant polyimide having a water absorption of 3.0% or less, and more preferably a heat-resistant polyamide having a water absorption of 2.5% or less. If a heat-resistant polyamide of 2.0% or less is applied to the light-emitting diode reflector, epoxy bonding can be performed without performing a preliminary drying operation such as a heating operation required in the conventional technology. The idea was that there would be no delamination or bubbles when sealing with epoxy or epoxy.
  • the heat-resistant polyamide obtained by the conventional technology uses an operation (such as a heating operation) for previously removing moisture that was naturally contained in the heat-resistant polyamide. If the pre-drying operation is not performed, heat-resistant polyamides that do not require a pre-drying operation will be generated in view of the problems of the conventional technology that peeling and bubbles will occur during epoxy bonding and epoxy sealing.
  • epoxy bonding and epoxy encapsulation can be performed without the need for preliminary drying operations such as heating operations, which were required in conventional technologies.
  • Aromatic dicarboxylic acids, and Z or aliphatic dicarboxylic acid having a carbon atom number of 4-2 0 0-4 0 mole 0/0 derived from dicarboxylic acid-derived constituent unit - a made of Polyamide with (a 2) in the molecule Provided is a polyamide resin used for a light-emitting diode reflector, characterized by comprising:
  • the polyamide resin composition for a light-emitting diode reflector according to the present invention comprises, as component (A), 1,9-diaminononane 50-: L 0 0 mol%, and a straight-chain aliphatic having 6-12 carbon atoms.
  • the inorganic filler of the component (B) of the present invention is a group consisting of glass fiber, talc, wollastonite, potassium titanate, zinc oxide, titanium dioxide, calcium carbonate, barium sulfate, and calcined kaolin clay. Including at least one inorganic filler selected from among the following is one of preferred embodiments of the present invention.
  • the present invention provides a light-emitting diode reflector including the above-described polyamide resin.
  • the present invention provides a light-emitting diode reflector comprising the above-described polyamide resin composition.
  • the present invention relates to a 1,9-diaminononane of 50 to 100 mol%, a linear aliphatic diamine having 6 to 12 carbon atoms, and an aliphatic group having Z or a side chain having 6 to 12 carbon atoms.
  • Diamin-derived structural unit (a-1) derived from 0 to 50 mol% of diamin, and terephthalic acid 60 to: L 00 mol 0 /.
  • an aromatic dicarboxylic acid other than terephthalic acid and a dicarboxylic acid-derived structural unit (a-2) derived from 0 to 40 mol% of Z or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms in the molecule.
  • An epoxy characterized by comprising a polyamide
  • a resin composition for a molded product for resin bonding is provided.
  • Epoxy resin bonding molded article resin composition of the present invention as the component (A), 1, 9 - diamine Nononan 5 0: 1 0 0 mole 0/0, 6-1 2 carbon atoms linear aliphatic Jiami down, and Roh or aliphatic Jiamin 0-5 0 mole 0/0 derived Jiamin derived structural units have a side chain with carbon number 6 ⁇ 1 2 (a _ 1) , terephthalic acid 6 0-1 0 0 mole 0/0, the aromatic dicarboxylic acid other than terephthalic acid, and / or carbon atoms 4-2 0 aliphatic dicarboxylic acids 0-4 0 mole% derived from dicarboxylic acid-derived constituent unit It is preferable to include 100 parts by weight of a polyamide having (a-2) in a molecule, and 1 to 200 parts by weight of an inorganic filler as the component (B).
  • the term “light-emitting diode reflector” used in the present application uses the Chinese character “plate”, the concept of this word is limited to only those having a “plate” shape. At least, the casing in the direction of emitting light is open or not open.Cases including housing in general, more specifically those having a box-like or box-like shape, funnel-like Plates (planes) such as those having a shape, those having a bowl shape, those having a parabona shape, those having a columnar shape, those having a conical shape, those having a honeycomb shape, etc. , A spherical surface, a curved surface, or the like) as a surface for reflecting light.
  • the light-emitting diode reflector is generally formed by injection molding, melt molding, extrusion molding, or inflation molding of polyamide resin or a resin composition containing polyamide resin and an inorganic filler. It is formed into a desired shape by heat molding such as blow molding.
  • the light emitting diode reflector is usually a light emitting diode. Encapsulation, bonding, bonding, etc. are performed with a chip element and other components and epoxy resin.
  • polyamide resin As the polyamide resin, the following polyamide resin (component (A)) is used.
  • the polyamide resin (component (A)) is polymerized from a diamine-derived structural unit (a-1) and a dicarboxylic acid-derived structural unit (a-2).
  • Polyamide resin (component (A)) is a heat-resistant polyamide resin having a water absorption of 3.5% or less, when "water absorption” described later in the section of "Examples” is adopted as an evaluation scale. Is a heat-resistant polyamide resin of 3.0% or less, more preferably a heat-resistant polyamide resin of 2.5 ° / 0 or less, and more preferably a polyamide resin of 2.0% or less.
  • Polyamide resin (component (A)) generally has a water absorption of 1.5 to 3.5% when the “water absorption” described later in the section of “Examples” is adopted as a scale of evaluation.
  • Heat-resistant polyamide resin preferably 1.5 to 3.0% heat-resistant polyamide resin, more preferably 1.5 to 2.5% heat-resistant polyamide resin, and still more preferably 1.5 to 2.5% It is a polyamide resin of 2.0 or less.
  • the structural unit ( a -1) derived from the diamine constituting the polyamide resin (component (A)) used in the present invention is composed of 1,9-diaminononane and a linear or Z- or side-chain carbon atom having 6 or more carbon atoms. derived from ⁇ 1 2 aliphatic Jiamin, 1, 9 Jiamino nonane 5 0-1 0 0 mole 0 /. It is preferable to synthesize from a diamine-derived structural unit containing 0 to 50 mol% of an aliphatic diamine having 6 to 12 carbon atoms having a straight chain, Z or a side chain.
  • linear aliphatic diamine component constituting the diamine-derived structural unit (a-1) together with 1,9-diaminononane include 1,6-diaminohexane, 1,7- Diaminoheptane, 1,8-diaminooctane, 1,9 diaminononane, 1,10-diaminodecane, 1,11-diaminopendecane, and 1,12-diaminododecane You. Among these, 1,6-diaminohexane is particularly preferred.
  • the aliphatic diamine component having 6 to 12 carbon atoms and having a side chain which constitutes the diamine-derived structural unit (a-1) together with 1,9-diaminononane is particularly an aliphatic diamine having a side chain alkyl group.
  • specific examples include 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1, 8-diaminooctane, 2-methyl-1, 9 diamino nononane, 2-methinolate 1, 10-diaminodecane, 2-methinole 1, 1 1 1 diamino undecane and the like.
  • structural units derived from 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, and 2_methyl-1,9-diaminononane are preferred, and particularly, 2— Methyl 1,8-diaminooctane is preferred.
  • the above diamine component, which is formed together with 1,9-diaminononane can be used by mixing a linear aliphatic diamine component and an aliphatic diamine component having a side chain alkyl group at an arbitrary ratio. It is preferred to use the component alone or the aliphatic diamine component having a side chain alkyl group alone.
  • the dicarboxylic acid-derived structural unit (a-2) constituting the polyamide resin (component (A)) used in the present invention has a terephthalic acid-derived structural unit of 60 to 100 mol%, and an aromatic other than terephthalic acid. It is preferable to polymerize from 0 to 40 mol% of a dicarboxylic acid-derived structural unit, and from 0 to 40 mol% of a dicarboxylic acid-derived structural unit having 4 to 20 carbon atoms.
  • examples of the structural unit derived from an aromatic dicarboxylic acid other than terephthalic acid include isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, and combinations thereof.
  • the structural unit derived from an aliphatic dicarboxylic acid particularly limits the number of carbon atoms. It is preferably, but not exclusively, derived from 4-20, more preferably 6-12 aliphatic dicarboxylic acids.
  • the aliphatic dicarboxylic acid used to derive such an aliphatic dicarboxylic acid-derived structural unit include, for example, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, pendecanediene Force olevonic acid, dodecanedicarboxylic acid and the like. Of these, adipic acid is particularly preferred.
  • the structural unit derived from terephthalic acid-derived structural unit is 60 to 1 0 0 mole 0/0, preferably 8 0-1 0 0 mole 0/0 is contained in an amount of a structural unit derived from an aromatic dicarboxylic acid-derived constituent units other than terephthalic Le acid
  • 0-4 0 mole 0/0 preferably be contained in an amount of 0-2 0 mole 0/0, and / 'or a carbon atom number 4 2 0, preferably 4 to from 1 2 aliphatic dicarboxylic acid constitutional
  • the structural unit derived from the unit is contained in an amount of 0 to 40 mol%, preferably 0 to 20 mol% .
  • the dicarboxylic acid-derived structural unit (a-2) a small amount, for example, about 10 mol% or less of a polyvalent carboxylic acid-derived structural unit may be contained together with the terephthalic acid-derived structural unit and the aliphatic dicarboxylic acid-derived structural unit as described above.
  • Specific examples of such a polycarboxylic acid-derived structural unit include tribasic acids and polybasic acids such as trimellitic acid and pyromellitic acid.
  • the diamine-derived structural unit (a-1) and the dicarboxylic acid-derived structural unit (a-2) as described above are added. It can be produced by heating in the presence of a catalyst. In this reaction, it is preferable that the total number of moles of the diamine-derived structural unit (a-1) is larger than the total number of moles of the dicarboxylic acid-derived structural unit (a-2).
  • the structural unit derived from dicarboxylic acid is 100 mol%
  • the total structural unit derived from diamine is 100 to 100 mol%. It is 120 mol%.
  • This reaction is usually performed in an inert gas atmosphere, and the inside of the reaction vessel is generally replaced with an inert gas such as nitrogen gas.
  • an inert gas such as nitrogen gas.
  • Catalysts that can be used to produce the polyamide resin (component (A)) used in the present invention include: phosphoric acid, salts thereof and ester compounds of phosphoric acid; And its salt and ester compounds; and hypophosphorous acid and its salt and ester compounds.
  • phosphoric acid, sodium phosphate, sodium phosphite, potassium hypophosphite, sodium hypophosphite and the like are preferable.
  • These phosphoric acid compounds can be used alone or in combination.
  • the dicarboxylic acids such as described above, typically 0.0 0 1-5 mole 0/0, preferably used in a ratio of 0.0 0 2-2 mol 0/0.
  • a terminal blocking agent As the terminal blocking agent, benzoic acid, an alkali metal salt of benzoic acid, acetic acid and the like can be used. Such an end capping agent is generally used in an amount of 0.01 to 5 mol, preferably 0.01 to 2 mol, per 1 mol of the dicarboxylic acid.
  • the limiting viscosity [ ⁇ ] of the resulting polycondensate can be controlled by adjusting the amount of the terminal blocking agent used.
  • the reaction conditions for preparing such a polycondensate are, specifically, a reaction temperature of usually 200 to 290, preferably 220 to 280, and a reaction time of usually 0.5. 55 hours, preferably 1-3 hours. Further, this reaction can be carried out under any conditions from normal pressure to pressurization, but it is preferable to carry out the reaction under pressurized conditions, and the reaction pressure is usually 20 to 60 kg / cm 2, preferably 2 to 60 kg / cm 2. Set within the range of 5 to 50 [kg] / cm2.
  • the intrinsic viscosity [] measured in concentrated sulfuric acid at 30 ° C. is usually 0.05 to 0.6 dlZg, preferably 0.08 dlZg.
  • a low-order condensate within the range of 0.3 dl / g can be obtained.
  • the polyamide low-order condensate thus formed in the aqueous medium is separated from the reaction solution.
  • a method such as filtration or centrifugation can be employed.However, the reaction solution containing the low-condensation product of the generated semi-aromatic polyamide can be used. The method of performing solid-liquid separation by flushing into the atmosphere through a nozzle is efficient.
  • post-polymerization is performed using the polyamide low-order condensate obtained as described above.
  • the post-polymerization is preferably carried out by drying the polyamide low-order condensate, heating it to a molten state, and applying a shear stress to the melt.
  • the mixture is heated to a temperature at which the dried polyamide low-order condensate at least melts.
  • it is heated to a temperature equal to or higher than the melting point of the low-density condensate of the dried polyamide, and preferably 10 to 60 ° C higher than this melting point.
  • the shear stress can be applied to the melt by using, for example, a twin-screw extruder with a vent or a kneader. It is considered that by applying shear stress to the melt in this way, the low-order condensate of the dried polyamide in the molten state is polycondensed with each other, and the polycondensation reaction of the condensate also proceeds.
  • the above polyamide low-order condensate is subjected to solid-state polymerization by a generally known method, and the intrinsic viscosity [] is reduced to 0.1. Polyamides in the range of 5 to 2.0 [d1 / g] can be prepared.
  • solid-state polymerization of the above polyamide low-order condensate is carried out by a generally known method to obtain an intrinsic viscosity. [7?] Was prepared in the range of 0.5 to 1.5 [d1 / g].
  • the polyamide resin (component (A)) used in the present invention can be heated to a temperature not lower than the melting point of the polyamide and lower than the decomposition temperature, and can be molded into a desired shape using a usual molding apparatus. .
  • the light-emitting diode reflector can be efficiently formed by injection molding.
  • the polyamide resin (component (A)) having the above composition range can have excellent moldability, low water absorption, and heat resistance.
  • the polyamide resin used in the present invention has an intrinsic viscosity of 0.5 to 3.0 [ £ 11], preferably 0.5 to 2.5 [dl Zg], particularly 0.6 to 2.0, measured in 96.5% sulfuric acid at 25 ° C. [d 1 / g] is preferable. In such a range, the moldability and the strength properties of the molded product are excellent.
  • the polyamide resin (component (A)) used in the present invention has a melting point measured by DSC of 260 ° C. or more and less than 330 ° C., and particularly, from 27 ° C. to 320 ° C.
  • the melting point was measured by using a DSC (differential scanning calorimeter) once at 330 ° C for 5 minutes, then cooled down to 23 ° C at a rate of 10 ° C, then cooled down. The heating was performed at 10 [° CZ min]. The endothermic peak based on the melting at this time was defined as the melting point (Tm).
  • the inorganic filler inorganic filler
  • the following inorganic fillers are preferably used.
  • the following fillers are added in an amount of 1 to 200 parts by weight based on 100 parts by weight of the polyamide resin (component (A)) as long as the effects of the present invention are not impaired.
  • Fibrous fillers especially glass fibers, aramide fibers, carbon fibers, etc.
  • powdered, granular, plate-like and needle-like fillers especially silica, alumina, calcium carbonate, titanium dioxide, talc, wollastonite
  • Caso earth especially silica, alumina, calcium carbonate, titanium dioxide, talc, wollastonite
  • Caso earth brewing power Orinkley, clay, kaolin, spherical glass, My power, magnesium oxide, calcium carbonate, barium sulfate, zinc oxide, potassium titanate, whisker, etc.
  • Glass fiber, talc, ⁇ Olastonite, potassium titanate, zinc oxide, titanium oxide, calcium carbonate, barium sulfate, and calcined kaolin clay are preferred, and include at least one or more inorganic fillers selected from these.
  • additives ie, antioxidants (hindered phenols), heat stabilizers (phosphorus compounds, lactones) are used according to the intended use within a range that does not impair the effects of the present invention.
  • Other polymers olefins, modified polyolefins, ethylene 'propylene copolymer, ethylene.
  • each component is mixed by various known methods, for example, a Hensile mixer, a V-blender, a ribbon blender, a tumbler blender, etc. Alternatively, a method of melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer or the like after mixing, and then granulating or pulverizing may be adopted.
  • the polyamide composition according to the present invention comprises an inorganic filler as a component (B) while heating and maintaining the polyamide (A) in a molten state, for example, at 280 to 360 ° C.
  • the polyamide resin (component (A)) composition prepared as described above may be formed into a powder, pellet, or other shape by compression molding, injection molding, extrusion molding, or the like. By using it, it can be made into various molded products.
  • Intrinsic viscosity Dissolve 0.5 [g] of polyamide resin in 50 [ml] of 96.5% sulfuric acid solution, and use an Ubbelohde viscometer to sample under the condition of 25.0 ⁇ 0.05 ° C. The number of seconds for the solution to flow was measured, and calculated based on the following equation.
  • NMDA 1,9-S ', aminononane
  • MODA 2-Methyl-1,8-S'aminooctane
  • HMDA 1,6-S
  • Aminohexane TA Terephthal
  • AA V / H. 0.06 [kg] (0.6 mol) of sodium hypophosphite monohydrate and 27.4 [kg] of distilled water were placed in an autoclave, and the inside of the reactor was sufficiently replaced with nitrogen. While stirring, the internal temperature was raised to 250 ° C over 4 hours. The reaction was continued for 1 hour as it was to obtain a polyamide low-order condensate. This polyamide low-order condensate was subjected to solid-state polymerization at 190 ° C. for 12 hours under vacuum. Then
  • Example 1 The molar ratio of diamine-derived structural units and dicarboxylic acid component shown in the table Thus, a polyamide resin was obtained in the same manner as in Example 1. A polyamide resin composition was obtained in the same manner as in Example 1. These were evaluated in the same manner as in Example 1, and the results are shown in the table.
  • Example 1 In the same manner as in Example 1, except that the type of diamine was changed to 1,6-diaminohexane, the molar ratio of the diamine-derived structural unit and dicarboxylic acid component shown in the table was used. A polyamide resin and a polyamide resin composition were obtained by the above method. As a result of evaluating these in the same manner as in Example 1, the water absorption was high. Industrial Applicability One of the effects of the present invention is that, based on the knowledge obtained by the present inventors, in the heat-resistant polyamide according to the conventional technology, the moisture that the heat-resistant polyamide naturally contained in advance is removed.
  • the removal operation (preliminary drying operation such as heating operation) is not performed, the preliminary drying operation is not performed in consideration of the problem of the conventional technology that peeling and bubbles are generated during epoxy bonding and epoxy sealing.
  • An unnecessary heat-resistant polyamide for a light emitting diode reflector can be provided.
  • One of the effects of the present invention is that peeling and bubbles are not generated during epoxy bonding or epoxy sealing without a special drying operation such as a heating operation during manufacturing. It is possible to provide a light-emitting diode reflecting plate including the resin composition.
  • the effect of the present invention is to solve the problems in the prior art, and is a polyamide resin composition suitable for a molded article material of a light emitting diode reflector, which is excellent in low water absorption and heat resistance.
  • An object, a light-emitting diode reflector including the resin, and a light-emitting diode reflector formed by molding the resin can be provided.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A resin composition useful in the production of light-emitting diode reflectors is provided, which can suppress delamination or bubbling in epoxy bonding or epoxy sealing even when preliminary drying such as heating is not carried out. The resin composition is characterized by comprising 100 parts by weight of a polyamide resin and 1 to 200 parts by weight of an inorganic filler (B), the polyamide resin being one comprising diamine units consisting of 50 to 100 mole % of 1,9-diaminononane and 0 to 50 mole % of a linear aliphatic diamine having 6 to 12 carbon atoms and/or an aliphatic diamine having a C6-12 side chain and dicarboxylic acid units consisting of 60 to 100 mole % of terephthalic acid and 0 to 40 mole % of an aromatic dicarboxylic acid except terephthalic acid and/or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms.

Description

明細書 発光ダイォード反射板用樹脂組成物 技術分野 本発明は、 発光ダイオード反射板の成形品材料に好適な、 低吸水性、 お ょぴ耐熱性に優れるポリァミ ド樹脂組成物、およびその成形品に関する。 背景技術  TECHNICAL FIELD The present invention relates to a polyimide resin composition suitable for a molded article material of a light-emitting diode reflector, having low water absorption and excellent heat resistance, and a molded article thereof. . Background art
[技術的背景] [Technical background]
従来、 発光ダイオードは赤色と緑色だけであつたが、 近年、 青色が開 発されたことによって光の 3原色が揃った。 これによつて、 発光ダイォ —ドはフルカラー化が可能となり、 携帯電話の液晶バックライ ト、 種々 のディスプレイや照明などの多くの分野で利用されつつある。 発光ダイ ォードには大きく分けて、 エポキシ樹脂で成形された砲弾型と樹脂製反 射板付きの二つがある。 後者の発光ダイォードは樹脂から成形された反 射板に発光ダイォードを設置した後、 エポキシで封止して製造される。 この発光ダイオード反射板を成形する樹脂には、 高い光線反射率、 高い 耐光性、 エポキシ封止材との高い密着性、 エポキシ封止工程の硬化温度 で変色しにくい耐熱性などの性能が求められる。  In the past, light emitting diodes were only red and green, but recently the development of blue has brought the three primary colors of light together. As a result, light emitting diodes can be made full color, and are being used in many fields such as liquid crystal backlights for mobile phones, various displays and lighting. Light-emitting diodes are broadly divided into two types: a shell type made of epoxy resin and a resin reflector. The latter light-emitting diode is manufactured by installing a light-emitting diode on a reflector formed of resin and sealing it with epoxy. The resin used to mold this light-emitting diode reflector must have performance such as high light reflectance, high light resistance, high adhesion to the epoxy encapsulant, and heat resistance that does not easily discolor at the curing temperature of the epoxy encapsulation process. .
例えば、 この分野では、 L C P (液晶ポリマー） や耐熱ポリアミ ドが 使用されてきた。 L C Pは耐熱性と耐光性に優れているが、 エポキシ封 止材との密着性が非常に悪いという欠点を有している。 また、 従来の技 術による耐熱ポリアミ ドは、エポキシ封止材との密着性は良好であるが、 エポキシ封止材硬化時に、 エポキシ封止材の剥離や気泡を発生する等の 問題があった。  For example, in this field, LCP (liquid crystal polymer) and heat-resistant polyamide have been used. LCP is excellent in heat resistance and light resistance, but has the drawback that adhesion to an epoxy sealing material is very poor. In addition, the heat-resistant polyamide produced by the conventional technology has good adhesion to the epoxy encapsulant, but has problems such as peeling off of the epoxy encapsulant and bubbles during curing of the epoxy encapsulant. .
この問題の対策として、 いわゆる当業者は、 経験的に、 耐熱性ポリア の際に、 剥離や気泡が発生しないであろうと着想した。 [発明が解決しよう とする課題] As a countermeasure to this problem, those skilled in the art have empirically found that At that time, I imagined that there would be no separation or bubbles. [Problems to be solved by the invention]
本発明が解決しよう とする課題の一つは、本発明者らが得た知見に基づ き、 従来の技術による耐熱性ポリアミ ドでは、 予め耐熱性ポリアミ ドが 自然に孕んでいた水分を除去する操作 （加熱操作等の予備的乾燥操作） をしないと、 エポキシ接着やエポキシ封止の際に、 剥離や気泡が発生す るという、 従来の技術の問題点に鑑み、 予備的乾燥操作が不要な発光ダ ィオード反射板甩耐熱ポリアミ ドを提供することである。  One of the problems to be solved by the present invention is that based on the knowledge obtained by the present inventors, the heat-resistant polyamide according to the conventional technique removes water that was previously naturally contained in the heat-resistant polyamide. If the pre-drying operation is not performed (preliminary drying operation such as heating operation), the pre-drying operation is not necessary in view of the problem of the conventional technology that peeling and bubbles occur during epoxy bonding and epoxy sealing. Another object of the present invention is to provide a light-emitting diode reflector and a heat-resistant polyamide.
本発明が解決しょうとする課題の一つは、 製造の際に、 特段の加熱操 作等の予備的乾燥操作を行なわなくても、 エポキシ接着やエポキシ封止 の際に、 剥離や気泡が発生しないことを特徴とする、 この樹脂組成物を 含んで構成される発光ダイォード反射板を提供することである。  One of the problems to be solved by the present invention is that peeling and bubbles are generated during epoxy bonding or epoxy sealing without a special drying operation such as a heating operation during manufacturing. It is another object of the present invention to provide a light-emitting diode reflector including the resin composition.
すなわち、本発明が解決しようとする課題は、上記のような従来の技術 における問題点を解決しょうとするものであって、 発光ダイオード反射 板の成形品材料に好適な、 低吸水性及び耐熱性に優れるポリアミ ド樹脂 組成物、 この樹脂を含んで構成される発光ダイオード反射板、 並びに、 この樹脂を成形してなる発光ダイォード反射板を提供することを目的と している。 発明の開示 本発明者は、 上記問題点を克服するために、 ポリアミ ド樹脂を構成する 成分についてさらに詳しく検討した結果、 低吸水性を有し、 さらに耐熱 性に優れる樹脂を見出した。  That is, the problem to be solved by the present invention is to solve the problems in the conventional technology as described above, and is suitable for a molded article material of a light emitting diode reflector, low water absorption and heat resistance. It is an object of the present invention to provide a polyamide resin composition having excellent properties, a light-emitting diode reflector including the resin, and a light-emitting diode reflector formed by molding the resin. DISCLOSURE OF THE INVENTION In order to overcome the above-mentioned problems, the present inventors have studied the components constituting the polyamide resin in more detail, and as a result, have found a resin having low water absorption and further excellent heat resistance.
本発明は、 1 , 9 —ジアミノノナン 5 0〜 1 0 0モル0 /0と、 炭素数 6 〜 1 2の直鎖脂肪族ジァミン、 および Zまたは、 炭素数 6〜 1 2の側鎖 を有する脂肪族ジァミン 0〜 5 0モル％由来のジァミン由来構成単位 ( a - 1 ) と、 テレフタル酸 6 0〜 1 0 0モル0 /0と、 テレフタル酸以外 2 ミ ドを、 各工程で、 加工前にべ一キング （加熱処理） をしてきた。 The present invention, 1, 9 - and Diaminononane 5 0-1 0 0 mole 0/0, fats having linear aliphatic Jiamin a carbon number of 6 to 1 2, and Z or the side chain of 6-1 2 carbon atoms family Jiamin 0-5 0 mole% derived from Jiamin derived constituent unit - and (a 1), and terephthalic acid 6 0-1 0 0 mole 0/0, other than terephthalic acid In each process, 2 meds were baked (heat treated) before processing.
[従来の技術における問題点]  [Problems in conventional technology]
本発明者らは、 従来の技術による耐熱ポリアミ ドは、 加工前にべーキ ング （加熱処理） をしないと、 エポキシ封止材硬化時に、 エポキシ封止 材の剥離や気泡を発生するという現象に着目 し、 耐熱性ポリアミ ドは吸 水性であるために、 耐熱性ポリアミ ドが自然に孕んでいた水分が原因と なり、 エポキシ封止材硬化時に、 エポキシ封止材の剥離や気泡を発生す るのであろう との作業仮説を立て、 鋭意検討を進めた。 その結果、 本出 願明細書の [実施例] の欄において後述する 『吸水率』 を評価の尺度と して採用すると、 従来の技術による耐熱ポリアミ ドの吸水率は、 概ね、 3 . 9 %以上であった。 そして、 本発明者らは、 耐熱性ポリアミ ドにつ いて、 0〜3 . 9 %の水分率の領域において、 エポキシ封止材硬化時に、 エポキシ封止材の剥離や気泡を発生させない水分率の臨界値 （閾値） を 求めたところ、 吸水率 3 . 5 %以下、 好ましくは 3 . 0 %以下、 より好 ましくは 2 . 5 %以下、 さらに好ましく は 2 . 0 %以下では、 エポキシ 封止材の剥離や気泡が発生しないという知見を得た。 本発明者らは、 こ の知見に基づき、 吸水率 3 . 5 %以下の耐熱性ポリァミ ド、 好ましく は 3 . 0 %以下の耐熱性ポリアミ ド、 より好ましくは 2 . 5 %以下の耐熱 性ポリアミ ド、 さらに好ましく は 2 . 0 %以下の耐熱性ポリアミ ドを、 発光ダイオード反射板に応用すれば、 従来の技術では必要であった加熱 操作等の予備的乾燥操作を行なわなくても、 エポキシ接着やエポキシ封 止の際に、 剥離や気泡が発生しないであろう と着想した。  The present inventors have reported that the conventional heat-resistant polyamide, if not baked (heat-treated) before processing, would cause the epoxy encapsulant to peel off or generate bubbles when the epoxy encapsulant is cured. Since the heat-resistant polyamide is water-absorbing, the moisture that the heat-resistant polyamide naturally occupies may cause peeling of the epoxy encapsulant and bubbles during curing of the epoxy encapsulant. We made a working hypothesis that it might As a result, when the “water absorption” described later in the “Examples” section of the present application specification was adopted as the evaluation scale, the water absorption of the heat-resistant polyamide according to the conventional technology was approximately 3.9%. That was all. The inventors of the present invention have found that the heat-resistant polyamide has a moisture content in a range of 0 to 3.9% of moisture content that does not cause peeling of the epoxy sealing material or generation of bubbles when the epoxy sealing material is cured. When the critical value (threshold value) was determined, the epoxy absorption was found to be 3.5% or less, preferably 3.0% or less, more preferably 2.5% or less, and even more preferably 2.0% or less. It has been found that neither exfoliation nor bubbles occur. Based on this finding, the present inventors have found that a heat-resistant polyamide having a water absorption of 3.5% or less, preferably a heat-resistant polyimide having a water absorption of 3.0% or less, and more preferably a heat-resistant polyamide having a water absorption of 2.5% or less. If a heat-resistant polyamide of 2.0% or less is applied to the light-emitting diode reflector, epoxy bonding can be performed without performing a preliminary drying operation such as a heating operation required in the conventional technology. The idea was that there would be no delamination or bubbles when sealing with epoxy or epoxy.
すなわち、 本発明者らは、 本発明者らが得た知見に基づき、 従来の技 術による耐熱性ポリアミ ドでは、 予め耐熱性ポリアミ ドが自然に孕んで いた水分を除去する操作 （加熱操作等の予備的乾燥操作） をしないと、 エポキシ接着やエポキシ封止の際に、 剥離や気泡が発生するという、 従 来の技術の問題点に鑑み、 予備的乾燥操作が不要な耐熱ポリアミ ドを発 光ダイォード反射板に応用すれば、 従来の技術では必要であった加熱操 作等の予備的乾燥操作を行なわなく ても、 エポキシ接着やエポキシ封止 の芳香族ジカルボン酸、 および Zまたは、 炭素原子数 4〜 2 0の脂肪族 ジカルボン酸 0〜 4 0モル0 /0由来のジカルボン酸由来構成単位（ a — 2 ) を分子内に有するポリアミ ドを含んでなることを特徴とする、 発光ダイ オード反射板に用いられるポリアミ ド樹脂を提供する。 In other words, based on the knowledge obtained by the present inventors, the heat-resistant polyamide obtained by the conventional technology uses an operation (such as a heating operation) for previously removing moisture that was naturally contained in the heat-resistant polyamide. If the pre-drying operation is not performed, heat-resistant polyamides that do not require a pre-drying operation will be generated in view of the problems of the conventional technology that peeling and bubbles will occur during epoxy bonding and epoxy sealing. When applied to optical diode reflectors, epoxy bonding and epoxy encapsulation can be performed without the need for preliminary drying operations such as heating operations, which were required in conventional technologies. Aromatic dicarboxylic acids, and Z or aliphatic dicarboxylic acid having a carbon atom number of 4-2 0 0-4 0 mole 0/0 derived from dicarboxylic acid-derived constituent unit - a made of Polyamide with (a 2) in the molecule Provided is a polyamide resin used for a light-emitting diode reflector, characterized by comprising:
本発明の発光ダイォード反射板用ポリアミ ド樹脂組成物は、 成分 （A ) と して、 1 , 9 —ジアミノノナン 5 0〜： L 0 0モル％と、 炭素数 6〜 1 2の直鎖脂肪族ジァミ ン、 および Zまたは、 炭素数 6〜 1 2の側鎖を有 する脂肪族ジァミン 0〜 5 0モル％由来のジァミン由来構成単位 （ a― 1 ) と、 テレフタル酸 6 0〜 1 0 0モル0 /0と、 テレフタル酸以外の芳香 族ジカルボン酸、 および Zまたは、 炭素原子数 4〜 2 0の脂肪族ジカル ボン酸 0〜 4 0モル％由来のジカルボン酸由来構成単位 （ a— 2 ) を分 子内に有するポリアミ ド 1 0 0重量部と、 成分 （B ) と して、 無機充填 材 1〜 2 0 0重量部とを含むことが好ましい。 The polyamide resin composition for a light-emitting diode reflector according to the present invention comprises, as component (A), 1,9-diaminononane 50-: L 0 0 mol%, and a straight-chain aliphatic having 6-12 carbon atoms. Diamine and Z or a diamine-derived structural unit (a-1) derived from 0 to 50 mol% of an aliphatic diamine having a side chain having 6 to 12 carbon atoms, and 60 to 100 mol of terephthalic acid 0/0, the aromatic dicarboxylic acid other than terephthalic acid, and Z or carbon atom number 4-2 0 aliphatic dicarboxylic acids 0-4 0 mole% derived from dicarboxylic acid-derived constituent units (a- 2) It is preferable to include 100 parts by weight of the polyamide contained in the molecule and 1 to 200 parts by weight of the inorganic filler as the component (B).
本発明の成分 （B ) の無機充填材は、 ガラス繊維、 タルク、 ウォラス トナイ ト、 チタン酸カリ ウム、 酸化亜鉛、 二酸化チタン、 炭酸カルシゥ ム、 硫酸バリ ウム、 及び、 培焼カオリ ンクレイからなる群から選択され る少なく とも一つの無機充填材を含むことは本発明の好ましい態様の 1 つでる。  The inorganic filler of the component (B) of the present invention is a group consisting of glass fiber, talc, wollastonite, potassium titanate, zinc oxide, titanium dioxide, calcium carbonate, barium sulfate, and calcined kaolin clay. Including at least one inorganic filler selected from among the following is one of preferred embodiments of the present invention.
本発明は、 上記記載のポリアミ ド樹脂を含んで構成される発光ダイォ ド反射板を提供する。  The present invention provides a light-emitting diode reflector including the above-described polyamide resin.
本発明は、 上記記載のポリアミ ド樹脂組成物を含んで構成される発光 ダイォード反射板を提供する。  The present invention provides a light-emitting diode reflector comprising the above-described polyamide resin composition.
本発明は、 1 , 9 —ジアミノノナン 5 0〜 1 0 0モル％と、 炭素数 6 〜 1 2の直鎖脂肪族ジァミ ン、 および Zまたは、 炭素数 6〜 1 2の側鎖 を有する脂肪族ジァミ ン 0〜 5 0モル％由来のジアミ ン由来構成単位 ( a - 1 ) と、 テレフタル酸 6 0〜： L 0 0モル0 /。と、 テレフタル酸以外 の芳香族ジカルボン酸、 および Zまたは、 炭素原子数 4〜 2 0の脂肪族 ジカルボン酸 0〜 4 0モル％由来のジカルボン酸由来構成単位（ a — 2 ) を分子内に有するポリアミ ドを含んでなることを特徴とする、 エポキシ 樹脂接合用成形加工品用樹脂組成物を提供する。 The present invention relates to a 1,9-diaminononane of 50 to 100 mol%, a linear aliphatic diamine having 6 to 12 carbon atoms, and an aliphatic group having Z or a side chain having 6 to 12 carbon atoms. Diamin-derived structural unit (a-1) derived from 0 to 50 mol% of diamin, and terephthalic acid 60 to: L 00 mol 0 /. And an aromatic dicarboxylic acid other than terephthalic acid, and a dicarboxylic acid-derived structural unit (a-2) derived from 0 to 40 mol% of Z or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms in the molecule. An epoxy, characterized by comprising a polyamide Provided is a resin composition for a molded product for resin bonding.
本発明のエポキシ樹脂接合用成形加工品用樹脂組成物は、 成分 （A ) と して、 1， 9 —ジアミ ノノナン 5 0〜： 1 0 0モル0 /0と、 炭素数 6〜 1 2の直鎖脂肪族ジァミ ン、 およびノまたは、 炭素数 6〜 1 2の側鎖を有 する脂肪族ジァミン 0〜 5 0モル0 /0由来のジァミン由来構成単位 （ a _ 1 ) と、 テレフタル酸 6 0〜 1 0 0モル0 /0と、 テレフタル酸以外の芳香 族ジカルボン酸、 および /または、 炭素原子数 4〜 2 0の脂肪族ジカル ボン酸 0〜 4 0モル％由来のジカルボン酸由来構成単位 （ a— 2 ) を分 子内に有するポリアミ ド 1 0 0重量部と、 成分 （B ) として、 無機充填 材 1〜 2 0 0重量部とを含むことが好ましい。 発明を実施するための最良の形態 以下、 本発明に係るポリアミ ド樹脂、 ポリアミ ド樹脂組成物、 その成 形品、 発光ダイオード反射板について具体的に説明する。 Epoxy resin bonding molded article resin composition of the present invention, as the component (A), 1, 9 - diamine Nononan 5 0: 1 0 0 mole 0/0, 6-1 2 carbon atoms linear aliphatic Jiami down, and Roh or aliphatic Jiamin 0-5 0 mole 0/0 derived Jiamin derived structural units have a side chain with carbon number 6~ 1 2 (a _ 1) , terephthalic acid 6 0-1 0 0 mole 0/0, the aromatic dicarboxylic acid other than terephthalic acid, and / or carbon atoms 4-2 0 aliphatic dicarboxylic acids 0-4 0 mole% derived from dicarboxylic acid-derived constituent unit It is preferable to include 100 parts by weight of a polyamide having (a-2) in a molecule, and 1 to 200 parts by weight of an inorganic filler as the component (B). BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a polyamide resin, a polyamide resin composition, a molded product thereof, and a light emitting diode reflector according to the present invention will be specifically described.
[発光ダイォード反射板]  [Light emitting diode reflector]
本出願明細書において使用する 『発光ダイォード反射板』なる語には、 『板』 なる漢字を使用してはいるが、 この語の概念は、 『板』状の形状を 有するもののみに限定されず、 少なく とも光を放射する方向の面が解放 された、又は、 解放されていないケーシングゃハウジング一般を包含し、 より具体的には、 箱状又は函状の形状を有するもの、 漏斗状の形状を有 するもの、 お椀状の形状を有するもの、パラボナ状の形状を有するもの、 円柱状の形状を有するもの、 円錐状の形状を有するもの、 ハニカム状の 形状を有するもの等、 板 （平面、 球面、 曲面等の面） を光を反射する面 として有する三次元形状一般をも包含する。 本発明において発光ダイォ ード反射板は、 通常、 ポリアミ ド樹脂、 又は、 ポリアミ ド樹脂と無機充 填材とを含んでなる樹脂組成物を、 射出成形、 溶融成形、 押出成形、 ィ ンフレーシヨ ン成形、 ブロー成形等の加熱成形により、 所望の形状に賦 形される。 本発明において発光ダイオード反射板は、 通常、 発光ダイォ ー ド素子その他の部品と、 エポキシ樹脂により、 封止、 接合、 接着等が 行なわれる。 Although the term “light-emitting diode reflector” used in the present application uses the Chinese character “plate”, the concept of this word is limited to only those having a “plate” shape. At least, the casing in the direction of emitting light is open or not open.Cases including housing in general, more specifically those having a box-like or box-like shape, funnel-like Plates (planes) such as those having a shape, those having a bowl shape, those having a parabona shape, those having a columnar shape, those having a conical shape, those having a honeycomb shape, etc. , A spherical surface, a curved surface, or the like) as a surface for reflecting light. In the present invention, the light-emitting diode reflector is generally formed by injection molding, melt molding, extrusion molding, or inflation molding of polyamide resin or a resin composition containing polyamide resin and an inorganic filler. It is formed into a desired shape by heat molding such as blow molding. In the present invention, the light emitting diode reflector is usually a light emitting diode. Encapsulation, bonding, bonding, etc. are performed with a chip element and other components and epoxy resin.
[ポリアミ ド樹脂]  [Polyamide resin]
ポリアミ ド樹脂と しては、 下記のポリアミ ド樹脂 （成分 （A)) が使用 される。 ポリアミ ド樹脂 （成分 （A)) は、 ジァミン由来構成単位 （ a - 1 ) とジカルボン酸由来構成単位 （ a— 2) とから重合される。 ポリア ミ ド樹脂 （成分 （A)) は、 [実施例] の欄において後述する 『吸水率』 を評価の尺度と して採用すると、 吸水率 3. 5 %以下の耐熱性ポリアミ ド樹脂、 好ましく は 3. 0 %以下の耐熱性ポリアミ ド樹脂、 より好まし くは 2. 5 °/0以下の耐熱性ポリアミ ド樹脂、 さ らに好ましく は 2. 0 % 以下のポリアミ ド樹脂である。 ポリアミ ド樹脂 （成分 （A)) は、 [実施 例] の欄において後述する 『吸水率』 を評価の尺度と して採用すると、 一般的には、 吸水率 1. 5〜3. 5 %の耐熱性ポリアミ ド樹脂、 好まし く は 1. 5〜 3. 0 %の耐熱性ポリアミ ド樹脂、 より好ましくは 1. 5 〜2. 5 %の耐熱性ポリアミ ド樹脂、 さらに好ましくは 1. 5〜2. 0 以下のポリアミ ド樹脂である。 As the polyamide resin, the following polyamide resin (component (A)) is used. The polyamide resin (component (A)) is polymerized from a diamine-derived structural unit (a-1) and a dicarboxylic acid-derived structural unit (a-2). Polyamide resin (component (A)) is a heat-resistant polyamide resin having a water absorption of 3.5% or less, when "water absorption" described later in the section of "Examples" is adopted as an evaluation scale. Is a heat-resistant polyamide resin of 3.0% or less, more preferably a heat-resistant polyamide resin of 2.5 ° / 0 or less, and more preferably a polyamide resin of 2.0% or less. Polyamide resin (component (A)) generally has a water absorption of 1.5 to 3.5% when the “water absorption” described later in the section of “Examples” is adopted as a scale of evaluation. Heat-resistant polyamide resin, preferably 1.5 to 3.0% heat-resistant polyamide resin, more preferably 1.5 to 2.5% heat-resistant polyamide resin, and still more preferably 1.5 to 2.5% It is a polyamide resin of 2.0 or less.
[ジァミン由来構成単位 （ a — 1 )]  [Structural unit derived from diamine (a-1)]
本発明で使用するポリアミ ド樹脂 （成分 （A)) を構成するジアミン由 来構成単位 （ a — 1 ) は、 1， 9—ジァミノノナンと、 直鎖および Zま たは側鎖を有する炭素数 6〜 1 2の脂肪族ジァミンから誘導され、 1， 9ージアミノ ノナンを 5 0〜1 0 0モル0 /。、 直鎖および Zまたは側鎖を 有する炭素数 6〜 1 2の脂肪族ジァミ ンを 0〜 5 0モル％含有するジァ ミン由来構成単位から合成することが好ましい。 The structural unit ( a -1) derived from the diamine constituting the polyamide resin (component (A)) used in the present invention is composed of 1,9-diaminononane and a linear or Z- or side-chain carbon atom having 6 or more carbon atoms. derived from ~ 1 2 aliphatic Jiamin, 1, 9 Jiamino nonane 5 0-1 0 0 mole 0 /. It is preferable to synthesize from a diamine-derived structural unit containing 0 to 50 mol% of an aliphatic diamine having 6 to 12 carbon atoms having a straight chain, Z or a side chain.
[直鎖脂肪族ジァミン成分]  [Linear aliphatic diamine component]
ジァミン由来構成単位 （ a — 1 ) を、 1 , 9—ジアミ ノノナンと共に 構成する直鎖脂肪族ジァミン成分の具体的な例と しては、 1， 6—ジァ ミノへキサン、 1 , 7—ジァミノヘプタン、 1 , 8—ジァミ ノオクタン、 1， 9ージアミノノナン、 1 , 1 0—ジァミノデカン、 1 , 1 1 -ジアミ ノ ゥンデカン、 および 1 , 1 2—ジァミノ ドデカンを挙げることができ る。 これらの中でも、 1， 6—ジァミノへキサンが特に好ましい。 Specific examples of the linear aliphatic diamine component constituting the diamine-derived structural unit (a-1) together with 1,9-diaminononane include 1,6-diaminohexane, 1,7- Diaminoheptane, 1,8-diaminooctane, 1,9 diaminononane, 1,10-diaminodecane, 1,11-diaminopendecane, and 1,12-diaminododecane You. Among these, 1,6-diaminohexane is particularly preferred.
[側鎖を有する脂肪族ジァミン成分]  [Aliphatic diamine component having a side chain]
ジァミン由来構成単位 （ a — 1 ) を、 1 , 9—ジアミノノナンと共に 構成する側鎖を有する炭素原子数 6〜 1 2の脂肪族ジァミン成分は、 側 鎖アルキル基を有する脂肪族ジァミンであれば特に制限はないが、 具体 的な例と しては、 2—メチルー 1， 5 —ジァミ ノペンタン、 2 —メチル - 1 , 6 —ジァミノへキサン、 2—メチルー 1， 7—ジァミノヘプタン、 2—メチルー 1 , 8 —ジァミノオクタン、 2 —メチルー 1， 9ージアミ ノノナン、 2—メチノレー 1， 1 0—ジァミノデカン、 2 —メチノレ一 1， 1 1ージアミ ノ ウンデカン等が挙げられる。 これらの中では、 2—メチ ル一 1， 7 —ジァミノヘプタン、 2 —メチル一 1 , 8—ジアミノォクタ ン、 2 _メチル一 1， 9 —ジァミノノナンから誘導される由来構成単位 が好ましく、 特に、 2 —メチル一 1 , 8 —ジアミノォクタンが好ましレ、。 1， 9 —ジアミノノナンと共に構成する上記ジァミン成分は、 直鎖脂肪 族ジァミン成分と側鎖アルキル基を有する脂肪族ジァミン成分を任意の 割合で混合して使用する事ができるが、 直鎖脂肪族ジァミン成分、 もし くは側鎖アルキル基を有する脂肪族ジァミン成分を単独で使用すること が好ましい。  The aliphatic diamine component having 6 to 12 carbon atoms and having a side chain which constitutes the diamine-derived structural unit (a-1) together with 1,9-diaminononane is particularly an aliphatic diamine having a side chain alkyl group. Although there is no limitation, specific examples include 2-methyl-1,5-diaminopentane, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1, 8-diaminooctane, 2-methyl-1, 9 diamino nononane, 2-methinolate 1, 10-diaminodecane, 2-methinole 1, 1 1 1 diamino undecane and the like. Of these, structural units derived from 2-methyl-1,7-diaminoheptane, 2-methyl-1,8-diaminooctane, and 2_methyl-1,9-diaminononane are preferred, and particularly, 2— Methyl 1,8-diaminooctane is preferred. The above diamine component, which is formed together with 1,9-diaminononane, can be used by mixing a linear aliphatic diamine component and an aliphatic diamine component having a side chain alkyl group at an arbitrary ratio. It is preferred to use the component alone or the aliphatic diamine component having a side chain alkyl group alone.
[ジカルボン酸由来構成単位 （ a — 2 ) ]  [Structural unit derived from dicarboxylic acid (a-2)]
本発明で使用するポリアミ ド樹脂 （成分 （A ) ) を構成するジカルボン 酸由来構成単位 （ a — 2 ) は、 テレフタル酸由来構成単位 6 0〜 1 0 0 モル％と、 テレフタル酸以外の芳香族ジカルボン酸由来構成単位 0〜 4 0モル％、 およぴノまたは炭素原子数 4〜 2 0の脂肪族ジカルボン酸由 来構成単位 0〜4 0モル％から重合されることが好ましい。 このうちテ レフタル酸以外の芳香族ジカルボン酸由来構成単位としては、 例えばィ ソフタル酸、 2 -メチルテレフタル酸、 ナフタレンジカルボン酸およびこ れらの組み合わせなどが挙げられる。  The dicarboxylic acid-derived structural unit (a-2) constituting the polyamide resin (component (A)) used in the present invention has a terephthalic acid-derived structural unit of 60 to 100 mol%, and an aromatic other than terephthalic acid. It is preferable to polymerize from 0 to 40 mol% of a dicarboxylic acid-derived structural unit, and from 0 to 40 mol% of a dicarboxylic acid-derived structural unit having 4 to 20 carbon atoms. Among these, examples of the structural unit derived from an aromatic dicarboxylic acid other than terephthalic acid include isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, and combinations thereof.
[脂肪族ジカルボン酸成分]  [Aliphatic dicarboxylic acid component]
また、 脂肪族ジカルボン酸由来構成単位は、 その炭素数を特に制限す るものではないが、 好ましくは 4〜 2 0、 さらに好ましく は 6〜 1 2の 脂肪族ジカルボン酸から誘導される。 このよ うな脂肪族ジカルボン酸由 来構成単位を誘導するために用いられる脂肪族ジカルボン酸の例と して は、 例えば、 アジピン酸、 スベリ ン酸、 ァゼライン酸、 セバシン酸、 デ カンジカルボン酸、 ゥンデカンジ力ノレボン酸およぴドデカンジカルボン 酸等が挙げられる。 これらの中でも、 アジピン酸が特に好ましい。 In addition, the structural unit derived from an aliphatic dicarboxylic acid particularly limits the number of carbon atoms. It is preferably, but not exclusively, derived from 4-20, more preferably 6-12 aliphatic dicarboxylic acids. Examples of the aliphatic dicarboxylic acid used to derive such an aliphatic dicarboxylic acid-derived structural unit include, for example, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, pendecanediene Force olevonic acid, dodecanedicarboxylic acid and the like. Of these, adipic acid is particularly preferred.
[テレフタル酸成分 zテレフタル酸以外のジカルボン酸成分比] 本発明においては、 ジカルボン酸由来構成単位を 1 0 0モル％とする とき、 テレフタル酸由来構成単位から誘導される構成単位は、 6 0〜 1 0 0モル0 /0、 好ましく は 8 0〜 1 0 0モル0 /0の量で含有され、 テレフタ ル酸以外の芳香族ジカルボン酸由来構成単位から誘導される構成単位は[Terphthalic acid component z Ratio of dicarboxylic acid component other than terephthalic acid] In the present invention, when the dicarboxylic acid-derived structural unit is 100 mol%, the structural unit derived from terephthalic acid-derived structural unit is 60 to 1 0 0 mole 0/0, preferably 8 0-1 0 0 mole 0/0 is contained in an amount of a structural unit derived from an aromatic dicarboxylic acid-derived constituent units other than terephthalic Le acid
0〜 4 0モル0 /0、 好ましくは 0〜 2 0モル0 /0の量で含有され、 および/" または炭素原子数 4〜 2 0、 好ましく は 4〜 1 2の脂肪族ジカルボン酸 由来構成単位から誘導される構成単位が 0〜4 0モル％、 好ましくは 0 〜 2 0モル％の量で含有することが好ましい。 また、 本発明においては、 ジカルボン酸由来構成単位 （ a— 2 ) と して、 上記のよ うなテレフタル 酸由来構成単位および脂肪族ジカルボン酸由来構成単位と共に、 少量、 例えば、 1 0モル％以下程度の量の多価カルボン酸由来構成単位が含ま れていてもよい。 このよ うな多価カルボン酸由来構成単位と して具体的 には、 ト リメ リ ッ ト酸およびピロメ リ ッ ト酸等のよ うな三塩基酸おょぴ 多塩基酸を挙げることができる。 0-4 0 mole 0/0, preferably be contained in an amount of 0-2 0 mole 0/0, and / 'or a carbon atom number 4 2 0, preferably 4 to from 1 2 aliphatic dicarboxylic acid constitutional The structural unit derived from the unit is contained in an amount of 0 to 40 mol%, preferably 0 to 20 mol% .In the present invention, the dicarboxylic acid-derived structural unit (a-2) Then, a small amount, for example, about 10 mol% or less of a polyvalent carboxylic acid-derived structural unit may be contained together with the terephthalic acid-derived structural unit and the aliphatic dicarboxylic acid-derived structural unit as described above. Specific examples of such a polycarboxylic acid-derived structural unit include tribasic acids and polybasic acids such as trimellitic acid and pyromellitic acid.
[ポリアミ ド樹脂 （成分 （A)) の製造方法]  [Production method of polyamide resin (component (A))]
本発明で使用するポリアミ ド樹脂 （成分 （A)) を製造するためには、 上記のよ うなジァミン由来構成単位 （a— 1 ) とジカルボン酸由来構成 単位 （ a — 2 ) とを加えて、 触媒の存在下に加熱する事により製造する ことができる。 また、 この反応において、 ジァミ ン由来構成単位 （ a — 1 ) の全モル数が、 ジカルボン酸由来構成単位 （ a— 2 ) の全モル数よ り多く配合されることが好ましく、 特に好ましくは全ジカルボン酸由来 構成単位を 1 0 0モル％と した時、 全ジァミン由来構成単位が 1 0 0〜 1 2 0モル％である。 この反応は、 通常は不活性ガス雰囲気下で行なわ れ、 一般には反応容器内を窒素ガスなどの不活性ガスで置換する。 また、 ポリアミ ドの重縮合反応を制御するために、 水を予め封入しておく こと が望ましく、 水に可溶な有機溶媒、 例えばメタノール、 エタノールなど のアルコール類が含有されていてもよレ、。 In order to produce the polyamide resin (component (A)) used in the present invention, the diamine-derived structural unit (a-1) and the dicarboxylic acid-derived structural unit (a-2) as described above are added. It can be produced by heating in the presence of a catalyst. In this reaction, it is preferable that the total number of moles of the diamine-derived structural unit (a-1) is larger than the total number of moles of the dicarboxylic acid-derived structural unit (a-2). When the structural unit derived from dicarboxylic acid is 100 mol%, the total structural unit derived from diamine is 100 to 100 mol%. It is 120 mol%. This reaction is usually performed in an inert gas atmosphere, and the inside of the reaction vessel is generally replaced with an inert gas such as nitrogen gas. In order to control the polycondensation reaction of the polyamide, it is desirable to enclose water in advance, and it may contain an organic solvent soluble in water, for example, alcohols such as methanol and ethanol. .
[触媒]  [Catalyst]
本発明で使用するポリァミ ド樹脂 （成分 （A)) を製造するためにに使 用することができる触媒と しては、 リ ン酸、 その塩およびリ ン酸エステ ル化合物 ； 亜リ ン酸、 その塩おょぴエステル化合物 ； 並びに、 次亜リ ン 酸、 その塩おょぴエステル化合物を使用することができる。 これらの中 でも、 リン酸ナト リ ウム、 亜リン酸ナト リ ウム、 次亜リ ン酸カリ ウム、 次亜リ ン酸ナト リ ウム等が好ましい。 これらのリ ン酸化合物は、 単独で あるいは組み合わせて使用することができる。 このようなリ ン系化合物 は、 上記のようなジカルボン酸に対して、 通常は 0.0 0 1〜 5モル0 /0、 好ましくは 0.0 0 2〜 2モル0 /0の割合で用いられる。 Catalysts that can be used to produce the polyamide resin (component (A)) used in the present invention include: phosphoric acid, salts thereof and ester compounds of phosphoric acid; And its salt and ester compounds; and hypophosphorous acid and its salt and ester compounds. Among these, sodium phosphate, sodium phosphite, potassium hypophosphite, sodium hypophosphite and the like are preferable. These phosphoric acid compounds can be used alone or in combination. Such re down based compound, the dicarboxylic acids such as described above, typically 0.0 0 1-5 mole 0/0, preferably used in a ratio of 0.0 0 2-2 mol 0/0.
[末端封止剤]  [Terminal sealant]
本発明で使用するポリアミ ド樹脂 （成分 （A)) を製造するためには、 末端封止剤を使用することが好ましい。 この末端封止剤と しては、 安息 香酸、 安息香酸のアルカリ金属塩、 酢酸等を使用することができる。 こ のような末端封止剤は、 ジカルボン酸 1モルに対して、 通常は 0.0 0 1 〜 5モル、 好ましく は 0.0 1〜 2モルの量で使用される。 この末端封止 剤の使用量を調整することにより、 得られる重縮合物の極限粘度 [η ]を 制御することができる。  In order to produce the polyamide resin (component (A)) used in the present invention, it is preferable to use a terminal blocking agent. As the terminal blocking agent, benzoic acid, an alkali metal salt of benzoic acid, acetic acid and the like can be used. Such an end capping agent is generally used in an amount of 0.01 to 5 mol, preferably 0.01 to 2 mol, per 1 mol of the dicarboxylic acid. The limiting viscosity [η] of the resulting polycondensate can be controlled by adjusting the amount of the terminal blocking agent used.
[ポリアミ ド低次縮合物を製造するための反応条件]  [Reaction conditions for producing low-order condensate of polyamide]
このような重縮合物を調製する際の反応条件は、 具体的には、 反応温 度は通常 2 0 0〜 2 9 0で、 好ましくは 2 2 0〜 2 8 0で、 反応時間は 通常 0.5〜 5時間、 好ましくは 1〜 3時間である。 さらにこの反応は常 圧から加圧のいずれの条件で行うことができるが、 加圧条件で反応を行 う ことが好ましく、 反応圧は、 通常 2 0〜 6 0 kg/ cm 2、 好ましくは 2 5 〜 5 0 [ k g ] / cm 2の範囲内に設定される。 そして、 このようにし て重縮合反応を行うことにより、 3 0 °Cの濃硫酸中で測定した極限粘度 [ ]が、 通常は 0 . 0 5 〜 0 . 6 dlZ g、 好ましくは 0 . 0 8 〜 0 . 3 dl/ gの 範囲内にある低次縮合物を得ることができる。 こう して水性媒体中に生 成したポリアミ ド低次縮合物は、 反応液と分離される。 このポリアミ ド 低次縮合物と反応液との分離には、 例えば濾過、 遠心分離等の方法を採 用することもできるが、 生成した半芳香族ポリアミ ド低次縮合物を含有 する反応液を、 ノズルを介して大気中にフラッシュすることにより、 固 液分離する方法が効率的である。 The reaction conditions for preparing such a polycondensate are, specifically, a reaction temperature of usually 200 to 290, preferably 220 to 280, and a reaction time of usually 0.5. 55 hours, preferably 1-3 hours. Further, this reaction can be carried out under any conditions from normal pressure to pressurization, but it is preferable to carry out the reaction under pressurized conditions, and the reaction pressure is usually 20 to 60 kg / cm 2, preferably 2 to 60 kg / cm 2. Set within the range of 5 to 50 [kg] / cm2. By conducting the polycondensation reaction in this manner, the intrinsic viscosity [] measured in concentrated sulfuric acid at 30 ° C. is usually 0.05 to 0.6 dlZg, preferably 0.08 dlZg. A low-order condensate within the range of 0.3 dl / g can be obtained. The polyamide low-order condensate thus formed in the aqueous medium is separated from the reaction solution. For separation of the low-condensation product of the polyamide from the reaction solution, for example, a method such as filtration or centrifugation can be employed.However, the reaction solution containing the low-condensation product of the generated semi-aromatic polyamide can be used. The method of performing solid-liquid separation by flushing into the atmosphere through a nozzle is efficient.
[後重合]  [Post-polymerization]
本発明では上記のようにして得られたポリアミ ド低次縮合物を用いて 後重合を行う。 この後重合は、 上記ポリアミ ド低次縮合物を乾燥した後 に加熱して、 溶融状態にし、 この溶融物に剪断応力を付与しながら行な うことが好ましい。 この反応に際しては、 乾燥ポリアミ ド低次縮合物が 少なく とも溶融する温度に加熱する。 一般には、 乾燥ポリアミ ド低次縮 合物の融点以上の温度、 好ましくはこの融点より も 1 0 〜 6 0 °C高い温 度に加熱される。 剪断応力は、 例えばベント付き二軸押出機、 ニーダー 等を用いることにより溶融物に付与することができる。 こう して溶融物 に剪断応力を付与することにより、 溶融状態にある乾燥ポリアミ ド低次 縮合物が相互に重縮合すると共に、 縮合物の重縮合反応も進行するもの と考えられる。  In the present invention, post-polymerization is performed using the polyamide low-order condensate obtained as described above. The post-polymerization is preferably carried out by drying the polyamide low-order condensate, heating it to a molten state, and applying a shear stress to the melt. In this reaction, the mixture is heated to a temperature at which the dried polyamide low-order condensate at least melts. Generally, it is heated to a temperature equal to or higher than the melting point of the low-density condensate of the dried polyamide, and preferably 10 to 60 ° C higher than this melting point. The shear stress can be applied to the melt by using, for example, a twin-screw extruder with a vent or a kneader. It is considered that by applying shear stress to the melt in this way, the low-order condensate of the dried polyamide in the molten state is polycondensed with each other, and the polycondensation reaction of the condensate also proceeds.
[固相重合 ·溶融重合等]  [Solid state polymerization, melt polymerization, etc.]
本発明で使用されるポリアミ ド樹脂 （成分 （A ) ) の製造に関する他の 方法として、 上記ポリアミ ド低次縮合物を一般公知の方法にて固相重合 させて、 極限粘度 [ ] が 0 . 5 〜 2 . 0 [ d 1 / g ] の範囲のポリアミ ド を調製することができる。 本発明で使用されるポリアミ ド樹脂 （成分 ( A ) ) の製造に関する、 さらに他の方法と して、 上記ポリアミ ド低次縮 合物を一般公知の方法にて固相重合させて、 極限粘度 [ 7? ] が 0 . 5 〜 1 . 5 [ d 1 / g ] の範囲のポリァミ ド前駆体を調製し、 さらにこの前駆体 を溶融重合させて、 極限粘度 [ 77 ] が 0.8〜 3.0 [ d 1 /g ] の範囲に することができる。 また、 本発明で使用するポリァミ ド樹脂 （成分 （A)) は、 このポリアミ ドの融点以上、 分解温度未満に加熱して、 通常の成形 装置を使用して所望の形状に成形することができる。 特に、 射出成形に よって、 発光ダイオード反射板を効率よく成形することができる。 As another method for producing the polyamide resin (component (A)) used in the present invention, the above polyamide low-order condensate is subjected to solid-state polymerization by a generally known method, and the intrinsic viscosity [] is reduced to 0.1. Polyamides in the range of 5 to 2.0 [d1 / g] can be prepared. As still another method for producing the polyamide resin (component (A)) used in the present invention, solid-state polymerization of the above polyamide low-order condensate is carried out by a generally known method to obtain an intrinsic viscosity. [7?] Was prepared in the range of 0.5 to 1.5 [d1 / g]. Can be melt-polymerized to have an intrinsic viscosity [77] in the range of 0.8 to 3.0 [d1 / g]. Further, the polyamide resin (component (A)) used in the present invention can be heated to a temperature not lower than the melting point of the polyamide and lower than the decomposition temperature, and can be molded into a desired shape using a usual molding apparatus. . In particular, the light-emitting diode reflector can be efficiently formed by injection molding.
[ポリアミ ド樹脂 （成分 （A)) の特性]  [Characteristics of polyamide resin (component (A))]
上記組成の範囲にあるポリアミ ド樹脂 （成分 （A)) によって、 優れた 成形性、 低吸水性、 および耐熱性を有することができる。 本発明で用い られるポリアミ ド樹脂は、 2 5 °Cの 9 6.5 %硫酸中で測定した極限粘度 、 0.5〜 3.0 [ £1 1 ]、 好ましく は 0.5〜 2.5 [d l Zg]、 特 に 0.6〜 2.0 [ d 1 / g ] であることが好ましい。 このような範囲にあ る場合、 成形性や成形品の強度特性等に優れる。 また、 本発明で使用さ れるポリアミ ド樹脂 （成分 （A)) は、 DSC で測定した融点が 2 6 0°C 以上、 3 3 0 °C未満、 特に 2 7 0°C〜 3 2 0°Cの範囲内にあることが好 ましい。 このよ うな範囲にあるポリアミ ド樹脂では、 特に優れた耐熱性 を有する。 融点測定は、 D S C (示差走査熱量計） を用いて、 一旦、 3 3 0°Cで 5分間保持し、 次いで 1 0 [°Cノ分] の速度で 2 3 °Cまで降温 せしめた後、 1 0 [°CZ分] で昇温して行なった。 このときの融解に基 づく吸熱ピークを融点 （Tm) と した。 The polyamide resin (component (A)) having the above composition range can have excellent moldability, low water absorption, and heat resistance. The polyamide resin used in the present invention has an intrinsic viscosity of 0.5 to 3.0 [ £ 11], preferably 0.5 to 2.5 [dl Zg], particularly 0.6 to 2.0, measured in 96.5% sulfuric acid at 25 ° C. [d 1 / g] is preferable. In such a range, the moldability and the strength properties of the molded product are excellent. The polyamide resin (component (A)) used in the present invention has a melting point measured by DSC of 260 ° C. or more and less than 330 ° C., and particularly, from 27 ° C. to 320 ° C. It is preferably within the range of C. Polyamide resins in such a range have particularly excellent heat resistance. The melting point was measured by using a DSC (differential scanning calorimeter) once at 330 ° C for 5 minutes, then cooled down to 23 ° C at a rate of 10 ° C, then cooled down. The heating was performed at 10 [° CZ min]. The endothermic peak based on the melting at this time was defined as the melting point (Tm).
[無機充填材]  [Inorganic filler]
無機充填材 （無機充填剤） と しては、 下記の無機充填材が好ましく使 用される。 本発明では、 発明の効果を損なわない範囲で、 以下の充填剤 をポリアミ ド樹脂 （成分 （A)) 1 0 0重量部に対し、 1〜 2 0 0重量部 の割合で添加する。 繊維状の充填材 （特にガラス繊維、 ァラミ ド繊維、 炭素繊維等）、 粉末状、 粒状、 板状、 針状の充填材 （特にシリカ、 アルミ ナ、 炭酸カルシウム、 二酸化チタン、 タルク、 ウォラス トナイ ト、 ケィ ソゥ土、 培焼力オリンク レイ、 クレー、 カオリ ン、 球状ガラス、 マイ力、 酸化マグネシウム、 炭酸カルシウム、 硫酸バリ ウム、 酸化亜鉛、 チタン 酸カリ ウム、 ウイスカ等）、 この中では、 特に、 ガラス繊維、 タルク、 ゥ オラス トナイ ト、 チタン酸カリウム、 酸化亜鉛、 酸化チタン、 炭酸カル シゥム、 硫酸バリ ウム、 培焼カオリンクレイが好ましく、 これらから選 ばれる少なく とも 1種類又は 2種類以上の無機充填材を含む。 As the inorganic filler (inorganic filler), the following inorganic fillers are preferably used. In the present invention, the following fillers are added in an amount of 1 to 200 parts by weight based on 100 parts by weight of the polyamide resin (component (A)) as long as the effects of the present invention are not impaired. Fibrous fillers (especially glass fibers, aramide fibers, carbon fibers, etc.), powdered, granular, plate-like and needle-like fillers (especially silica, alumina, calcium carbonate, titanium dioxide, talc, wollastonite) , Caso earth, brewing power Orinkley, clay, kaolin, spherical glass, My power, magnesium oxide, calcium carbonate, barium sulfate, zinc oxide, potassium titanate, whisker, etc.) Glass fiber, talc, ゥ Olastonite, potassium titanate, zinc oxide, titanium oxide, calcium carbonate, barium sulfate, and calcined kaolin clay are preferred, and include at least one or more inorganic fillers selected from these.
[添加剤] また、 本発明では、 発明の効果を損なわない範囲で、 用途に 応じて、 以下の添加剤、 すなわち、 酸化防止剤 （ヒンダードフエノール 類）、 耐熱安定剤 （リン化合物、 ラク トン化合物、 ビタミン E類、 ィォゥ 化合物、 ハイ ドロキノン類、 ハロゲン化銅、 ョゥ素化合物等）、 耐光安定 剤 （ベンゾ ト リ アゾール類、 ト リ アジン類、 ベンゾフエノ ン類、 ベンゾ エート類、 ヒンダードアミ ン類）、 他の重合体 （ォレフイ ン類、 変性ポリ ォレフィ ン類、 エチレン ' プロ ピレン共重合体、 エチレン . 1 ーブテン 共重合体、 プロ ピレン ' エチレン共重合体、 プロ ピレン ' 1 —ブテン共 重合体等のォレフィ ン共重合体、 ポリ スチレン、 ポリアミ ド、 ポリカー ボネー ト、 ポリ アセタール、 ポリ スルフォン、 ポリ フエ二レンォキシ ド、 弗素樹脂、 シリ コーン樹脂、 L C P等）、 蛍光増白剤、 可塑剤、 増粘剤、 帯電防止剤、 離型剤、 顔料、 染料、 核剤、 種々公知の配合剤を添加する ことができる。  [Additives] In the present invention, the following additives, ie, antioxidants (hindered phenols), heat stabilizers (phosphorus compounds, lactones) are used according to the intended use within a range that does not impair the effects of the present invention. Compounds, vitamin Es, zeo compounds, hydroquinones, copper halides, iodine compounds, etc., light stabilizers (benzotriazoles, triazines, benzophenones, benzoates, hindered amines) ), Other polymers (olefins, modified polyolefins, ethylene 'propylene copolymer, ethylene. 1-butene copolymer, propylene' ethylene copolymer, propylene '1-butene copolymer Olefin copolymer, polystyrene, polyamide, polycarbonate, polyacetal, polysulfone, poly Add phenylene oxide, fluorine resin, silicone resin, LCP, etc.), fluorescent brightener, plasticizer, thickener, antistatic agent, release agent, pigment, dye, nucleating agent, and various known compounding agents. can do.
[ポリアミ ド樹脂組成物 （成分 （A ) ) の調製方法]  [Method for Preparing Polyamide Resin Composition (Component (A))]
本発明で使用するポリアミ ド樹脂組成物 （成分 （A ) ) を調製するには- 各成分を、 種々公知の方法、 例えばヘンシヱルミキサー、 V-ブレンダー, リボンプレンダー、 タンブラーブレンダ一等で混合する方法、 あるいは 混合後、 一軸押出機、 多軸押出機、 ニーダー、 バンバリ一ミキサー等で 溶融混練後、 造粒あるいは粉砕する方法を採用すればよい。 本発明に係 るポリアミ ド組成物は、 上記ポリアミ ド （A ) を溶融状態、 例えば、 2 8 0〜 3 6 0 °Cに加熱 ·維持しながら、 成分 （B ) として、 無機充填材、 必要により上記繊維状充填剤、 粉末状充填剤、 各種添加剤を配合して混 練するなどの方法により調製することができる。 この際、 押出し機、 二 ーダ一等の通常の混練装置を用いることができる。 例えば上記のように して調製されたポリアミ ド樹脂 （成分 （A ) ) 組成物は、 粉末、 ペレツ ト 状その他の形状にして、 圧縮成形法、 射出成形法、 押出し成形法などを 利用することにより、 各種成形品にすることができる。 実施例 次に、 実施例を挙げて本発明をより具体的に説明するが、 本発明はそ の要を超えないかぎりこれらの例に何ら制限されるものではなレ、。なお、 実施例および比較例に記した分析おょぴ測定は以下の方法に従って測定 した。 To prepare the polyamide resin composition (component (A)) used in the present invention-Each component is mixed by various known methods, for example, a Hensile mixer, a V-blender, a ribbon blender, a tumbler blender, etc. Alternatively, a method of melt-kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer or the like after mixing, and then granulating or pulverizing may be adopted. The polyamide composition according to the present invention comprises an inorganic filler as a component (B) while heating and maintaining the polyamide (A) in a molten state, for example, at 280 to 360 ° C. Thus, it can be prepared by a method such as blending and kneading the above fibrous filler, powdery filler and various additives. At this time, an ordinary kneading device such as an extruder or a kneader can be used. For example, the polyamide resin (component (A)) composition prepared as described above may be formed into a powder, pellet, or other shape by compression molding, injection molding, extrusion molding, or the like. By using it, it can be made into various molded products. EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples unless it exceeds the necessity. The analysis and measurement described in Examples and Comparative Examples were measured according to the following methods.
①極限粘度 [ 7] ] : ポリアミ ド樹脂 0.5 [ g ] を 9 6.5 %硫酸溶液 5 0 [m l ] に溶解し、 ウベローデ粘度計を使用し、 2 5.0 ± 0.0 5°Cの条 件下で試料溶液の流下秒数を測定し、 以下の式に基づき算出した。 [ ] = η SP/[C( 1 +0.2 0 5 η SP) ] η SP=( t - t 0 ) / t 0 [ rj ]：極限粘 度 [ d 1 Z g ] 77 SP：比粘度 C ：試料濃度 [ g/ d 1 ] t ：試料溶液の 流下秒数 [秒] t 0 ： ブランク硫酸の流下秒数 [秒]  (1) Intrinsic viscosity [7]: Dissolve 0.5 [g] of polyamide resin in 50 [ml] of 96.5% sulfuric acid solution, and use an Ubbelohde viscometer to sample under the condition of 25.0 ± 0.05 ° C. The number of seconds for the solution to flow was measured, and calculated based on the following equation. [] = η SP / [C (1 +0.20 5 η SP)] η SP = (t-t 0) / t 0 [rj]: Ultimate viscosity [d 1 Z g] 77 SP: Specific viscosity C: Sample concentration [g / d1] t: Seconds of sample solution flowing down [seconds] t0: Seconds of flowing blank sulfuric acid [seconds]
②融点 （Tm) : P e r k i n E l m e r社製 D S C 7型を用いて、 一旦 3 3 0 °Cで 5分間保持し、 次いで 1 0 [°CZ分] の速度で 2 3 °Cまで降 温せしめた後、 1 0 [°C /分] で昇温して行なった。 このときの融解に 基づく吸熱ピークを融点とした。 (2) Melting point (Tm): Hold once at 330 ° C for 5 minutes using DSC Model 7 manufactured by Perkin Elmer, then cool to 23 ° C at a rate of 10 [° CZ min]. After that, the temperature was raised at 10 [° C / min]. The endothermic peak based on the melting at this time was taken as the melting point.
③吸水率： ポリアミ ド樹脂組成物を、 射出圧力 1 0 0 0 [k gZ c m 2 ]. シリンダー温度を樹脂の融点より 1 0°C高い温度に設定し、 金型温度 1 ③ Water absorption: Injection pressure of polyamide resin composition is set to 100,000 [kg g cm 2]. Cylinder temperature is set to 10 ° C higher than melting point of resin, and mold temperature is set to 1
2 0 [°C] にて射出成形し、 長さ 6 4 [mm], 幅 6 [mm], 厚さ 0.Injection molding at 20 [° C], length 6 4 [mm], width 6 [mm], thickness 0.
8 [mm] の試験片を得た。 この試験片を 4 0 [°C]、 相対湿度 9 5 %の 恒温恒湿室に保管して吸水させた。 9 6時間吸水させた後、 試験片重量 を精密天抨で測定した。 吸水率（重量％) は、 次の式で求めた。 M= (M 2 -M 1 ) /M 1 X 1 0 0 M： 吸水率 （重量％) M l ：試験片の絶乾重 量 (g) M 2 ： 吸水後の試験片重量 (g) An 8 mm test piece was obtained. The test piece was stored in a constant temperature and humidity room at 40 ° C. and a relative humidity of 95% to absorb water. After absorbing water for 96 hours, the test piece weight was measured with a precision balance. The water absorption (% by weight) was determined by the following equation. M = (M 2 -M 1) / M 1 X 100 M: Water absorption (% by weight) M l: Absolute dry weight of test piece (g) M 2: Weight of test piece after water absorption (g)
[実施例 1]  [Example 1]
テレフタル酸 4 6.5 [k g] ( 2 8 0モル）、 1， 9ージアミノ ノナン を 44.7 [ k g] ( 2 8 3モル）、 安息香酸 0.4 3 [ k g ] ( 3.5モル）、 卖施剁 比較例 Terephthalic acid 46.5 [kg] (280 mol), 1,9-diaminononane 44.7 [kg] (283 mol), Benzoic acid 0.43 [kg] (3.5 mol), Comparative example
1 2 3 4 5 1 シ'ァミン中の NMDA純度 (モル％ ) 100 100 90 90 50  1 2 3 4 5 1 NMDA purity in shamamine (mol%) 100 100 90 90 50
他のシ 'ァミンの種類 MODA MODA MODA  Other types of shamamine MODA MODA MODA
なし なし なし および純度 (モル％) 10 10 50  None None None and purity (mol%) 10 10 50
シ'カルホ'ン酸 (モル比） TA 100 85 100 85 100 55  Ci'carphoic acid (molar ratio) TA 100 85 100 85 100 55
AA 0 15 0 15 0 45 in! (di/g) 0.9 1 1 1.1 1 1.1  AA 0 15 0 15 0 45 in! (Di / g) 0.9 1 1 1.1 1 1.1
Tm(°C) 317 310 312 300 270 310 吸水率（重量％) 1.6 1.8 1.8 1.9 3.2 3.9 Tm (° C) 317 310 312 300 270 310 Water absorption (% by weight) 1.6 1.8 1.8 1.9 3.2 3.9
NMDA ： 1， 9—シ'、アミノノナン、 MODA： 2—メチルー 1, 8—シ'ァミノオクタン、 HMDA ： 1, 6—シ、、ァミノへキサン TA： テレフタル 、 AA： V/ヒ。ン 次亜リン酸ナトリ ウム一水和物 0.0 6 [k g] (0.6モル） および蒸留 水 2 7.4 [k g] をオートクレーブに入れ、 反応釜内部を十分に窒素置 換した。 攪拌しながら内部温度を 4時間かけて 25 0°Cに昇温した。 そ のまま 1時間反応を続け、 ポリアミ ド低次縮合物を得た。 このポリアミ ド低次縮合物を真空下 1 9 0°Cで、 1 2時間固相重合した。 その後、 ス NMDA: 1,9-S ', aminononane, MODA: 2-Methyl-1,8-S'aminooctane, HMDA: 1,6-S, Aminohexane TA: Terephthal, AA: V / H. 0.06 [kg] (0.6 mol) of sodium hypophosphite monohydrate and 27.4 [kg] of distilled water were placed in an autoclave, and the inside of the reactor was sufficiently replaced with nitrogen. While stirring, the internal temperature was raised to 250 ° C over 4 hours. The reaction was continued for 1 hour as it was to obtain a polyamide low-order condensate. This polyamide low-order condensate was subjected to solid-state polymerization at 190 ° C. for 12 hours under vacuum. Then
> クリュ一径 3 7 [mm], L/D = 3 6の二軸押出機にて、 ポリアミ ドの 融点より 30°C高いバ レル設定温度でス ク リ ユー回転数 300 [ r p m], 1 0 [k g/h] の樹脂供給速度で溶融重合して、 ポリアミ ド樹脂を得 た。 このポリアミ ド樹脂の [ 7] ]、 融点 （Tm) を表に示す。 当該ポリア ミ ド樹脂 70重量部に対し、 ガラス繊維 2 0重量部、 酸化チタ ン 1 0重 量部、 タルク 1重量部を加え、 二軸押出機にてポリアミ ド樹脂の融点よ り 1 0〜 3 0°C高い温度にて溶融混練してポリアミ ド樹脂組成物を得た c このポリアミ ド樹脂組成物を射出成形し、 吸水率を測定した。 その結果 を表に示す。 > Screw speed of 300 [rpm], 1 at a barrel setting temperature of 30 ° C higher than the melting point of polyamide using a twin screw extruder with a screw diameter of 3 7 [mm] and L / D = 36. Melt polymerization was performed at a resin supply rate of 0 [kg / h] to obtain a polyamide resin. The [7]] and melting point (Tm) of this polyamide resin are shown in the table. 20 parts by weight of glass fiber, 10 parts by weight of titanium oxide, and 1 part by weight of talc are added to 70 parts by weight of the polyamide resin. A polyamide resin composition was obtained by melt-kneading at a high temperature of 30 ° C. c. The polyamide resin composition was injection molded, and the water absorption was measured. The results are shown in the table.
[実施例 2〜 5] [Examples 2 to 5]
表に示すジァミン由来構成単位、 およぴジカルボン酸成分のモル比に て、 実施例 1 と同様にポリァミ ド樹脂を得た。 また、 実施例 1 と同様に ポリアミ ド樹脂組成物を得た。 これらを実施例 1 と同様に評価し、 その 結果を表に示す。 The molar ratio of diamine-derived structural units and dicarboxylic acid component shown in the table Thus, a polyamide resin was obtained in the same manner as in Example 1. A polyamide resin composition was obtained in the same manner as in Example 1. These were evaluated in the same manner as in Example 1, and the results are shown in the table.
[比較例 1 ]実施例 1において、 ジァミンの種類を 1， 6—ジァミノへキ サンにした以外は、 表に示すジァミン由来構成単位、 およびジカルボン 酸成分のモル比にて、 実施例 1 と同様の方法にてポリアミ ド樹脂、 およ ぴポリアミ ド樹脂組成物を得た。 これらを実施例 1 と同様に評価した結 果、 吸水率が高い。 産業上の利用可能性 本発明の効果の一つは、 本発明者らが得た知見に基づき、 従来の技術 による耐熱性ポリアミ ドでは、 予め耐熱性ポリアミ ドが自然に孕んでい た水分を除去する操作 （加熱操作等の予備的乾燥操作） をしないと、 ェ ポキシ接着やエポキシ封止の際に、 剥離や気泡が発生するという、 従来 の技術の問題点に鑑み、 予備的乾燥操作が不要な発光ダイォード反射板 用耐熱ポリアミ ドを提供することができることである。 本発明の効果の 一つは、 製造の際に、 特段の加熱操作等の予備的乾燥操作を行なわなく ても、 エポキシ接着やエポキシ封止の際に、 剥離や気泡が発生しないこ とを特徴とする、 この樹脂組成物を含んで構成される発光ダイオード反 射板を提供することができることである。 すなわち、 本発明の効果は、 従来の技術における問題点を解決しようとするものであって、 発光ダイ ォード反射板の成形品材料に好適な、 低吸水性及び耐熱性に優れるポリ アミ ド樹脂組成物、この樹脂を含んで構成される発光ダイォード反射板、 並びに、 この樹脂を成形してなる発光ダイオード反射板を提供すること ができることである。  [Comparative Example 1] In the same manner as in Example 1, except that the type of diamine was changed to 1,6-diaminohexane, the molar ratio of the diamine-derived structural unit and dicarboxylic acid component shown in the table was used. A polyamide resin and a polyamide resin composition were obtained by the above method. As a result of evaluating these in the same manner as in Example 1, the water absorption was high. Industrial Applicability One of the effects of the present invention is that, based on the knowledge obtained by the present inventors, in the heat-resistant polyamide according to the conventional technology, the moisture that the heat-resistant polyamide naturally contained in advance is removed. If the removal operation (preliminary drying operation such as heating operation) is not performed, the preliminary drying operation is not performed in consideration of the problem of the conventional technology that peeling and bubbles are generated during epoxy bonding and epoxy sealing. An unnecessary heat-resistant polyamide for a light emitting diode reflector can be provided. One of the effects of the present invention is that peeling and bubbles are not generated during epoxy bonding or epoxy sealing without a special drying operation such as a heating operation during manufacturing. It is possible to provide a light-emitting diode reflecting plate including the resin composition. That is, the effect of the present invention is to solve the problems in the prior art, and is a polyamide resin composition suitable for a molded article material of a light emitting diode reflector, which is excellent in low water absorption and heat resistance. An object, a light-emitting diode reflector including the resin, and a light-emitting diode reflector formed by molding the resin can be provided.

Claims

請求の範囲 The scope of the claims
1 . 1 , 9—ジァミ ノ ノナン 5 0〜 1 0 0モル0 /0と、 炭素数 6〜 1 2 の直鎖脂肪族ジァミ ンおよび Zまたは炭素数 6〜 1 2の側鎖を有する脂 肪族ジァミ ン 0〜 5 0モル％由来のジァミン由来構成単位 （ a— 1 ) と、 テレフタル酸 6 0〜 1 0 0モル0 /0と、 テレフタル酸以外の芳香族ジカル ボン酸および または炭素原子数 4〜 2 0の脂肪族ジカルボン酸 0〜 4 0モル％由来のジカルボン酸由来構成単位 （ a — 2 ) を分子内に有する ポリアミ ド （A ) を含んでなることを特徴とする発光ダイオード反射板 用樹脂。 1.1, 9-Jiami Bruno nonane and 5 0-1 0 0 mole 0/0, fats having a linear aliphatic Jiami emissions and Z or the side chain with carbon number 6-1 2 with carbon number 6-1 2 the family Jiami down 0-5 0 mole% derived from Jiamin derived constituent units (a- 1), terephthalic acid 6 0-1 0 0 mole 0/0, the aromatic dicarboxylic acids other than terephthalic acid and or number of carbon atoms A light-emitting diode reflector comprising a polyamide (A) having a dicarboxylic acid-derived structural unit (a-2) derived from 0 to 40 mol% of 4 to 20 aliphatic dicarboxylic acids in a molecule. For resin.
2 . 成分 （A ) と して、 1， 9 —ジアミ ノ ノナン 5 0〜 1 0 0モル0 /0 と、 炭素数 6〜 1 2の直鎖脂肪族ジァミンおよび Zまたは炭素数 6〜 1 2の側鎖を有する脂肪族ジァミ ン 0〜 5 0モル％由来のジァミ ン由来構 成単位 ( a - 1 ) と、 テレフタル酸 6 0〜 1 0 0モル0 /0と、 テレフタル 酸以外の芳香族ジカルボン酸および/または炭素原子数 4〜 2 0の脂肪 族ジカルボン酸 0〜 4 0モル％由来のジカルボン酸由来構成単位 （ a— 2 ) を分子内に有するポリアミ ド 1 0 0重量部と、 成分 （B ) と して無 機充填材 1〜 2 0 0重量部とを含んでなることを特徴とする、 発光ダイ ォード反射板用樹脂組成物。 . 2 as the component (A), 1, 9 - diamine Bruno nonane 5 0-1 0 0 mole 0/0, linear aliphatic number 6-1 2 carbon Jiamin and Z or carbon number 6-1 2 aliphatic Jiami down 0-5 0 mole% derived Jiami emissions from configuration units having a side chain of (a - 1) and, terephthalic acid 6 0-1 0 0 mole 0/0, the aromatic other than terephthalic acid 100 parts by weight of a polyamide having a dicarboxylic acid-derived structural unit (a-2) derived from 0 to 40 mol% of a dicarboxylic acid and / or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms in a molecule, and (B) A resin composition for a light-emitting diode reflecting plate, comprising 1 to 200 parts by weight of an inorganic filler.
3 . 成分 （B ) の無機充填材が、 ガラス繊維、 タルク、 ウォラス トナ イ ト、 チタン酸カリ ウム、 酸化亜鉛、 二酸化チタン、 炭酸カルシウム、 硫酸バリ ウム、 及ぴ、 培焼カオリ ンクレイからなる群から選択される少 なく とも一つの無機充填材を含んでなるものであることを特徴とする請 求項 2に記載した発光ダイォー ド反射板用樹脂組成物。 3. The inorganic filler of component (B) is a group consisting of glass fiber, talc, wollastonite, potassium titanate, zinc oxide, titanium dioxide, calcium carbonate, barium sulfate, and calcined kaolin clay. 3. The resin composition for a light emitting diode reflector according to claim 2, comprising at least one inorganic filler selected from the group consisting of:
4 . 請求項 1 に記載した樹脂を含んで構成される発光ダイォード反射 板。 4. A light-emitting diode reflector comprising the resin according to claim 1.
5 . 請求項 2又は 3に記載した榭脂組成物を用いて構成される発光ダ ィォ一ド反射板。  5. A light-emitting diode reflecting plate constituted by using the resin composition according to claim 2 or 3.
6 . 1 , 9 —ジアミノ ノナン 5 0〜： L 0 0モル0 /0と、 炭素数 6〜： 1 2 の直鎖脂肪族ジァミンおよび/または炭素数 6〜 1 2の側鎖を有する脂 肪族ジァミン 0〜 5 0モル0 /0由来のジァミン由来構成単位 （ a— 1 ) と、 テレフタル酸 6 0〜 1 0 0モル％とテレフタル酸以外の芳香族ジカルボ ン酸およびノまたは炭素原子数 4〜 2 0の脂肪族ジカルボン酸 0〜4 0 モル％由来のジカルボン酸由来構成単位 （ a— 2 ) を分子内に有するポ リアミ ドを含んでなることを特徴とする、 エポキシ樹脂接合用成形加工. 6 1, 9 - diamino nonane 5 0: and L 0 0 mole 0/0, 6 carbon atoms: 1 2 A straight-chain aliphatic Jiamin and / or cycloaliphatic aliphatic Jiamin 0-5 0 mole 0/0 derived Jiamin derived constituent units having a side chain with carbon number 6~ 1 2 (a- 1), terephthalic acid 6 0 100 mol% of an aromatic dicarboxylic acid other than terephthalic acid and a dicarboxylic acid-derived structural unit (a-2) derived from a dicarboxylic acid derived from 0 to 40 mol% of an aromatic dicarboxylic acid having 4 to 20 carbon atoms. Molding process for epoxy resin bonding, characterized in that it comprises a polyamide inside
PP用樹脂組成物。 Resin composition for PP.
7. 成分 （A) と して、 1 , 9—ジアミノノナン 5 0〜： 1 0 0モル0 /0 と、 炭素数 6〜 1 2の直鎖脂肪族ジァミンおよび Zまたは炭素数 6〜 1 2の側鎖を有する脂肪族ジァミン 0〜 5 0モル％由来のジァミン由来構 成単位 （ a — 1 ) と、 テレフタル酸 6 0〜 1 0 0モル0 /0と、 テレフタル 酸以外の芳香族ジカルボン酸および または炭素原子数 4〜 2 0の脂肪 族ジカルボン酸 0〜 4 0モル％由来のジカルボン酸由来構成単位 （ a — 2) を分子内に有するポリアミ ド （A) 1 0 0重量部と、 成分 （B) と して無機充填材 1〜 2 0 0重量部とを含んでなることを特徴とする、 ェ ポキシ樹脂接合用成形加工品用樹脂組成物。 7. with component (A), 1, 9-diaminononane 5 0: 1 0 0 mole 0/0, the number 6-1 2 linear aliphatic Jiamin and Z or the number 6-1 2 carbon atoms aliphatic Jiamin 0-5 0 mole% derived Jiamin from configuration units having a side chain (a - 1) and, terephthalic acid 6 0-1 0 0 mole 0/0, the aromatic dicarboxylic acid other than terephthalic acid and Alternatively, 100 parts by weight of a polyamide (A) having a dicarboxylic acid-derived constituent unit (a-2) derived from 0 to 40 mol% of an aliphatic dicarboxylic acid having 4 to 20 carbon atoms in a molecule, and a component ( A resin composition for molded articles for epoxy resin bonding, comprising 1 to 200 parts by weight of an inorganic filler as B).
8. 1， 9一ジァミ ノ ノナン 5 0〜 1 0 0モル0 /0と、 炭素数 6〜 1 2 の直鎖脂肪族ジァミ ン、 および Zまたは、 炭素数 6〜 1 2の側鎖を有す る脂肪族ジァミン 0〜 5 0モル％由来のジァミン由来構成単位（ a - 1 ) と、 テレフタル酸 6 0〜 1 0 0モル％と、 テレフタル酸以外の芳香族ジ カルボン酸、 および または、 炭素原子数 4〜 2 0の脂肪族ジカルボン 酸 0〜 4 0モル％由来のジカルボン酸由来構成単位 （ a— 2) を分子内 に有するポリアミ ド （A) 1 0 0重量部と、 酸化チタン 1〜 2 0 0重量 部を含んでなることを特徴とする発光ダイォード反射板用樹脂組成物。 8. Yes 1, 9 one Jiami Bruno nonane 5 0-1 0 0 mole 0/0, a straight-chain aliphatic Jiami emissions of carbon number 6-1 2, and Z or the side chain of 6-1 2 carbon atoms Diamine derived structural unit (a-1) derived from 0 to 50 mol% of aliphatic diamine, 60 to 100 mol% of terephthalic acid, aromatic dicarboxylic acid other than terephthalic acid, and / or carbon 100 parts by weight of a polyamide (A) having a dicarboxylic acid-derived structural unit (a-2) derived from 0 to 40 mol% of an aliphatic dicarboxylic acid having 4 to 20 atoms in a molecule, and titanium oxide 1 to A resin composition for a light-emitting diode reflector, comprising 200 parts by weight.
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