WO2024004933A1 - Composition de résine de polyamide pour plaque réfléchissante, et plaque réfléchissante - Google Patents

Composition de résine de polyamide pour plaque réfléchissante, et plaque réfléchissante Download PDF

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Publication number
WO2024004933A1
WO2024004933A1 PCT/JP2023/023562 JP2023023562W WO2024004933A1 WO 2024004933 A1 WO2024004933 A1 WO 2024004933A1 JP 2023023562 W JP2023023562 W JP 2023023562W WO 2024004933 A1 WO2024004933 A1 WO 2024004933A1
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Prior art keywords
polyamide resin
acid
resin composition
reflector
aromatic
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PCT/JP2023/023562
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English (en)
Japanese (ja)
Inventor
孝志 北島
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大塚化学株式会社
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Publication of WO2024004933A1 publication Critical patent/WO2024004933A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V7/00—Reflectors for light sources
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V7/00—Reflectors for light sources
    • F21V7/22—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors
    • F21V7/24—Reflectors for light sources characterised by materials, surface treatments or coatings, e.g. dichroic reflectors characterised by the material

Definitions

  • the present invention relates to a polyamide resin composition for a reflector plate containing a polyamide resin, and a reflector obtained by molding the polyamide resin composition for a reflector plate.
  • LEDs Light-emitting devices using light-emitting diode elements
  • LEDs Light-emitting diode elements
  • an LED light emitting device has various favorable characteristics, such as vivid colors, excellent visibility, and relatively low power consumption.
  • the practical application of white LED light-emitting devices that combine blue LEDs and phosphors has led to the use of backlights for liquid crystal display screens in mobile phones, computers, televisions, etc., as well as automobile headlights, instrument panels, lighting equipment, etc. It is attracting a lot of attention as a light source.
  • An LED light emitting device usually consists of an LED that is a light emitting part, a reflector that also serves as a housing, a transparent sealant that seals and protects the LED, and lead wires.
  • Silicone resin is usually used as a sealant for LEDs because of its high light resistance and heat resistance.
  • the reflector of the LED light emitting device is required to have high adhesion to the silicone resin.
  • Patent Document 1 discloses a resin composition containing a polyamide resin, titanium oxide, inorganic fiber, and a silanol condensate. It is described that the reflective plate obtained from the resin composition of Patent Document 1 has high adhesiveness with the silicone resin constituting the sealant.
  • Patent Document 2 describes a polyamide resin, an inorganic filler, a white pigment, and an epoxy resin composition.
  • a resin composition is disclosed that includes a resin.
  • JP2013-091737A Japanese Patent Application Publication No. 2007-271834
  • the present invention solves such problems and provides a polyamide resin composition for a reflector plate and a polyamide resin composition for the reflector plate, which can provide a reflector plate with excellent adhesion to a sealant used in a light emitting device such as an LED.
  • the purpose is to provide a reflective plate obtained by molding an object.
  • the present invention provides a polyamide resin composition for a reflector having the following configuration, and a reflector obtained by molding the resin composition for a reflector.
  • a polyamide resin composition for a reflective plate comprising a polyamide resin (A), an inorganic fiber (B), a colorant (C), and a polyhydric carboxylic acid (D).
  • Item 2 The polyamide resin composition for a reflector plate according to item 1, wherein the polyhydric carboxylic acid (D) has a melting point of 150°C to 300°C.
  • Item 3 The polyamide resin composition for a reflective plate according to Item 1 or 2, wherein the polycarboxylic acid (D) is an aromatic polycarboxylic acid compound.
  • Item 4 Any of Items 1 to 3, wherein the polyhydric carboxylic acid (D) is one or more selected from the group consisting of aromatic dicarboxylic acids, aromatic tricarboxylic acids, and acid anhydrides thereof.
  • the polyamide resin composition for a reflective plate according to the invention is one or more selected from the group consisting of aromatic dicarboxylic acids, aromatic tricarboxylic acids, and acid anhydrides thereof.
  • the polyhydric carboxylic acid (D) is one or more selected from the group consisting of phthalic acid, trimellitic acid, and acid anhydrides thereof, according to any one of Items 1 to 4.
  • Item 6 The polyamide resin composition for a reflector plate according to any one of Items 1 to 5, wherein the polyamide resin (A) has a melting point of 280° C. or higher.
  • Item 7 The polyamide for reflective plates according to any one of Items 1 to 6, wherein the proportion of structural units derived from aromatic monomers among all the structural units constituting the polyamide resin (A) is 20 mol% or more. Resin composition.
  • Item 8 The polyamide resin composition for a reflector plate according to any one of Items 1 to 7, wherein the polyamide resin (A) is a semi-aromatic polyamide resin containing an aromatic dicarboxylic acid and an aliphatic alkylene diamine as constituent units. thing.
  • Item 9 The polyamide resin for a reflector according to any one of Items 1 to 8, wherein the inorganic fiber (B) is one or more selected from the group consisting of wollastonite fibers and potassium titanate fibers. Composition.
  • Item 10 A reflector plate that is a molded article of the polyamide resin composition for a reflector plate according to any one of Items 1 to 9.
  • Item 11 The reflecting plate according to Item 10, wherein the reflecting plate is for an LED.
  • a polyamide resin composition for a reflector plate and a polyamide resin composition for a reflector plate can be molded, which makes it possible to obtain a reflector plate with excellent adhesion to a sealant used in a light emitting device such as an LED. It is possible to provide a reflector plate obtained by doing so.
  • the polyamide resin composition for a reflector of the present invention is a resin composition containing a polyamide resin (A), an inorganic fiber (B), a colorant (C), and a polycarboxylic acid (D).
  • the polyamide resin composition for a reflector of the present invention contains a polyamide resin (A), an inorganic fiber (B), a colorant (C), and a polyhydric carboxylic acid (D), so that it can be used to emit light such as an LED. It is possible to obtain a reflective plate that has excellent adhesion to the sealant used in the device. In particular, it is possible to obtain a reflective plate that has excellent adhesion to the sealant even when exposed to harsh conditions such as outdoor use for a long period of time.
  • the polyamide resin composition for reflective plates of the present invention can be colored in various colors, and improves the mechanical strength and heat resistance of molded products, especially the adhesion to the epoxy sealant of LEDs, to a high level. can be done.
  • the melting point of the polyhydric carboxylic acid (D) is preferably 150°C to 300°C. It is more preferable that the polycarboxylic acid (D) is an aromatic polycarboxylic acid compound.
  • the melting point of the polyamide resin (A) is preferably 280°C or higher.
  • the proportion of structural units derived from aromatic monomers in all structural units constituting the polyamide resin (A) is preferably 20 mol% or more.
  • the polyamide resin (A) is preferably a semi-aromatic polyamide resin containing aromatic dicarboxylic acid and aliphatic alkylene diamine as structural units.
  • the inorganic fiber (B) is preferably one or more selected from the group consisting of wollastonite fibers and potassium titanate fibers, and more preferably wollastonite fibers.
  • polyamide resin (A), inorganic fiber (B), colorant (C), and polyhydric carboxylic acid (D) that constitute such a polyamide resin composition for a reflective plate are used, it is easy to color the polyamide resin composition in various colors. In addition, it is possible to improve the mechanical strength, heat resistance, and adhesion of the reflective plate to a sealant used in a light emitting device such as an LED to an even higher level.
  • the reflective plate of the present invention is a molded article of the above polyamide resin composition for a reflective plate.
  • the reflector of the present invention can be suitably used for LEDs (light emitting diode elements).
  • the polyamide resin composition for a reflector of the present invention contains a polyamide resin (A), an inorganic fiber (B), a colorant (C), and a polyhydric carboxylic acid (D), and other additions as necessary. It may also contain an agent.
  • Polyamide resin (A) As the polyamide resin (A) used in the present invention, various aliphatic monomers and aromatic monomers can be used as monomer components, and any polyamide resin can be used without particular restriction.
  • the polyamide resin (A) used in the present invention preferably has a melting point of 280° C. or higher in order to suppress deformation, discoloration, etc. of the reflector during reflow soldering. Further, in order to suppress thermal decomposition of the polyamide resin (A) during melt processing such as melt kneading and injection molding, the melting point is preferably 350°C or lower, more preferably 330°C or lower. The melting point can be measured according to JIS-K7121.
  • the polyamide resin (A) used in the present invention is preferably a semi-aromatic polyamide resin in order to suppress deformation and deterioration of physical properties due to moisture absorption.
  • the semi-aromatic polyamide resin is preferably a semi-aromatic polyamide resin containing an aromatic dicarboxylic acid and an aliphatic alkylene diamine.
  • An example of a polymer composed of one type of structural unit is an aminocarboxylic acid polymer. Examples of those composed of multiple types of structural units include copolymers of diamine and dicarboxylic acid, copolymers of diamine, dicarboxylic acid, and aminocarboxylic acid, and the like.
  • the copolymerization ratio, copolymerization form such as random copolymer, block copolymer, alternating copolymer, etc. can be arbitrarily selected.
  • the proportion of structural units derived from aromatic monomers in all structural units constituting the polyamide resin (A) is preferably 20 mol% or more, more preferably 25 mol%. Above, more preferably 25 mol% to 60 mol%.
  • the polyamide resin (A) is preferably a semi-aromatic polyamide resin containing a structural unit derived from an aromatic dicarboxylic acid and a structural unit derived from an aliphatic diamine as a structural unit; It is more preferable that it is a semi-aromatic polyamide resin containing a structural unit derived from an aliphatic dicarboxylic acid, a structural unit derived from an aliphatic dicarboxylic acid, and a structural unit derived from an aliphatic diamine.
  • the mole fraction of the structural units derived from the aromatic monomer in the polyamide resin (A) means the mole fraction of the aromatic monomer in all the monomers used in the polymerization raw material.
  • the physical properties such as the melting point can be adjusted as appropriate.
  • Examples of structural units derived from aliphatic monomers include aliphatic dicarboxylic acids, aliphatic diamines, aliphatic aminocarboxylic acids, alicyclic dicarboxylic acids, alicyclic diamines, alicyclic aminocarboxylic acids, and the like.
  • aliphatic dicarboxylic acids examples include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, and 1,11-undecanedicarboxylic acid.
  • acids include acids.
  • adipic acid is preferred as the aliphatic dicarboxylic acid. These can be used alone or in combination of two or more.
  • aliphatic diamines include aliphatic alkylene diamines.
  • aliphatic diamines include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1 , 10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 3-methyl-1,5-diaminopentane, 2-ethyltetramethylenediamine, etc.
  • preferred aliphatic diamines are hexamethylene diamine, 1,9-diaminononane, 1,10-diaminodecane, and 2-methylpentamethylene diamine. These can be used alone or in combination of two or more.
  • aliphatic aminocarboxylic acids examples include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, etc. can be mentioned.
  • lactams corresponding to these may also be used. These can be used alone or in combination of two or more.
  • alicyclic dicarboxylic acid examples include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid.
  • 1,4-cyclohexanedicarboxylic acid is preferred as the alicyclic dicarboxylic acid.
  • alicyclic diamines examples include 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, and 1,3-bis(aminomethyl) Examples include cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, isophoronediamine, and piperazine. These can be used alone or in combination of two or more.
  • alicyclic aminocarboxylic acids include aminocycloalkanecarboxylic acids, specifically aminocyclopropanecarboxylic acids such as 2-aminomethylcyclopropanecarboxylic acid, 4-aminocyclohexanecarboxylic acid, Examples include aminocyclohexanecarboxylic acids such as 3-aminocyclohexanecarboxylic acid, 4-(aminomethyl)cyclohexanecarboxylic acid, and 3-(aminomethyl)cyclohexanecarboxylic acid. These can be used alone or in combination of two or more.
  • Examples of structural units derived from aromatic monomers include aromatic dicarboxylic acids, aromatic diamines, aromatic aminocarboxylic acids, and the like.
  • aromatic dicarboxylic acids examples include terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, naphthalene dicarboxylic acid, and the like.
  • the aromatic dicarboxylic acid is preferably terephthalic acid or isophthalic acid, and more preferably terephthalic acid. These can be used alone or in combination of two or more.
  • aromatic diamine examples include p-phenylenediamine, o-phenylenediamine, m-phenylenediamine, p-xylylenediamine, o-xylylenediamine, m-xylylenediamine, and the like. These can be used alone or in combination of two or more.
  • aromatic aminocarboxylic acids examples include p-aminobenzoic acid and p-aminomethylbenzoic acid. These can be used alone or in combination of two or more.
  • polyamide resin (A) examples include polyamide MXD6, polyamide 6T, polyamide 9T, polyamide 10T, and the like.
  • the content of the polyamide resin (A) is preferably 30% by mass to 98.9% by mass, and preferably 40% by mass to 70% by mass with respect to 100% by mass of the total amount of the polyamide resin composition for a reflector. %, even more preferably 45% to 65% by weight, even more preferably 50% to 65% by weight, particularly 55% to 60% by weight. preferable.
  • inorganic fiber (B) examples of the inorganic fiber (B) used in the present invention include glass fiber, glass milled fiber, carbon fiber, carbon milled fiber, zinc oxide fiber, sodium titanate fiber, potassium titanate fiber, aluminum borate fiber, and boric acid fiber. Examples include magnesium fiber, magnesium oxide fiber, aluminum silicate fiber, silicon nitride fiber, and wollastonite fiber.
  • the inorganic fiber (B) one or more types selected from the group consisting of the above-mentioned inorganic fibers can be used, and the mechanical strength, dimensional stability, and heat resistance of the resulting resin composition can be improved. Can be done.
  • the inorganic fiber (B) used in the present invention is selected from the group consisting of wollastonite fibers and potassium titanate fibers or It is preferable to use two or more types, and from the viewpoint of whiteness, it is more preferable to use wollastonite fiber.
  • Wollastonite fiber is an inorganic fiber made of calcium metasilicate.
  • the dimensions of the wollastonite fibers are not particularly limited, but the average fiber length is preferably 5 ⁇ m to 180 ⁇ m, more preferably 10 ⁇ m to 100 ⁇ m, even more preferably 20 ⁇ m to 40 ⁇ m, particularly preferably 20 ⁇ m to 30 ⁇ m.
  • the average fiber diameter of the wollastonite fibers is preferably 0.1 ⁇ m to 15 ⁇ m, more preferably 1 ⁇ m to 10 ⁇ m, even more preferably 2 ⁇ m to 7 ⁇ m, particularly preferably 2 ⁇ m to 5 ⁇ m.
  • the average aspect ratio of the wollastonite fibers is preferably 3 or more, more preferably 3 to 30, even more preferably 3 to 15, even more preferably 3 to 10, particularly preferably 3 to 8.5.
  • wollastonite fibers can also be used as commercially available products, such as "Vistal W” manufactured by Otsuka Chemical Co., Ltd. (average fiber length 25 ⁇ m, average fiber diameter 3 ⁇ m).
  • the potassium titanate fiber a wide variety of conventionally known fibers can be used, such as potassium tetratitanate fiber, potassium hexatitanate fiber, potassium octitanate fiber, and the like.
  • the dimensions of the potassium titanate fibers are not particularly limited, but the average fiber length is preferably 1 ⁇ m to 50 ⁇ m, more preferably 3 ⁇ m to 30 ⁇ m, even more preferably 3 ⁇ m to 20 ⁇ m.
  • the average fiber diameter of the potassium titanate fibers is preferably 0.01 ⁇ m to 1 ⁇ m, more preferably 0.05 ⁇ m to 0.8 ⁇ m, and still more preferably 0.1 ⁇ m to 0.7 ⁇ m.
  • the average aspect ratio of the potassium titanate fibers is preferably 10 or more, more preferably 10 to 100, and even more preferably 15 to 35.
  • potassium titanate fibers can also be used as commercial products, such as "TISMO D” (average fiber length 15 ⁇ m, average fiber diameter 0.5 ⁇ m) and “TISMO N” (average fiber length 15 ⁇ m, average fiber diameter) manufactured by Otsuka Chemical Co., Ltd. diameter of 0.5 ⁇ m), etc. can be used.
  • TISMO D average fiber length 15 ⁇ m, average fiber diameter 0.5 ⁇ m
  • TISMO N average fiber length 15 ⁇ m, average fiber diameter manufactured by Otsuka Chemical Co., Ltd. diameter of 0.5 ⁇ m
  • the average fiber length and average fiber diameter of the inorganic fiber (B) can be measured by observation with a scanning electron microscope, and the average aspect ratio (average fiber length/average fiber diameter) of the inorganic fiber (B) ) can be calculated from the average fiber length and average fiber diameter.
  • a plurality of inorganic fibers (B) are photographed using a scanning electron microscope, 300 inorganic fibers (B) are arbitrarily selected from the observed image, and their fiber lengths and fiber diameters are measured.
  • the sum of all fiber diameters and dividing by the number of fibers can be determined as the average fiber length, and the sum of all fiber diameters and dividing by the number of fibers can be determined as the average fiber diameter.
  • the inorganic fiber (B) may be subjected to surface treatment in order to further improve the physical properties such as mechanical strength of the resulting resin composition.
  • the inorganic fiber (B) is preferably an inorganic fiber whose surface is at least partially covered with a treatment layer made of a surface treatment agent.
  • the treated layer preferably covers 50% or more of the surface of the inorganic fiber, and more preferably covers 80% or more. However, it is particularly preferable that the treated layer covers the entire surface of the inorganic fiber.
  • the inorganic fibers (B) include inorganic fibers whose surfaces are at least partially covered with a treatment layer composed of a surface treatment agent, and inorganic fibers whose surfaces are covered with a surface treatment agent, within a range that does not impair their preferable physical properties.
  • a mixture of unprocessed inorganic fibers may also be used.
  • the surface treatment agent is preferably a hydrophobic surface treatment agent.
  • hydrophobic surface treatment agent examples include a silane coupling agent, a titanium coupling agent, and an aluminate coupling agent.
  • a silane coupling agent is preferred as the hydrophobic surface treatment agent.
  • the silane coupling agent is preferably an amino-based silane coupling agent, an epoxy-based silane coupling agent, or an alkyl-based silane coupling agent, and more preferably an amino-based silane coupling agent (aminosilane).
  • the above hydrophobic surface treating agents may be used alone or in combination of two or more.
  • amino-based silane coupling agents examples include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane.
  • epoxy silane coupling agent examples include 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, triethoxy(3-glycidyloxypropyl)silane, Examples include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.
  • alkyl silane coupling agent examples include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, and isobutyltriethoxysilane. , n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane and the like.
  • a dry method and a wet method are known as a method of treating the surface of the inorganic fiber (B) with a surface treatment agent in advance, and either method is used. be able to.
  • the surface treatment concentration at this time is, for example, approximately 0.1% by mass to 3.0% by mass based on 100% by mass of the inorganic fiber (B).
  • a known surface treatment method can be used to form a treatment layer made of a surface treatment agent on the surface of the inorganic fiber (B). Dry method, etc. in which a solution of the surface treatment agent (if liquid) or a solution of the surface treatment agent dissolved in a solvent that promotes hydrolysis (e.g., water, alcohol, or a mixed solvent thereof) is sprayed onto the reinforcing material while stirring. It is done in
  • the amount of the surface treatment agent when treating the surface of the inorganic fiber (B) used in the present invention is not particularly limited, but in the case of a dry method, for example, based on 100 parts by mass of the inorganic fiber (B).
  • a solution of the surface treating agent may be sprayed so that the amount of the surface treating agent is 0.1 parts by mass to 20 parts by mass.
  • the amount of the surface treatment agent within the above range, the adhesion between the polyamide resin (A) and the polycarboxylic acid (D) is further improved, and the dispersibility of the inorganic fiber (B) is further improved. be able to.
  • the content of the inorganic fiber (B) in the polyamide resin composition for a reflector of the present invention is preferably 0.5% by mass to 50% by mass based on 100% by mass of the total amount of the polyamide resin composition for a reflector, It is more preferably 5% by mass to 48% by mass, even more preferably 10% by mass to 45% by mass, and particularly preferably 15% by mass to 45% by mass.
  • the coloring agent (C) used in the present invention may be appropriately selected depending on its use, and for example, pigments such as organic pigments or inorganic pigments, dyes such as organic dyes, etc. can be used.
  • the colorant (C) a plurality of types may be used to adjust the chromaticity and the like, and one or more types of pigments and dyes may be used.
  • the colorant (C) examples include organic pigments such as azo pigments, anthraquinone pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketopyrrolopyrrole pigments, and dioxazine pigments; Black pigments such as carbon black, titanium black, and cobalt black, white pigments such as titanium oxide, inorganic pigments such as ultramarine blue, cobalt blue, and Bengara; extender pigments such as calcium carbonate and barium sulfate; azo dyes, anthraquinone dyes and organic dyes such as perylene dyes. It is also possible to use pigments and dyes in combination; in this case, dyes such as various oil-soluble dyes and disperse dyes, and pigments processed with higher fatty acids, synthetic resins, etc. may be used.
  • organic pigments such as azo pigments, anthraquinone pigments, phthalocyanine pigments, quinacridone pigments
  • the colorant (C) used in the present invention is preferably a white pigment, and more preferably titanium oxide, from the viewpoint of further improving the whiteness of the reflective plate.
  • the colorant (C) is preferably a black pigment, more preferably carbon black, from the viewpoint of further reducing reflection of light from external light. Further, as the colorant (C), a white pigment and a black pigment may be used in combination.
  • titanium oxide in various crystal forms such as anatase type, rutile type, monograph type, etc.
  • the titanium oxide is preferably a rutile type, which has a high refractive index and good photostability.
  • the titanium oxide may be treated with a known surface treatment agent such as alumina, silica, a silane coupling agent, or a titanium coupling agent, if necessary.
  • the titanium oxide mentioned above can be powdered in various shapes such as particulate, fibrous, plate-like (including flaky, scaly, mica-like, etc.), and it is preferable to use particulate powder. .
  • the size of the white pigment used in the present invention is not particularly limited, but from the viewpoint of increasing whiteness, the average particle diameter thereof is preferably 0.05 ⁇ m to 0.5 ⁇ m, more preferably 0.1 ⁇ m to 0.5 ⁇ m. It is 3 ⁇ m.
  • the average particle diameter of the white pigment can be measured by laser diffraction.
  • the white pigment used in the present invention one or more of the above-mentioned white pigments can be used.
  • the dimensions of the black pigment used in the present invention are not particularly limited, but from the viewpoint of further reducing the reflection of light from external light, the average particle diameter is preferably 1 nm to 100 nm, and preferably 5 nm to 80 nm. It is more preferable that the particle diameter is within the range of 10 nm to 60 nm.
  • the content of the colorant (C) in the polyamide resin composition for a reflector of the present invention is preferably 0.5% by mass to 40% by mass based on 100% by mass of the total amount of the resin composition.
  • its content is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and even more preferably 0.5% by mass, based on 100% by mass of the total amount of the polyamide resin composition for a reflector.
  • the content is 7% by mass or more, preferably 5% by mass or less, more preferably 4.5% by mass or less, even more preferably 3% by mass or less.
  • a white pigment When using a white pigment, its content is preferably 1% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, based on 100% by mass of the total amount of the polyamide resin composition for a reflector. , preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less.
  • the content of the white pigment is within the above range, a resin composition with good moldability and appearance and better mechanical strength can be obtained.
  • the polyvalent carboxylic acid (D) used in the present invention is not particularly limited as long as it is a polyvalent carboxylic acid or its equivalent and has two or more carboxy groups in one molecule. can.
  • the polyvalent carboxylic acid (D) may be an acid anhydride of a compound having two or more carboxy groups in one molecule.
  • the number of carboxy groups contained in one molecule is preferably 2 to 4, particularly preferably 3.
  • the polycarboxylic acid (D) is one or more selected from the group consisting of aliphatic polycarboxylic acid compounds, alicyclic polycarboxylic acid compounds, and aromatic polycarboxylic acid compounds. is preferred, and aromatic polycarboxylic acid compounds are more preferred.
  • aliphatic polycarboxylic acid compounds include adipic acid, 1,6-hexanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1, Examples include 10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, and 1,12-dodecanedicarboxylic acid. These may be used alone or in combination of two or more. Among the above aliphatic polycarboxylic acid compounds, aliphatic polycarboxylic acid compounds having 6 to 20 carbon atoms are preferred.
  • alicyclic polycarboxylic acid compounds include hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, etc. . These may be used alone or in combination of two or more. Among the above alicyclic polycarboxylic acid compounds, alicyclic polycarboxylic acid compounds having 8 to 20 carbon atoms are preferred.
  • any aromatic compound having two or more carboxy groups and its acid anhydride can be used without particular limitation.
  • the aromatic compound may be any compound that exhibits aromaticity, and includes benzene-based aromatic compounds having an aromatic ring in which one or more benzene rings are condensed or connected, and a benzene ring-containing compound. Examples include non-benzene aromatic compounds that exhibit aromatic properties. Among these, benzene-based aromatic compounds are preferably used, and the number of aromatic rings in which benzene rings are condensed or connected is usually 1 to 3 from the viewpoint of increasing the content of carboxy groups per molecular mass. , preferably one.
  • aromatic polycarboxylic acid compounds include phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid and other naphthalenedicarboxylic acids that are positional isomers thereof, and 1,1'-biphenyl- Aromatic dicarboxylic acids such as 4,4'-dicarboxylic acid and other biphenyldicarboxylic acids that are positional isomers thereof, 2,6-anthracenedicarboxylic acid and other anthracenedicarboxylic acids that are positional isomers thereof; trimellitic acids, hemimellitic acid, trimesic acid, 2,3,6-naphthalenetricarboxylic acid and other positional isomers thereof; naphthalenetricarboxylic acid, 2,3,6-anthracentric acid and other positional isomers thereof; Aromatic tricarboxylic acids such as anthracenic acid; merophane acid, prenitic acid,
  • aromatic polycarboxylic acid compounds one or two selected from the group consisting of aromatic dicarboxylic acids having 8 to 20 carbon atoms, aromatic tricarboxylic acids having 8 to 20 carbon atoms, and acid anhydrides thereof. It is preferably one or more selected from the group consisting of aromatic dicarboxylic acids having 8 to 14 carbon atoms, aromatic tricarboxylic acids having 8 to 14 carbon atoms, and acid anhydrides thereof.
  • phthalic acid More preferably, one or more selected from the group consisting of phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and acid anhydrides thereof; phthalic acid, trimellitic acid, It is particularly preferably trimellitic acid or trimellitic anhydride, and most preferably trimellitic acid or trimellitic anhydride.
  • the melting point of the polycarboxylic acid (D) is preferably 150°C to 300°C, more preferably 150°C to 250°C.
  • the content of polyhydric carboxylic acid (D) in the polyamide resin composition for a reflector of the present invention is preferably 0.1% by mass to 2% by mass, and 0.1% by mass to 2% by mass, based on 100% by mass of the total amount of the resin composition. .1% by mass to 1% by mass, more preferably 0.2% to 0.8% by mass, particularly preferably 0.3% to 0.7% by mass. .
  • By setting the content of polycarboxylic acid (D) within this range it is possible to further improve the adhesion between the polyamide resin composition and the epoxy sealant while maintaining mechanical strength.
  • the polyamide resin composition for reflective plates of the present invention contains inorganic fillers, antioxidants, heat stabilizers, flame retardants, plasticizers, nucleating agents, mold release agents, and ultraviolet absorbers within the range that does not impair its desirable physical properties. It may contain additives such as. These may be used alone or in combination of two or more.
  • inorganic fillers examples include talc, silica, zinc oxide (including tetrapod-shaped ones), mica, barium sulfate, and the like.
  • antioxidants examples include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
  • phenolic antioxidants include triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-(3,5 -di-tert-butyl-4-hydroxyphenyl)propionate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyester, N,N'-hexamethylenebis(3,5-di- tert-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
  • phenolic antioxidants include pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylene bis(3-( 3,5-di-tert-butyl-4-hydroxyphenyl)-propanamide is preferred.
  • phosphorus antioxidants include tris(2,4-di-tert-butylphenyl)phosphite, 2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d ,f][1.3.2]dioxaphosphepin-6-yl]oxy]-N,N-bis[2-[[2,4,8,10-tetrakis(1,1 dimethylethyl)dibenzo [d,f][1.3.2]dioxaphosphevin-6-yl]oxy]-ethyl]ethanamine, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphos Examples include fights.
  • sulfur-based antioxidants examples include 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tetrakis[methylene-3-(dodecylthio)propionate] ]Methane, etc.
  • the amount of additives other than the above-mentioned essential components that may be used in the present invention is not particularly limited as long as it does not impair the preferred physical properties of the resin composition of the present invention.
  • the amount of additives other than the above-mentioned essential components is usually 10% by mass or less, preferably 7% by mass or less, and more preferably 5% by mass or less, based on 100% by mass of the total resin composition.
  • the polyamide resin composition for reflective plates of the present invention is prepared by mixing a mixture containing polyamide resin, inorganic fibers, colorants, and polycarboxylic acids in various blending ratios, and other additives as necessary. and heating (especially melt-kneading).
  • a known melt-kneading device such as a twin-screw extruder can be used.
  • the heating temperature in melt-kneading is not particularly limited as long as it is a temperature at which the polyamide resin can be melted, and can usually be set to a temperature equal to or higher than the melting point of the polyamide resin and lower than the decomposition start temperature. Usually, the temperature inside the cylinder of the melt-kneading device used for melt-kneading is adjusted within this temperature range. In this way, the polyamide resin composition for a reflective plate of the present invention that exhibits the desired effects is produced.
  • a reflective plate of the present invention by using the polyamide resin composition for a reflective plate of the present invention, a reflective plate that has excellent adhesion to a sealant used in a light emitting device such as an LED can be obtained. Among these, it is possible to improve the adhesion with the epoxy sealant.
  • the resin composition of the present invention can be produced by known resin molding methods such as injection molding, insert molding, compression molding, extrusion molding, blow molding, and inflation molding, depending on the type, use, shape, etc. of the intended molded product. It can be made into various molded products. Further, a molding method that is a combination of the above molding methods can also be employed.
  • the reflector obtained by molding the resin composition of the present invention has excellent adhesion to the epoxy resin as a sealant, and is therefore suitable as an LED reflector, preferably an LED reflector used outdoors. Moreover, since it has excellent color fastness, it can be used as an LED reflecting plate without plating the light reflecting surface.
  • the reflector of the present invention means a reflector for a light emitting device.
  • a reflective "plate” its shape is not particularly limited as long as it has the ability to reflect light, and is not limited to a "plate”-like planar shape.
  • it includes three-dimensional shapes such as a box shape, a conical shape, and a parabolic shape.
  • the reflector plate of the present invention can be applied not only to LED light emitting devices but also to other uses that reflect light.
  • various electrical and electronic components automobile keyless entry systems, refrigerator lighting, LCD backlights, automobile front panel lighting devices, lighting stands, bed lights, home appliance indicators, and optical communication equipment such as infrared communication.
  • a reflecting plate for a ceiling lighting device etc.
  • the present invention will be specifically explained below based on Examples and Comparative Examples, but the present invention is not limited thereto.
  • the polyamide resin, epoxy resin, inorganic fiber, coloring agent, and polyhydric carboxylic acid used in the present examples and comparative examples are specifically as follows.
  • the melting point of the polyamide resin is determined by the endothermic peak obtained by raising the temperature from 25°C at a rate of 10°C/min under a nitrogen stream using a differential scanning calorimeter (manufactured by Seiko Instruments, trade name "DSC6200"). And so.
  • the melting point of the polyhydric carboxylic acid was measured using an automatic melting point measuring device (Melting Point System MP70, manufactured by Mettler Toledo) based on the light transmission method of JIS K 0064.
  • Polyamide resin Semi-aromatic polyamide resin obtained by polymerizing hexamethylene diamine, terephthalic acid, and adipic acid in proportions of 50 mol%, 27.5 mol%, and 22.5 mol%, respectively, manufactured by DuPont, product name "Zytel” HTN502HF”, melting point 310°C
  • Epoxy resin 1 melting point 107°C, manufactured by Mitsubishi Chemical Corporation, product name “JER YX4000HK”
  • Epoxy resin 2 Softening point 76°C, manufactured by Daicel Corporation, product name "EHPE3150"
  • Wollastonite fiber average fiber length 25 ⁇ m, average fiber diameter 3 ⁇ m, manufactured by Otsuka Chemical Co., Ltd., product name “Vistal W”
  • Carbon masterbatch carbon black (50% by mass) and polyamide MXD6 (50% by mass), manufactured by Ota Kasei Co., Ltd., product name "NB-35 Grain Black” Titanium oxide: average particle size 0.21 ⁇ m, manufactured by Teika, trade name “JR-405”
  • Polycarboxylic acid 1 trimellitic acid, melting point 231°C
  • Polycarboxylic acid 2 trimellitic anhydride, melting point 168°C
  • Polyhydric carboxylic acid 3 phthalic acid, melting point 210°C
  • Example 1 to Example 4 and Comparative Example 1 to Comparative Example 4 each material was melt-kneaded using a twin-screw extruder at the blending ratio shown in Table 1 to produce pellets. Note that the cylinder temperature of the twin-screw extruder was 320°C.
  • JIS test pieces and flat plates measuring 30 mm long x 30 mm wide x 3 mm thick were molded using an injection molding machine to form evaluation samples.
  • the cylinder temperature of the injection molding machine was 320°C, and the mold temperature was 150°C.
  • Examples 1 to 4 in which polyhydric carboxylic acid was added had improved both initial adhesion and adhesion after the water absorption test compared to Comparative Examples 1 to 4 in which polycarboxylic acid was not added. I understand that. On the other hand, in Comparative Examples 2 and 3 in which epoxy resin was added, the initial adhesion was slightly lower, but the adhesion was improved after the water absorption test. Therefore, although epoxy resin can be expected to improve in actual outdoor use, the polyhydric carboxylic acid added systems such as Examples 1 to 4 have significantly greater adhesion than the epoxy resin added systems at the initial stage and after the water absorption test. expensive. From this, it can be seen that the addition of polycarboxylic acid has a remarkable effect of improving adhesion, which is greater than that of the epoxy resin addition system.

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Abstract

L'invention concerne une composition de résine de polyamide qui est destinée à une plaque réfléchissante et à partir de laquelle une plaque réfléchissante, qui a une excellente adhérence à un agent d'étanchéité utilisé dans un dispositif électroluminescent tel qu'une DEL, peut être obtenue.　La composition de résine de polyamide pour une plaque réfléchissante comprend une résine de polyamide (A), une fibre inorganique (B), un colorant (C) et un acide carboxylique polyvalent (D).
PCT/JP2023/023562 2022-06-30 2023-06-26 Composition de résine de polyamide pour plaque réfléchissante, et plaque réfléchissante WO2024004933A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06329790A (ja) * 1993-05-21 1994-11-29 Sanyo Chem Ind Ltd 帯電防止剤および樹脂組成物
JPH11240995A (ja) * 1998-02-24 1999-09-07 Techno Polymer Kk 熱可塑性樹脂組成物
JP2001011309A (ja) * 1999-04-27 2001-01-16 Toray Ind Inc ポリアミド樹脂組成物および箱形成形品
WO2003085029A1 (fr) * 2002-04-05 2003-10-16 Mitsui Chemicals, Inc. Composition de resine pour reflecteurs a diodes electroluminescentes
JP2007271834A (ja) * 2006-03-31 2007-10-18 Mitsui Chemicals Inc 反射板用樹脂組成物および反射板
JP2009155551A (ja) * 2007-12-27 2009-07-16 Toyoda Gosei Co Ltd 複合材料組成物及び光反射部材
US20130217813A1 (en) * 2010-09-28 2013-08-22 Cheil Industries Inc. Polyamide Composition Having Surface Reflectance and Heat Resistance
JP2014019787A (ja) * 2012-07-18 2014-02-03 Sumitomo Electric Ind Ltd 接着剤組成物並びにそれを用いた補強板付きフレキシブルプリント配線板
JP5646120B1 (ja) * 2013-02-19 2014-12-24 ユニチカ株式会社 半芳香族ポリアミド樹脂組成物
WO2020230805A1 (fr) * 2019-05-16 2020-11-19 ユニチカ株式会社 Composition de résine polyamide

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06329790A (ja) * 1993-05-21 1994-11-29 Sanyo Chem Ind Ltd 帯電防止剤および樹脂組成物
JPH11240995A (ja) * 1998-02-24 1999-09-07 Techno Polymer Kk 熱可塑性樹脂組成物
JP2001011309A (ja) * 1999-04-27 2001-01-16 Toray Ind Inc ポリアミド樹脂組成物および箱形成形品
WO2003085029A1 (fr) * 2002-04-05 2003-10-16 Mitsui Chemicals, Inc. Composition de resine pour reflecteurs a diodes electroluminescentes
JP2007271834A (ja) * 2006-03-31 2007-10-18 Mitsui Chemicals Inc 反射板用樹脂組成物および反射板
JP2009155551A (ja) * 2007-12-27 2009-07-16 Toyoda Gosei Co Ltd 複合材料組成物及び光反射部材
US20130217813A1 (en) * 2010-09-28 2013-08-22 Cheil Industries Inc. Polyamide Composition Having Surface Reflectance and Heat Resistance
JP2014019787A (ja) * 2012-07-18 2014-02-03 Sumitomo Electric Ind Ltd 接着剤組成物並びにそれを用いた補強板付きフレキシブルプリント配線板
JP5646120B1 (ja) * 2013-02-19 2014-12-24 ユニチカ株式会社 半芳香族ポリアミド樹脂組成物
WO2020230805A1 (fr) * 2019-05-16 2020-11-19 ユニチカ株式会社 Composition de résine polyamide

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