WO2014104471A1 - Thermoplastic resin composition with excellent discoloration-resistance at high temperature and molded product using same - Google Patents

Thermoplastic resin composition with excellent discoloration-resistance at high temperature and molded product using same Download PDF

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Publication number
WO2014104471A1
WO2014104471A1 PCT/KR2013/001723 KR2013001723W WO2014104471A1 WO 2014104471 A1 WO2014104471 A1 WO 2014104471A1 KR 2013001723 W KR2013001723 W KR 2013001723W WO 2014104471 A1 WO2014104471 A1 WO 2014104471A1
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resin composition
thermoplastic resin
compound
weight
acrylic
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PCT/KR2013/001723
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French (fr)
Korean (ko)
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이상화
백인걸
임종철
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제일모직주식회사
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Publication of WO2014104471A1 publication Critical patent/WO2014104471A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article using the same. More specifically, the present invention relates to a thermoplastic resin composition having excellent discoloration resistance at a high temperature and a molded article using the same without deteriorating mechanical properties such as heat resistance, reflectivity and impact resistance.
  • PA polyamide
  • PA612 PA11, PA12, PA6T, PA6I, PA9T, copolymers, blends thereof, and so on. Maintain great demand.
  • Polyamide-based resins have been greatly improved by adding inorganic reinforcing materials such as glass fibers, and thus have excellent mechanical stiffness and heat resistance.
  • LED light emitting diode
  • EL organic electroluminescent
  • lead-free joining Due to environmental regulations, lead-free joining has become a major factor, and tin-silver alloys have been used as lead-free joining. These lead-free joints have a higher melting point (approximately 260 ° C.) than conventional soldering, and the materials applicable to them are limited to liquid crystal polymers (LCP), polyphenylene sulfides (PPS) and PPA-based resins.
  • LCP liquid crystal polymers
  • PPS polyphenylene sulfides
  • PPA-based resins PPA-based resins
  • LEDs generally consist of a semiconductor portion that emits light, a wire, a reflector that also serves as a housing, and a transparent enclosure that seals the semiconductor portion.
  • the reflector can be made of various materials, such as ceramics or heat-resistant plastics, but productivity is an issue for ceramics, and heat-resistant plastics, under injection molding, thermosetting of encapsulants, or under actual environmental conditions in use There is a problem that the optical reflectivity due to the change is reduced.
  • Korean Patent Publication No. 2012-00069798 discloses a polyamide resin composition having a low coefficient of thermal expansion and a constant impact strength by using an inorganic filler, a polyphenylene sulfide resin, and a nano filler in a polyamide resin. Corresponds to the polyamide-based resin composition for use.
  • the present inventors have developed a thermoplastic resin composition having excellent discoloration resistance at a high temperature that can replace a conventional ceramic or heat-resistant plastic that has been used as a material of the LED reflector.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in discoloration resistance at a high temperature.
  • Another object of the present invention is to provide a thermoplastic resin composition having excellent heat resistance.
  • Still another object of the present invention is to provide a thermoplastic resin composition having excellent reflectivity.
  • Another object of the present invention is to provide a thermoplastic resin composition excellent in impact resistance.
  • Still another object of the present invention is to provide a thermoplastic resin composition having excellent discoloration resistance at high temperature without deteriorating mechanical properties such as heat resistance, reflectivity, and impact resistance.
  • Still another object of the present invention is to provide a molded article using the thermoplastic resin composition.
  • thermoplastic resin composition of the present invention comprises (A) an aromatic polyamide resin, (B) an acrylic compound, (C) an inorganic filler, (D) a white pigment, (E) an optical stabilizer, and (F) a sodium phosphate salt. It is done.
  • thermoplastic resin composition of the present invention is an aromatic polyamide resin (A) 10 to 70% by weight, acrylic compound (B) 5 to 70% by weight, inorganic filler (C) 5 to 30% by weight and white pigment (D) 10 to 50 Based on 100 parts by weight of the base resin composition including the weight%, 0.01 to 2 parts by weight of the light stabilizer (E) and 0.01 to 2 parts by weight of the sodium foam salt (F) may be included.
  • the aromatic polyamide resin (A) is preferably prepared by polycondensation of monomers containing 10 to 100 mol% of aromatic dicarboxylic acid and C 4 to C 20 aliphatic or alicyclic diamines.
  • the aromatic polyamide resin (A) may include a repeating unit represented by the following formula (3).
  • n is an integer from 50 to 500.
  • an acryl-type compound (B) contains the acryl-type monomer or polymer of a linear structure.
  • the acrylic compound may include (meth) acrylic acid alkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid or a mixture thereof, and the acrylic compound may be poly (Meth) acrylic acid alkyl esters or copolymers thereof, poly (meth) acrylic acid aryl esters or copolymers thereof, poly (meth) acrylic acid cycloalkyl esters or copolymers thereof, poly (meth) acrylic acid or copolymers thereof, or mixtures thereof It may include.
  • the acrylic compound may include polymethyl (meth) acrylate, polyphenyl (meth) acrylate, polyphenyl (meth) acrylate-polymethyl (meth) acrylate copolymer, or a mixture thereof.
  • Acrylic monomers or polymers may be included in 40 to 100% by weight based on 100% by weight of the acrylic compound (B).
  • the acrylic compound (B) may further include a copolymer of an acrylic monomer and an aromatic vinyl compound, a vinyl cyanide compound, a heterocyclic compound, or a mixture thereof.
  • Inorganic fillers (C) include carbon fibers, glass fibers, boron fibers, glass beads, glass flakes, carbon black, talc, clay, kaolin, talc, mica, calcium carbonate, wollastonite, potassium titanate whisker, aluminum borate Zinc oxide whisker, calcium whisker or mixtures thereof.
  • Preferred inorganic filler (C) is wollastonite, the wollastonite is preferably an average length of 0.1 to 100 ⁇ m.
  • the white pigment (D) may be titanium oxide, zinc oxide, zinc sulfide, lead white, zinc sulfate, barium sulfate, calcium carbonate, aluminum oxide, or a mixture thereof.
  • the light stabilizer (E) may be a benzophenone compound, a salicylate compound, a benzotriazole compound, an acrylonitrile compound, a hindered amine compound, a hindered phenol compound or a mixture thereof.
  • Sodium phosphate salt (F) may be sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate or mixtures thereof.
  • thermoplastic resin composition of the present invention may further include an additive selected from the group consisting of optical brighteners, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing materials, inorganic additives, pigments, dyes or mixtures thereof.
  • an additive selected from the group consisting of optical brighteners, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing materials, inorganic additives, pigments, dyes or mixtures thereof.
  • this invention provides the molded article manufactured from the polyamide resin composition.
  • the molded article manufactured from the thermoplastic resin composition of the present invention has an initial reflectance of 92% or more measured at a wavelength of 440 nm with a color difference meter, and a reflectance decrease measured at a wavelength of 440 nm before and after 150 hours at a temperature of 85 ° C. and a relative humidity of 85%. Is less than 5%, and yellowness change ( ⁇ YI) measured before and after standing for 24 hours at a temperature of 170 ° C is less than 5.
  • the molded article prepared from the thermoplastic resin composition of the present invention has an Izod impact strength of 25 to 40 kgf ⁇ cm / cm measured on a 1/8 inch thick specimen in accordance with ASTM D256, and a 1/4 under 18.6 kgf load in accordance with ASTM D648.
  • the heat deflection temperature (HDT) measured for the inch-thick specimen is characterized in that 200 to 250 °C.
  • the present invention has the effect of providing a thermoplastic resin composition excellent in discoloration resistance at a high temperature and a molded article using the same without deteriorating mechanical properties such as heat resistance, reflectivity and impact resistance.
  • the present invention relates to a thermoplastic resin composition having excellent discoloration resistance at a high temperature and a molded article using the same without deteriorating mechanical properties such as heat resistance, reflectivity and impact resistance.
  • thermoplastic resin composition according to the present invention comprises (A) aromatic polyamide resin, (B) acrylic compound, (C) inorganic filler, (D) white pigment, (E) light stabilizer and (F) sodium phosphate salt. It features.
  • thermoplastic resin composition of the present invention is 10 to 70% by weight of aromatic polyamide resin (A), 5 to 70% by weight of acrylic compound (B), 5 to 30% by weight of inorganic filler (C), and 10 to white pigment (D). It is characterized by including 0.01-2 weight part of light stabilizers (E), and 0.01-2 weight part of sodium space salts (F) with respect to 100 weight part of base resin compositions containing 50 weight%. Each component is demonstrated concretely below.
  • the aromatic polyamide resin is a structure containing an aromatic ring in the main chain, dicarboxylic acid containing 10 to 100 mol% (mole%) of aromatic dicarboxylic acid (aromatic dicarboxylic acid) ) And C 4 to C 20 are prepared by condensation polymerization of monomers containing aliphatic or alicyclic diamines.
  • Monomers of the aromatic dicarboxylic acid are preferably terephthalic acid and isophthalic acid, which include aromatic rings in the main chain as shown in the following Chemical Formulas 1 and 2, respectively. Is characteristic.
  • aromatic polyamide resins may include repeating units represented by the following Formula 3:
  • n is an integer from 4 to 12 and n is from 50 to 500.
  • Aromatic polyamide resins useful in the present invention are polymers or copolymers containing aromatic rings in the main chain, and specific examples thereof include polyhexamethylene terephthalamide (PA6T), polycaproamide / polyhexamethylene terephthalamide copolymer (PA6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (PA66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (PA66 / 6I), polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (PA6T / 6I), polyhexamethylene terephthalamide / polydodecaamide copolymer (PA6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthal Amide copolymer (PA66 / 6T / 6I),
  • the aromatic polyamide resin (A) of the present invention is 10 to 10% by weight based on 100% by weight of the base resin composition containing the aromatic polyamide resin (A), the acrylic compound (B), the inorganic filler (C) and the white pigment (D). 70 wt%. Preferably from 30 to 60% by weight.
  • the content of the aromatic polyamide resin (A) is less than 10% by weight, the heat resistance of the thermoplastic resin composition may decrease, and when the content of the aromatic polyamide resin (A) exceeds 70% by weight, the high temperature discoloration resistance decreases. Can be.
  • an acrylic polymer or an acrylic copolymer is used as an impact modifier, but the acrylic compound of the present invention is used to improve discoloration resistance of the thermoplastic resin composition at a high temperature. Since the acrylic compound of the present invention includes an acrylic monomer or a polymer having a linear structure, the acrylic compound has a different structure from an acrylic polymer or an acrylic copolymer of a core-shell structure which is generally used for impact reinforcement.
  • the acrylic compound includes a linear acrylic monomer or polymer.
  • the acrylic compound is a (meth) acrylic acid alkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid or a mixture thereof, but is not limited thereto.
  • alkyl is a substituted or unsubstituted C 1 to C 10 alkyl group
  • aryl is a substituted or unsubstituted C 6 to C 20 aryl group
  • cycloalkyl is a substituted or unsubstituted C 6 to C 20 cycloalkyl group to be.
  • the acryl-based compound examples include n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth ) Acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxy (meth) acrylate, It may be selected from the group consisting of phenoxyethyl (meth) acrylate, and the like, but is not necessarily limited thereto, and may be used by mixing two or more kinds. Of these, methyl (meth) acrylate may be preferably used.
  • the acrylic compound may be poly (meth) acrylic acid alkyl ester or copolymer thereof, poly (meth) acrylic acid aryl ester or copolymer thereof, poly (meth) acrylic acid cycloalkyl ester or copolymer thereof, poly (meth) acrylic acid or air thereof Including, but not limited to, coalescing, or mixtures thereof.
  • Specific examples of the acryl-based compound include polymethyl (meth) acrylate, polyphenyl (meth) acrylate, polyphenyl (meth) acrylate-polymethyl (meth) acrylate copolymer, or a mixture thereof. It is not limited to this.
  • the said acryl-type compound can manufacture the raw material monomer containing an acryl-type compound by well-known polymerization methods, such as suspension polymerization method, block polymerization method, and emulsion polymerization method.
  • the acrylic monomer or polymer may be included in an amount of 40 to 100% by weight, preferably 50 to 100% by weight, based on 100% by weight of the acrylic compound (B).
  • the acrylic monomer or polymer is included in the above content range, the high temperature discoloration resistance of the thermoplastic resin composition is excellent.
  • the acrylic compound (B) may further include a copolymer of an acrylic monomer and an aromatic vinyl compound, a vinyl cyanide compound, a heterocyclic compound, or a mixture thereof.
  • a copolymer of an acrylic monomer, an aromatic vinyl compound, and a vinyl cyanide compound may be included.
  • Examples of the aromatic vinyl compound may include, but are not limited to, styrene, C 1 to C 10 alkyl substituted styrene, halogen substituted styrene, or a mixture thereof.
  • alkyl substituted styrenes include, but are not limited to, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, ⁇ -methyl styrene, and the like.
  • vinyl cyanide compound may include, but are not limited to, acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof.
  • heterocyclic compounds may include, but are not limited to, maleic anhydride, alkyl or phenyl N-substituted maleimides, or mixtures thereof.
  • the copolymer of the acrylic monomer, the aromatic vinyl compound and the vinyl cyanide compound may be composed of 40 to 99.8 wt% of the acrylic monomer, 0.1 to 40 wt% of the aromatic vinyl compound, and 0.1 to 20 wt% of the vinyl cyanide compound.
  • the amount is within the content range, the polymerization stability of the copolymer is excellent, the discoloration resistance is excellent at the high temperature of the thermoplastic resin composition, and the gloss of the molded article using the thermoplastic resin composition is excellent.
  • the weight average molecular weight of the acrylic polymer in the acrylic compound (B) is 10,000 to 200,000 g / mol, preferably 10,000 to 150,000 g / mol, and more preferably 20,000 to 120,000 g / mol.
  • the weight average molecular weight of the above range can be obtained excellent balance of physical properties of the flowability and impact resistance of the thermoplastic resin composition.
  • at least two kinds of acrylic polymers having different weight average molecular weights within this weight average molecular weight range may be used. As such, when two kinds of acrylic polymers having different weight average molecular weights are used, the fluidity and impact resistance of the thermoplastic resin composition can be adjusted.
  • the acrylic compound (B) of the present invention is 5 to 70% by weight based on 100% by weight of the base resin composition containing an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D). Contains% When the content of the acrylic compound (B) is less than 5% by weight, the high temperature discoloration resistance of the thermoplastic resin composition may be lowered. When the content of the acrylic compound (B) is more than 70% by weight, the heat resistance and the moldability of the thermoplastic resin composition may be reduced. Can be degraded.
  • thermoplastic resin composition in order to increase the mechanical properties, heat resistance and dimensional stability of the thermoplastic resin composition may include various inorganic fillers.
  • inorganic fillers can be used. Specific examples thereof include carbon fiber, glass fiber, boron fiber, glass beads, glass flakes, carbon black, talc, clay, kaolin, talc, mica, calcium carbonate, and mixtures thereof. Nitrate, potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, calcium whisker and mixtures thereof and the like.
  • Inorganic filler (C) may be used by coating the surface with a suitable organic material in order to improve the adhesion with the thermoplastic resin.
  • thermoplastic resin composition When the inorganic filler (C) is used in the thermoplastic resin composition, mechanical properties such as tensile strength, flexural strength, flexural modulus, and heat resistance such as heat deformation temperature of the molded article manufactured from the thermoplastic resin composition may be improved.
  • wollastonite may be used as the inorganic filler.
  • the average length of the wollastonite is preferably used in the range of 0.1 to 11 ⁇ m.
  • the bulk density (tapped) of the wollastonite is preferably used in the range of 0.1 to 2 g / cm 3, preferably 0.1 to 1 g / cm 3.
  • the cross section of wollastonite can change the cross section depending on the special use besides the square. In the present invention, any kind of wollastonite may be used.
  • Inorganic filler (C) of the present invention is 5 to 30% by weight based on 100% by weight of the base resin composition comprising an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D) Contains%
  • the content of the inorganic filler (C) is less than 5% by weight, mechanical and heat resistance properties such as impact strength of the thermoplastic resin composition may be lowered.
  • the content of the inorganic filler (C) is more than 30% by weight, The fluidity may be lowered and the appearance of the molded article manufactured from the thermoplastic resin composition may be deteriorated.
  • white pigment (D) should be used as an essential component.
  • Examples of the white pigment (D) to be used include titanium oxide, zinc oxide, zinc sulfide, lead white, zinc sulfate, barium sulfate, calcium carbonate and aluminum oxide. These white pigments can be used individually or in mixture of 2 or more types.
  • a white pigment (D) can also be used by processing with a silane coupling agent, a titanium coupling agent, etc. For example, it can surface-treat with silane type compounds, such as vinyl triethoxysilane, 3-aminopropyl triethoxysilane, and 3-glycidoxy propyl triethoxysilane.
  • titanium dioxide is preferable. By using titanium dioxide as the white pigment (D), optical characteristics such as reflectance and concealability are improved.
  • titanium dioxide general titanium dioxide may be used, and the production method and particle size are not limited.
  • titanium dioxide it is more preferable to use what was surface-treated with the inorganic surface treating agent or the organic surface treating agent.
  • Inorganic surface treatment agents include aluminum oxide (alumina, Al 2 O 3 ), silicon dioxide (silica, SiO 2 ), zirconium dioxide (zirconia, ZrO 2 ), sodium silicate, sodium aluminate, sodium aluminum silicate, zinc oxide, mica, etc. There is this.
  • Organic surface treating agents include polydimethylsiloxane, trimethyl propane (TMP), pentaerythritol, and the like.
  • the inorganic or organic surface treatment agent is surface treated to about 2 parts by weight or less based on 100 parts by weight of titanium dioxide.
  • titanium dioxide coated with less than 2 parts by weight of alumina (Al 2 O 3 ), which is an inorganic surface treatment agent, with respect to 100 parts by weight of titanium dioxide is preferable.
  • Titanium dioxide surface-treated with alumina is inorganic surface treatment agent such as silicon dioxide, zirconium dioxide, sodium silicate, sodium aluminate, sodium aluminum silicate, mica, or organic surface treatment such as polydimethylsiloxane, trimethylpropane (TMP), pentaerythritol Zero further modifications can be used.
  • inorganic surface treatment agent such as silicon dioxide, zirconium dioxide, sodium silicate, sodium aluminate, sodium aluminum silicate, mica, or organic surface treatment such as polydimethylsiloxane, trimethylpropane (TMP), pentaerythritol Zero further modifications can be used.
  • White pigment (D) of the present invention is 10 to 50% by weight based on 100% by weight of the base resin composition comprising an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D) Contains%
  • the content of the white pigment (D) is less than 10% by weight, the yellowing resistance and reflectivity of the thermoplastic resin composition may be lowered, and when the content of the white pigment (D) is more than 50% by weight, mechanical properties such as impact resistance of the thermoplastic resin composition This can be degraded.
  • a light stabilizer (E) can be used for the purpose of preventing discoloration of the thermoplastic resin composition of this invention and suppressing a fall of a reflectance.
  • the light stabilizer (E) absorbs ultraviolet rays such as benzophenone compounds, salicylate compounds, benzotriazole compounds, acrylonitrile compounds, and other resonance structure compounds.
  • a compound having a radical trapping ability such as an effective compound, a hindered amine compound, a hindered phenol compound, or a mixture of two or more thereof may be used.
  • a compound having an ultraviolet absorbing effect and a compound having a radical trapping ability are used in combination, a higher effect can be obtained.
  • the light stabilizer (E) of the present invention is 0.01 to 2 parts by weight based on 100 parts by weight of the base resin composition containing an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D). Parts, preferably 0.1 to 2 parts by weight.
  • the content of the light stabilizer (E) is less than 0.01 part by weight, the discoloration resistance and reflectivity of the thermoplastic resin composition may be lowered, and when it is more than 2 parts by weight, the high temperature discoloration resistance of the thermoplastic resin composition may be lowered.
  • the sodium space salt (F) of the present invention can be further used to realize sufficient reflectance of the thermoplastic resin composition while at the same time ensuring thermochromic stability, hydrolysis stability and light stability.
  • thermoplastic resin composition When simultaneously applying the white pigment (D) and the sodium phosphate salt (F), not only can the whiteness of the thermoplastic resin composition be ensured, but also the thermochromic stability becomes very excellent. Since sodium phosphate salt has high whiteness in itself, even if it is mixed, the reflectivity of a thermoplastic resin composition can be ensured enough. In addition, in this case, since the thermoplastic resin composition includes a sodium phosphate salt having excellent thermochromic stability and hydrolysis stability, little color change occurs even after being left at a high temperature / high humidity condition for a long time, and heat of which the reflectance hardly decreases. It is possible to secure discoloration stability and hydrolysis stability.
  • sodium phosphate salt (F) serves to effectively remove the acid (acid) that may occur during the molding operation using the thermoplastic resin composition to further improve the thermochromic stability and hydrolysis stability of the thermoplastic resin composition of the present invention.
  • sodium phosphate salt (F) examples include, but are not limited to, sodium dihydrogen phosphate, sodium monohydrogen phosphate, sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate, or a mixture thereof. Anything may be selected and used appropriately.
  • Sodium phosphate salt (F) is generally not limited to the manufacturing method, the particle size, may be used that is surface-treated with a surface treatment agent to improve compatibility with the thermoplastic resin and dispersibility in the thermoplastic resin matrix (matrix).
  • silane coupling agents such as silane and epoxy silane, titanium coupling agents, organic acids such as organic acids, polyols, and silicones may be used.
  • Sodium phosphate salt (F) of the present invention is 0.01 to 2 with respect to 100 parts by weight of the base resin composition containing an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D) It includes parts by weight. Preferably 0.1 to 2 parts by weight is included.
  • the content of sodium phosphate salt (F) is 0.01 parts by weight, the reflectivity of the thermoplastic resin composition may be reduced, and when the content of sodium phosphate salt (F) is more than 2 parts by weight, impact resistance and yellowing resistance of the thermoplastic resin composition This can be degraded.
  • thermoplastic resin composition of the present invention may further include a fluorescent brightener, a lubricant, a mold releasing agent, a nucleating agent, an antistatic agent, a stabilizer, a reinforcing agent, an inorganic additive, a pigment, a dye, and a mixture thereof according to each use, and the present invention is not limited thereto. It is not.
  • the additive (G) is 0.01 to 20 parts by weight based on 100 parts by weight of the base resin composition containing an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D). Can be used.
  • Fluorescent whitening agent serves to improve the reflectance of the thermoplastic resin composition
  • 4- (benzooxazol-2-yl) -4 '-(5-methylbenzooxazol-2-yl) stilbene or 4,4 Stilbene-bisbenzooxazole derivatives such as' -bis (benzooxazol-2-yl) stilbene and the like can be used.
  • fluorine-containing polymers silicone oils, metal salts of stearic acid, metal salts of montanic acid, montanic acid ester waxes or polyethylene waxes may be used, and talc or clay may be used as a nucleating agent.
  • thermoplastic resin composition according to the present invention can be produced by a known method for producing a resin composition.
  • the components of the present invention and other additives may be mixed at the same time and then melt-extruded in an extruder to produce pellets or chips.
  • the present invention also provides a molded article prepared from the thermoplastic resin composition.
  • a molded article prepared from the thermoplastic resin composition.
  • an extrusion, injection, hollow, compression or casting molding method may be applied. Such molding can be easily carried out by those skilled in the art.
  • the molded article prepared from the thermoplastic resin composition of the present invention has an initial reflectance of 92% or more measured with a color difference meter at a wavelength of 440 nm, and a reflectance decrease measured at a wavelength of 440 nm before / after 150 hours at a temperature of 85 ° C. and a relative humidity of 85%. Is less than 5%, and the yellowness change ( ⁇ YI) measured before and after standing for 24 hours at a temperature of 170 ° C. is less than 5.
  • the molded article prepared from the thermoplastic resin composition of the present invention has an Izod impact strength of 25 to 40 kgf ⁇ cm / cm measured on a 1/8 inch thick specimen in accordance with ASTM D256, and a 1/4 under 18.6 kgf load in accordance with ASTM D648. It is characterized in that the heat deflection temperature (HDT) measured for the inch-thick specimen is 200 to 250 °C.
  • HDT heat deflection temperature
  • thermoplastic resin composition of the present invention is excellent in reflectivity, heat resistance, impact resistance and discoloration resistance at high temperature, it can be preferably applied to molding of various products.
  • the thermoplastic resin composition of the present invention includes not only white pigments, light stabilizers, and sodium phosphate salts in suitable amounts at the same time, but also excellent in heat resistance, reflectivity and impact resistance, as well as reflectance and yellowing even after long time standing at high temperature / high humidity conditions. Since it is excellent in discoloration resistance, such as not falling, it can be used suitably as a material of the LED reflector which is continuously exposed in the environment of high temperature / high humidity.
  • thermoplastic resin composition of the present invention can be applied not only to the LED reflecting plate but also to any other application for reflecting other light rays.
  • it can be used as a reflecting plate for light emitting devices, such as various electrical and electronic components, indoor lighting, outdoor lighting, automobile lighting, display equipment, and headlights.
  • Aromatic polyamide resin (A) used in Examples and Comparative Examples of the present invention The specifications of the acrylic compound (B), inorganic filler (C), white pigment (D), light stabilizer (E), and sodium phosphate salt (F) are as follows.
  • PA10T an aromatic polyamide resin containing an aromatic ring, was used in the main chain prepared by condensation polymerization of terephthalic acid and 1,10-decane diamine.
  • PA6T an aromatic polyamide resin containing an aromatic ring, was used in the main chain prepared by condensation polymerization of terephthalic acid and hexamethylene diamine.
  • a phenylmethacrylate-methylmethacrylate copolymer having 30% by weight of phenylmethacrylate and 70% by weight of methylmethacrylate and having a weight average molecular weight of 20,000 g / mol was used.
  • Polymethylmethacrylate having a weight average molecular weight of 100,000 g / mol polymerized from the methylmethacrylate monomer was used.
  • NYCO NYAD 5000 was used as wollastonite with an average length of 2.2 ⁇ m and an apparent density of 0.77 g / cm 3.
  • Titanium dioxide, Kronos 2233 from titanium dioxide was used as a white pigment.
  • BASF CHIMASSORB 944 was used as a light stabilizer.
  • Innophos sodium sodium pyrophosphate was used as the sodium phosphate salt.
  • Each component was added according to the content of Table 1 and melted / kneaded in a twin screw melt extruder heated to 240 to 350 ° C. to prepare a resin composition in a pellet state.
  • the pellet thus obtained was dried at a temperature of 130 ° C. for at least 5 hours, and then a specimen for evaluation of physical properties was prepared using a screw injection machine heated to 240 to 330 ° C.
  • Heat resistance In accordance with ASTM D648, the heat deflection temperature (HDT) was measured for a 1/4 inch thick specimen under a load of 18.6 kgf.
  • Reflectivity Konica Minolta 3600D CIE Lab.
  • the initial reflectance (SCI, specular component included) at 440 nm wavelength was measured with a color difference meter, and the reflectance was measured again after 150 hours at 85 ° C. and 85% relative humidity to evaluate the decrease in reflectance.
  • Yellowing resistance Konica Minolta 3600D CIE Lab.
  • the initial yellowness index (YI) was measured with a color difference meter, and the yellowness was measured again after standing at a temperature of 170 ° C. for 24 hours to evaluate the change in yellowness.
  • Izod impact strength was measured for unnotched specimens of 1/8 inch thickness according to ASTM D256.
  • thermoplastic resin compositions of Examples 1 to 9 according to the composition of the present invention have the yellowness retention characteristics in the constant temperature / humidity evaluation and the reflectance retention characteristics and constant temperature evaluation without deteriorating heat resistance and impact resistance. It can be seen that it is excellent in high temperature discoloration resistance.
  • Comparative Example 2 when the acrylic compound (B) is not used as in Comparative Example 2, or when the acrylic compound (B) is used in a small amount outside the scope of the present invention as in Comparative Example 3, excellent yellowness retention characteristics cannot be secured, so that It turns out that discoloration resistance fell.
  • Comparative Example 1 in which the inorganic filler (C) is not used, has reduced heat resistance.

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Abstract

The present invention relates to a thermoplastic resin composition and a molded product using the same, the thermoplastic resin composition comprising: (A) an aromatic polyamide resin, (B) an acryl-based compound, (C) an inorganic filler, (D) a white pigment, (E) a photostabilizer and (F) a sodium phosphate salt. The thermoplastic resin composition and the molded product using the same do not have decreased mechanical properties such as heat-resistance, reflexibility and impact resistance, and have excellent discoloration-resistance at a high temperature.

Description

고온에서 내변색성이 우수한 열가소성 수지 조성물 및 이를 이용한 성형품Thermoplastic resin composition having excellent discoloration resistance at high temperature and molded article using same
본 발명은 열가소성 수지 조성물 및 이를 이용한 성형품에 관한 것이다. 보다 구체적으로, 본 발명은 내열성, 반사성 및 내충격성과 같은 기계적 특성은 저하되지 않고 고온에서 내변색성이 우수한 열가소성 수지 조성물 및 이를 이용한 성형품에 관한 것이다.The present invention relates to a thermoplastic resin composition and a molded article using the same. More specifically, the present invention relates to a thermoplastic resin composition having excellent discoloration resistance at a high temperature and a molded article using the same without deteriorating mechanical properties such as heat resistance, reflectivity and impact resistance.
엔지니어링 플라스틱(engineering plastic)으로서 폴리아미드(polyamide, PA) 수지의 역사는 이미 40년에 가깝지만 아직도 여전히 수요는 왕성하다. 폴리아미드 수지는 PA6, PA66, PA610, PA612, PA11, PA12, PA6T, PA6I, PA9T 및 이들의 공중합체, 블렌드(blend) 등 기본적으로 종류가 많으며, 제각기 유용한 특징이 있고 다양한 성능을 창출할 수 있으므로 큰 수요를 계속 유지하고 있다.The history of polyamide (PA) resins as engineering plastics is already close to 40 years, but still in high demand. There are many types of polyamide resins, such as PA6, PA66, PA610, PA612, PA11, PA12, PA6T, PA6I, PA9T, copolymers, blends thereof, and so on. Maintain great demand.
폴리아미드계 수지는 유리섬유와 같은 무기질 보강재를 첨가함으로써, 우수한 기계적 강성과 내열성이 크게 향상되어 구조재나 자동차의 내-외장재에 적용이 되고 있다.Polyamide-based resins have been greatly improved by adding inorganic reinforcing materials such as glass fibers, and thus have excellent mechanical stiffness and heat resistance.
저전력 소모, 장기간의 수명 및 기타 이점으로 인하여, 최근 발광다이오드(LED) 및 유기 전기발광(EL) 장치와 같은 신규 광원이 조명, 표시 장치 및 기타 요구로 증가하고 있다.Due to low power consumption, long lifespan and other benefits, new light sources such as light emitting diode (LED) and organic electroluminescent (EL) devices have recently increased to lighting, display devices and other needs.
특히, 뛰어난 에너지 효율 및 수명으로 인하여, 최근 기존의 많은 광원을 급속히 대체하며 각광을 받고 있는 LED의 부속인 리플렉터(reflector), 리플렉터 컵(reflector cup), 스크램블러(scrambler) 또는 하우징(housing) 등에 사용되는 소재로써, 유리섬유가 보강되고, 주사슬에 벤젠고리를 포함하는 고내열성 변성-폴리아미드계 수지, 즉 PPA(polyphthalamide)계 수지가 많이 사용되고 있다. 이는 수지가 LED의 제조 공정상에서 발생하는 높은 온도를 견뎌야 하고, 백색도가 높아 반사율이 뛰어나야 함과 동시에, 제품 사용시 지속적으로 조사되는 광원에 의한 황변화로 인해 백색도 저하를 최소화시켜야 하며, 또한 전기가 통하지 않아야 하기 때문이다.In particular, due to its excellent energy efficiency and longevity, it is rapidly replacing many conventional light sources and used in reflectors, reflector cups, scramblers or housings, which are the parts of LEDs that are in the spotlight. As the material, glass fibers are reinforced, and high heat-resistant modified-polyamide resins, that is, PPA (polyphthalamide) resins containing benzene rings in the main chain, are frequently used. This means that the resin must withstand the high temperature generated in the LED manufacturing process, the whiteness must be excellent in reflectance, and the whiteness must be minimized due to the yellow change by the light source continuously irradiated during the use of the product. Because it should not.
환경 규제로 인하여, 납이 없는 접합이 주요하게 되고, 납이 없는 접합으로 주석-은 합금 등이 사용되고 있다. 이들 납이 없는 접합은 통상적인 납땜보다 더 높은 용융점(대략 260 ℃)을 가지며, 이에 적용 될 수 있는 소재는 액정고분자(LCP), 폴리페닐렌 설파이드(PPS) 및 PPA계 수지에 한정된다.Due to environmental regulations, lead-free joining has become a major factor, and tin-silver alloys have been used as lead-free joining. These lead-free joints have a higher melting point (approximately 260 ° C.) than conventional soldering, and the materials applicable to them are limited to liquid crystal polymers (LCP), polyphenylene sulfides (PPS) and PPA-based resins.
LED는 일반적으로 빛을 발하는 반도체 부분, 전선, 또한 하우징으로서 제공되는 반사판(reflector), 및 반도체 부분을 봉합하는 투명 봉합체로 구성된다. 이들 부분 중, 반사판은 다양한 소재, 예컨대 세라믹 또는 내열 플라스틱으로 만들어질 수 있으나, 세라믹의 경우 생산성이 문제가 되고, 내열 플라스틱의 경우, 사출 성형 시, 봉합재의 열경화 시 또는 사용시 실제 환경 조건 하에서 색상 변화로 인한 광학 반사성이 감소되는 문제가 있다.LEDs generally consist of a semiconductor portion that emits light, a wire, a reflector that also serves as a housing, and a transparent enclosure that seals the semiconductor portion. Of these parts, the reflector can be made of various materials, such as ceramics or heat-resistant plastics, but productivity is an issue for ceramics, and heat-resistant plastics, under injection molding, thermosetting of encapsulants, or under actual environmental conditions in use There is a problem that the optical reflectivity due to the change is reduced.
한국공개특허 제2012-00069798호는 폴리아미드 수지에 무기충진재, 폴리페닐렌 설파이드 수지 및 나노 충진재를 사용하여 낮은 열팽창계수 및 일정한 충격강도를 갖는 폴리아미드계 수지 조성물을 개시하고 있지만, 이는 자동차 외판에 사용되기 위한 폴리아미드계 수지 조성물에 해당한다.Korean Patent Publication No. 2012-00069798 discloses a polyamide resin composition having a low coefficient of thermal expansion and a constant impact strength by using an inorganic filler, a polyphenylene sulfide resin, and a nano filler in a polyamide resin. Corresponds to the polyamide-based resin composition for use.
본 발명자는 LED 반사판의 소재로 사용되어온 종래의 세라믹이나 내열 플라스틱을 대체할 수 있는 고온에서 내변색성이 우수한 열가소성 수지 조성물을 개발하기에 이른 것이다.The present inventors have developed a thermoplastic resin composition having excellent discoloration resistance at a high temperature that can replace a conventional ceramic or heat-resistant plastic that has been used as a material of the LED reflector.
본 발명의 목적은 고온에서 내변색성이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a thermoplastic resin composition excellent in discoloration resistance at a high temperature.
본 발명의 다른 목적은 내열성이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a thermoplastic resin composition having excellent heat resistance.
본 발명의 또 다른 목적은 반사성이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.Still another object of the present invention is to provide a thermoplastic resin composition having excellent reflectivity.
본 발명의 또 다른 목적은 내충격성이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a thermoplastic resin composition excellent in impact resistance.
본 발명의 또 다른 목적은 내열성, 반사성, 및 내충격성과 같은 기계적 특성은 저하되지 않고 고온에서 내변색성이 우수한 열가소성 수지 조성물을 제공하기 위한 것이다.Still another object of the present invention is to provide a thermoplastic resin composition having excellent discoloration resistance at high temperature without deteriorating mechanical properties such as heat resistance, reflectivity, and impact resistance.
본 발명의 또 다른 목적은 상기 열가소성 수지 조성물을 이용한 성형품을 제공하기 위한 것이다.Still another object of the present invention is to provide a molded article using the thermoplastic resin composition.
본 발명의 상기 및 기타의 목적들은 하기 설명되는 본 발명에 의하여 모두 달성될 수 있다.The above and other objects of the present invention can be achieved by the present invention described below.
본 발명의 열가소성 수지 조성물은 (A) 방향족 폴리아미드 수지, (B) 아크릴계 화합물, (C) 무기충진재, (D) 백색안료, (E) 광안정제 및 (F) 소듐 포스페이트 염을 포함하는 것을 특징으로 한다.The thermoplastic resin composition of the present invention comprises (A) an aromatic polyamide resin, (B) an acrylic compound, (C) an inorganic filler, (D) a white pigment, (E) an optical stabilizer, and (F) a sodium phosphate salt. It is done.
본 발명의 열가소성 수지 조성물은 방향족 폴리아미드 수지(A) 10 내지 70 중량%, 아크릴계 화합물(B) 5 내지 70 중량%, 무기충진재(C) 5 내지 30 중량% 및 백색안료(D) 10 내지 50 중량%를 포함하는 기초 수지 조성물 100 중량부에 대하여, 광안정제(E) 0.01 내지 2 중량부 및 소듐 포스페이스 염(F) 0.01 내지 2 중량부를 포함할 수 있다.The thermoplastic resin composition of the present invention is an aromatic polyamide resin (A) 10 to 70% by weight, acrylic compound (B) 5 to 70% by weight, inorganic filler (C) 5 to 30% by weight and white pigment (D) 10 to 50 Based on 100 parts by weight of the base resin composition including the weight%, 0.01 to 2 parts by weight of the light stabilizer (E) and 0.01 to 2 parts by weight of the sodium foam salt (F) may be included.
방향족 폴리아미드 수지(A)는 방향족 디카르복실산이 10 내지 100 몰% 포함된 디카르복실산과 C4 내지 C20의 지방족 또는 지환족 디아민을 포함하는 단량체들의 축중합에 의하여 제조되는 것이 바람직하다.The aromatic polyamide resin (A) is preferably prepared by polycondensation of monomers containing 10 to 100 mol% of aromatic dicarboxylic acid and C 4 to C 20 aliphatic or alicyclic diamines.
방향족 폴리아미드 수지(A)는 하기 화학식 3으로 표시되는 반복단위를 포함할 수 있다.The aromatic polyamide resin (A) may include a repeating unit represented by the following formula (3).
[화학식 3][Formula 3]
Figure PCTKR2013001723-appb-I000001
Figure PCTKR2013001723-appb-I000001
(상기 식에서, m은 4 내지 12, n은 50 내지 500의 정수임).(Wherein m is an integer from 4 to 12, n is an integer from 50 to 500).
아크릴계 화합물(B)은 선형 구조의 아크릴계 단량체 또는 중합체를 포함하는 것이 바람직하다. 구체적으로, 상기 아크릴계 화합물은 (메타)아크릴산 알킬에스테르, (메타)아크릴산 아릴에스테르, (메타)아크릴산 사이클로알킬 에스테르, (메타)아크릴산 또는 이들의 혼합물을 포함할 수 있고, 또한, 상기 아크릴계 화합물은 폴리(메타)아크릴산 알킬에스테르 또는 이의 공중합체, 폴리 (메타)아크릴산 아릴에스테르 또는 이의 공중합체, 폴리(메타)아크릴산 사이클로알킬 에스테르 또는 이의 공중합체, 폴리(메타)아크릴산 또는 이의 공중합체, 또는 이들의 혼합물을 포함할 수 있다.It is preferable that an acryl-type compound (B) contains the acryl-type monomer or polymer of a linear structure. Specifically, the acrylic compound may include (meth) acrylic acid alkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid or a mixture thereof, and the acrylic compound may be poly (Meth) acrylic acid alkyl esters or copolymers thereof, poly (meth) acrylic acid aryl esters or copolymers thereof, poly (meth) acrylic acid cycloalkyl esters or copolymers thereof, poly (meth) acrylic acid or copolymers thereof, or mixtures thereof It may include.
아크릴계 화합물은 폴리메틸(메타)아크릴레이트, 폴리페닐(메타)아크릴레이트, 폴리페닐(메타)아크릴레이트-폴리메틸(메타)아크릴레이트 공중합체, 또는 이들의 혼합물을 포함할 수 있다.The acrylic compound may include polymethyl (meth) acrylate, polyphenyl (meth) acrylate, polyphenyl (meth) acrylate-polymethyl (meth) acrylate copolymer, or a mixture thereof.
아크릴계 단량체 또는 중합체는 상기 아크릴계 화합물(B) 100 중량%에 대하여 40 내지 100 중량%로 포함될 수 있다.Acrylic monomers or polymers may be included in 40 to 100% by weight based on 100% by weight of the acrylic compound (B).
아크릴계 화합물(B)은 아크릴계 단량체와 방향족 비닐 화합물, 시안화 비닐 화합물, 헤테로 고리 화합물 또는 이들의 혼합물의 공중합체를 더 포함할 수 있다.The acrylic compound (B) may further include a copolymer of an acrylic monomer and an aromatic vinyl compound, a vinyl cyanide compound, a heterocyclic compound, or a mixture thereof.
무기충진재(C)는 탄소섬유, 유리섬유, 붕소섬유, 유리비드, 유리플레이크, 카본블랙, 활석, 클레이, 카올린, 탈크, 마이카, 탄산칼슘, 월라스토나이트, 티탄산칼륨 휘스카, 붕산알미늄 휘스카, 산화아연 휘스카, 칼슘 휘스카 또는 이들의 혼합물일 수 있다. 바람직한 무기충진재(C)로 월라스토나이트가 있고, 상기 월라스토나이트는 평균길이가 0.1 내지 100 ㎛인 것이 바람직하다.Inorganic fillers (C) include carbon fibers, glass fibers, boron fibers, glass beads, glass flakes, carbon black, talc, clay, kaolin, talc, mica, calcium carbonate, wollastonite, potassium titanate whisker, aluminum borate Zinc oxide whisker, calcium whisker or mixtures thereof. Preferred inorganic filler (C) is wollastonite, the wollastonite is preferably an average length of 0.1 to 100 ㎛.
백색안료(D)는 산화티탄, 산화아연, 황화아연, 연백, 황산아연, 황산바륨, 탄산칼슘, 산화 알루미늄 또는 이들의 혼합물일 수 있다.The white pigment (D) may be titanium oxide, zinc oxide, zinc sulfide, lead white, zinc sulfate, barium sulfate, calcium carbonate, aluminum oxide, or a mixture thereof.
광안정제(E)는 벤조페논계 화합물, 살리실레이트계 화합물, 벤조트리아졸계 화합물, 아크릴로니트릴계 화합물, 힌더드아민계 화합물, 힌더드 페놀계 화합물 또는 이들의 혼합물일 수 있다.The light stabilizer (E) may be a benzophenone compound, a salicylate compound, a benzotriazole compound, an acrylonitrile compound, a hindered amine compound, a hindered phenol compound or a mixture thereof.
소듐 포스페이트 염(F)은 인산 일수소 나트륨, 인산 이수소 나트륨, 인산 나트륨, 피로인산 나트륨, 산성 피로인산 나트륨 또는 이들의 혼합물일 수 있다.Sodium phosphate salt (F) may be sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate or mixtures thereof.
본 발명의 열가소성 수지 조성물은 형광증백제, 활제, 이형제, 핵제, 대전방지제, 안정제, 보강재, 무기물 첨가제, 안료, 염료 또는 이들의 혼합물로 이루어진 군으로부터 선택되는 첨가제를 더 포함할 수 있다.The thermoplastic resin composition of the present invention may further include an additive selected from the group consisting of optical brighteners, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing materials, inorganic additives, pigments, dyes or mixtures thereof.
상기 다른 기술적 과제를 이루기 위하여, 본 발명은 폴리아미드 수지 조성물로부터 제조된 성형품을 제공한다.In order to achieve the above another technical problem, this invention provides the molded article manufactured from the polyamide resin composition.
본 발명의 열가소성 수지 조성물로부터 제조된 성형품은 색차계로 440 nm 파장에서 측정한 초기 반사율이 92% 이상이고, 온도 85 ℃, 상대습도 85%에서 150시간 방치 전/후 440 nm 파장에서 측정한 반사율 감소가 5% 미만이며, 온도 170 ℃에서 24시간 방치 전/후 측정한 황색도 변화(△YI)가 5 미만인 것을 특징으로 한다.The molded article manufactured from the thermoplastic resin composition of the present invention has an initial reflectance of 92% or more measured at a wavelength of 440 nm with a color difference meter, and a reflectance decrease measured at a wavelength of 440 nm before and after 150 hours at a temperature of 85 ° C. and a relative humidity of 85%. Is less than 5%, and yellowness change (ΔYI) measured before and after standing for 24 hours at a temperature of 170 ° C is less than 5.
본 발명의 열가소성 수지 조성물로부터 제조된 성형품은 ASTM D256에 준하여 1/8 inch 두께 시편에 대하여 측정한 Izod 충격강도가 25 내지 40 kgf·cm/cm이고, ASTM D648에 준하여 18.6 kgf 하중 하에서 1/4 inch 두께 시편에 대하여 측정한 열변형 온도(HDT)가 200 내지 250 ℃인 것을 특징으로 한다.The molded article prepared from the thermoplastic resin composition of the present invention has an Izod impact strength of 25 to 40 kgf · cm / cm measured on a 1/8 inch thick specimen in accordance with ASTM D256, and a 1/4 under 18.6 kgf load in accordance with ASTM D648. The heat deflection temperature (HDT) measured for the inch-thick specimen is characterized in that 200 to 250 ℃.
이하 본 발명의 구체적인 내용을 하기에 상세히 설명한다.Hereinafter, specific contents of the present invention will be described in detail below.
본 발명은 내열성, 반사성 및 내충격성과 같은 기계적 특성은 저하되지 않고 고온에서 내변색성이 우수한 열가소성 수지 조성물 및 이를 이용한 성형품을 제공하는 발명의 효과를 갖는다.The present invention has the effect of providing a thermoplastic resin composition excellent in discoloration resistance at a high temperature and a molded article using the same without deteriorating mechanical properties such as heat resistance, reflectivity and impact resistance.
본 발명은 내열성, 반사성 및 내충격성과 같은 기계적 특성은 저하되지 않고 고온에서 내변색성이 우수한 열가소성 수지 조성물 및 이를 이용한 성형품에 관한 것이다.The present invention relates to a thermoplastic resin composition having excellent discoloration resistance at a high temperature and a molded article using the same without deteriorating mechanical properties such as heat resistance, reflectivity and impact resistance.
열가소성 수지 조성물Thermoplastic resin composition
본 발명에 따른 열가소성 수지 조성물은 (A) 방향족 폴리아미드 수지, (B) 아크릴계 화합물, (C) 무기충진재, (D) 백색안료, (E) 광안정제 및 (F) 소듐 포스페이트 염을 포함하는 것을 특징으로 한다.The thermoplastic resin composition according to the present invention comprises (A) aromatic polyamide resin, (B) acrylic compound, (C) inorganic filler, (D) white pigment, (E) light stabilizer and (F) sodium phosphate salt. It features.
본 발명의 열가소성 수지 조성물은 방향족 폴리아미드 수지(A) 10 내지 70 중량%, 아크릴계 화합물(B) 5 내지 70 중량%, 무기충진재(C) 5 내지 30 중량%, 및 백색안료(D) 10 내지 50 중량%를 포함하는 기초 수지 조성물 100 중량부에 대하여, 광안정제(E) 0.01 내지 2 중량부, 및 소듐 포스페이스 염(F) 0.01 내지 2 중량부를 포함하는 것을 특징으로 한다. 이하 각 성분에 대하여 구체적으로 설명한다.The thermoplastic resin composition of the present invention is 10 to 70% by weight of aromatic polyamide resin (A), 5 to 70% by weight of acrylic compound (B), 5 to 30% by weight of inorganic filler (C), and 10 to white pigment (D). It is characterized by including 0.01-2 weight part of light stabilizers (E), and 0.01-2 weight part of sodium space salts (F) with respect to 100 weight part of base resin compositions containing 50 weight%. Each component is demonstrated concretely below.
(A) 방향족 폴리아미드 수지(A) Aromatic Polyamide Resin
본 발명에 있어서, 방향족 폴리아미드 수지는 주사슬에 방향족 고리를 포함하는 구조로 방향족 디카르복실산(aromatic dicarboxylic acid)이 10 내지 100 몰%(mole%)가 포함된 디카르복실산(dicarboxylic acid)과 C4 내지 C20의 지방족 또는 지환족 디아민(aliphatic or alicyclic diamine)을 포함하는 단량체(monomer)들의 축중합에 의하여 제조된다. In the present invention, the aromatic polyamide resin is a structure containing an aromatic ring in the main chain, dicarboxylic acid containing 10 to 100 mol% (mole%) of aromatic dicarboxylic acid (aromatic dicarboxylic acid) ) And C 4 to C 20 are prepared by condensation polymerization of monomers containing aliphatic or alicyclic diamines.
상기 방향족 디카르복실산의 단량체는 바람직하게는 테레프탈산(terephthalic acid)과 이소프탈산(isophthalic acid)이 있으며, 이들은 하기 화학식 1 및 2에 각각 나타낸 바와 같이 주사슬(main chain)에 방향족 고리를 포함하는 것이 특징이다.Monomers of the aromatic dicarboxylic acid are preferably terephthalic acid and isophthalic acid, which include aromatic rings in the main chain as shown in the following Chemical Formulas 1 and 2, respectively. Is characteristic.
화학식 1
Figure PCTKR2013001723-appb-C000001
 Formula 1
Figure PCTKR2013001723-appb-C000001
화학식 2
Figure PCTKR2013001723-appb-C000002
 Formula 2
Figure PCTKR2013001723-appb-C000002
대표적인 방향족 폴리아미드 수지는 하기 화학식 3으로 표시되는 반복단위를 포함할 수 있다:Representative aromatic polyamide resins may include repeating units represented by the following Formula 3:
화학식 3
Figure PCTKR2013001723-appb-C000003
 Formula 3
Figure PCTKR2013001723-appb-C000003
상기 식에서, m은 4 내지 12, n은 50 내지 500의 정수이다. Wherein m is an integer from 4 to 12 and n is from 50 to 500.
상기 화학식 3의 대표적인 예로는 PA6T(m=6), 및 PA10T(m=10)가 있다. PA6T(m=6)는 헥사메틸렌 디아민(hexamethylene diamine)과 테레프탈산(terephthalic acid)과의 축중합에 의해 제조되며, PA10T(m=10)는 1,10-데칸 디아민(1,10-decanediamine)과 테레프탈산(terephthalic acid)과의 축중합에 의해 제조된다.Representative examples of Formula 3 include PA6T (m = 6), and PA10T (m = 10). PA6T (m = 6) is prepared by the polycondensation of hexamethylene diamine with terephthalic acid. PA10T (m = 10) is produced by 1,10-decanediamine and It is prepared by polycondensation with terephthalic acid.
본 발명에서의 유용한 방향족 폴리아미드 수지는 주사슬에 방향족 고리를 포함하는 중합체 또는 공중합체로 구체적인 예로는, 폴리헥사메틸렌 테레프탈아미드(PA6T), 폴리카프로아미드/폴리헥사메틸렌 테레프탈아미드 공중합체(PA6/6T), 폴리헥사메틸렌 아디파미드/폴리헥사메틸렌 테레프탈아미드 공중합체(PA66/6T), 폴리헥사메틸렌 아디파미드/폴리헥사메틸렌 이소프탈아미드 공중합체(PA66/6I), 폴리헥사메틸렌 테레프탈아미드/폴리헥사메틸렌 이소프탈아미드 공중합체(PA6T/6I), 폴리헥사메틸렌 테레프탈아미드/폴리도데카아미드 공중합체(PA6T/12), 폴리헥사메틸렌 아디파미드/폴리헥사메틸렌 테레프탈아미드/폴리헥사메틸렌 이소프탈아미드 공중합체(PA66/6T/6I), 폴리헥사메틸렌 테레프탈아미드/폴리 2-메틸펜타메틸렌 테레프탈아미드 공중합체(PA6T/M5T), 폴리노나메틸렌 테레프탈아미드(PA9T), 폴리데카메틸렌 테레프탈아미드(PA10T) 또는 이들의 혼합물을 들 수 있다.Aromatic polyamide resins useful in the present invention are polymers or copolymers containing aromatic rings in the main chain, and specific examples thereof include polyhexamethylene terephthalamide (PA6T), polycaproamide / polyhexamethylene terephthalamide copolymer (PA6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (PA66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (PA66 / 6I), polyhexamethylene terephthalamide / Polyhexamethylene isophthalamide copolymer (PA6T / 6I), polyhexamethylene terephthalamide / polydodecaamide copolymer (PA6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthal Amide copolymer (PA66 / 6T / 6I), polyhexamethylene terephthalamide / poly 2-methylpentamethylene terephthalamide copolymer (PA6T / M5T), poly Linonamethylene terephthalamide (PA9T), polydecamethylene terephthalamide (PA10T), or mixtures thereof.
본 발명의 방향족 폴리아미드 수지(A)는 방향족 폴리아미드 수지(A), 아크릴계 화합물(B), 무기충진재(C) 및 백색안료(D)를 포함하는 기초 수지 조성물 100 중량%에 대하여, 10 내지 70 중량%를 포함한다. 바람직하게는 30 내지 60 중량%를 포함한다. 방향족 폴리아미드 수지(A)의 함량이 10 중량% 미만인 경우 열가소성 수지 조성물의 내열도가 저하될 수 있고, 방향족 폴리아미드 수지(A)의 함량이 70 중량%를 초과하는 경우 고온 내변색성이 저하될 수 있다.The aromatic polyamide resin (A) of the present invention is 10 to 10% by weight based on 100% by weight of the base resin composition containing the aromatic polyamide resin (A), the acrylic compound (B), the inorganic filler (C) and the white pigment (D). 70 wt%. Preferably from 30 to 60% by weight. When the content of the aromatic polyamide resin (A) is less than 10% by weight, the heat resistance of the thermoplastic resin composition may decrease, and when the content of the aromatic polyamide resin (A) exceeds 70% by weight, the high temperature discoloration resistance decreases. Can be.
(B) 아크릴계 화합물(B) Acrylic Compound
일반적으로 아크릴계 중합체 또는 아크릴계 공중합체는 충격보강제로 사용되나, 본 발명의 아크릴계 화합물은 고온에서 열가소성 수지 조성물의 내변색성을 향상시키기 위하여 사용된다. 본 발명의 아크릴계 화합물은 선형(linear) 구조를 갖는 아크릴계 단량체 또는 중합체를 포함하기 때문에 충격보강을 위하여 일반적으로 사용되는 코어-쉘 구조의 아크릴계 중합체 또는 아크릴계 공중합체와는 구조가 상이하다.Generally, an acrylic polymer or an acrylic copolymer is used as an impact modifier, but the acrylic compound of the present invention is used to improve discoloration resistance of the thermoplastic resin composition at a high temperature. Since the acrylic compound of the present invention includes an acrylic monomer or a polymer having a linear structure, the acrylic compound has a different structure from an acrylic polymer or an acrylic copolymer of a core-shell structure which is generally used for impact reinforcement.
아크릴계 화합물은 선형구조의 아크릴계 단량체 또는 중합체를 포함한다.The acrylic compound includes a linear acrylic monomer or polymer.
구체적으로, 아크릴계 화합물은 (메타)아크릴산 알킬에스테르, (메타)아크릴산 아릴에스테르, (메타)아크릴산 사이클로알킬 에스테르, (메타)아크릴산 또는 이들의 혼합물이며, 이에 한정되지 않는다. 이때 알킬은 치환 또는 비치환된 C1 내지 C10의 알킬기이고, 아릴은 치환 또는 비치환된 C6 내지 C20의 아릴기이고, 사이클로알킬은 치환 또는 비치환된 C6 내지 C20의 사이클로알킬기이다. 상기 아크릴계 화합물의 구체적인 예로는, n-부틸 (메타)아크릴레이트, t-부틸 (메타)아크릴레이트, 헥실 (메타)아크릴레이트, 2-에틸헥실 (메타)아크릴레이트, 2-히드록시에틸 (메타)아크릴레이트, 2-히드록시프로필 (메타)아크릴레이트, (메타)아크릴산, 페닐 (메타)아크릴레이트, 벤질 (메타)아크릴레이트, 사이클로헥실 (메타)아크릴레이트, 페녹시 (메타)아크릴레이트, 페녹시에틸 (메타)아크릴레이트 등으로 이루어진 군으로부터 선택될 수 있으나, 반드시 이에 제한되는 것은 아니며, 2종 이상을 혼합하여 사용할 수도 있다. 이 중 바람직하게는 메틸 (메타)아크릴레이트가 사용될 수 있다.Specifically, the acrylic compound is a (meth) acrylic acid alkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid or a mixture thereof, but is not limited thereto. Wherein alkyl is a substituted or unsubstituted C 1 to C 10 alkyl group, aryl is a substituted or unsubstituted C 6 to C 20 aryl group, and cycloalkyl is a substituted or unsubstituted C 6 to C 20 cycloalkyl group to be. Specific examples of the acryl-based compound include n-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth ) Acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylic acid, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxy (meth) acrylate, It may be selected from the group consisting of phenoxyethyl (meth) acrylate, and the like, but is not necessarily limited thereto, and may be used by mixing two or more kinds. Of these, methyl (meth) acrylate may be preferably used.
또한, 아크릴계 화합물은 폴리(메타)아크릴산 알킬에스테르 또는 이의 공중합체, 폴리 (메타)아크릴산 아릴에스테르 또는 이의 공중합체, 폴리(메타)아크릴산 사이클로알킬 에스테르 또는 이의 공중합체, 폴리(메타)아크릴산 또는 이의 공중합체, 또는 이들의 혼합물을 포함하며, 이에 한정되지 않는다. 상기 아크릴계 화합물의 구체적인 예로는, 폴리메틸(메타)아크릴레이트, 폴리페닐(메타)아크릴레이트, 폴리페닐(메타)아크릴레이트-폴리메틸(메타)아크릴레이트 공중합체, 또는 이들의 혼합물 등이 있으며, 이에 한정되지 않는다. 상기 아크릴계 화합물은 아크릴계 화합물을 포함하는 원료 단량체를 현탁중합법, 괴상중합법, 유화중합법 등의 공지의 중합법에 의해 제조할 수 있다. Also, the acrylic compound may be poly (meth) acrylic acid alkyl ester or copolymer thereof, poly (meth) acrylic acid aryl ester or copolymer thereof, poly (meth) acrylic acid cycloalkyl ester or copolymer thereof, poly (meth) acrylic acid or air thereof Including, but not limited to, coalescing, or mixtures thereof. Specific examples of the acryl-based compound include polymethyl (meth) acrylate, polyphenyl (meth) acrylate, polyphenyl (meth) acrylate-polymethyl (meth) acrylate copolymer, or a mixture thereof. It is not limited to this. The said acryl-type compound can manufacture the raw material monomer containing an acryl-type compound by well-known polymerization methods, such as suspension polymerization method, block polymerization method, and emulsion polymerization method.
아크릴계 단량체 또는 중합체는 아크릴계 화합물(B) 100 중량%에 대하여 40 내지 100 중량%, 바람직하게 50 내지 100 중량%로 포함될 수 있다. 아크릴계 단량체 또는 중합체가 상기 함량범위 내로 포함되는 경우 열가소성 수지 조성물의 고온 내변색성이 우수하다.The acrylic monomer or polymer may be included in an amount of 40 to 100% by weight, preferably 50 to 100% by weight, based on 100% by weight of the acrylic compound (B). When the acrylic monomer or polymer is included in the above content range, the high temperature discoloration resistance of the thermoplastic resin composition is excellent.
아크릴계 화합물(B)은 아크릴계 단량체와 방향족 비닐 화합물, 시안화 비닐 화합물, 헤테로 고리 화합물 또는 이들의 혼합물의 공중합체를 더 포함할 수 있다. 이 중 바람직하게는 아크릴계 단량체, 방향족 비닐 화합물 및 시안화 비닐 화합물의 공중합체를 포함할 수 있다.The acrylic compound (B) may further include a copolymer of an acrylic monomer and an aromatic vinyl compound, a vinyl cyanide compound, a heterocyclic compound, or a mixture thereof. Among these, preferably, a copolymer of an acrylic monomer, an aromatic vinyl compound, and a vinyl cyanide compound may be included.
방향족 비닐 화합물의 예로는 스티렌, C1 내지 C10의 알킬 치환 스티렌, 할로겐 치환 스티렌 또는 이들의 혼합물을 사용할 수 있으며 이에 한정되는 것은 아니다. 상기 알킬 치환 스티렌의 예로는 o-에틸 스티렌, m-에틸 스티렌, p-에틸 스티렌, α-메틸 스티렌 등을 들 수 있으며 이에 한정되는 것은 아니다.Examples of the aromatic vinyl compound may include, but are not limited to, styrene, C 1 to C 10 alkyl substituted styrene, halogen substituted styrene, or a mixture thereof. Examples of the alkyl substituted styrenes include, but are not limited to, o-ethyl styrene, m-ethyl styrene, p-ethyl styrene, α-methyl styrene, and the like.
시안화 비닐 화합물의 예로는 아크릴로니트릴, 메타크릴로니트릴, 에타크릴로니트릴 또는 이들의 혼합물을 사용할 수 있으며 이에 한정되는 것은 아니다.Examples of the vinyl cyanide compound may include, but are not limited to, acrylonitrile, methacrylonitrile, ethacrylonitrile or mixtures thereof.
헤테로 고리 화합물의 예로는 무수말레인산, 알킬 또는 페닐 N-치환 말레이미드 또는 이들의 혼합물을 사용할 수 있으며 이에 한정되는 것은 아니다.Examples of heterocyclic compounds may include, but are not limited to, maleic anhydride, alkyl or phenyl N-substituted maleimides, or mixtures thereof.
아크릴계 단량체, 방향족 비닐 화합물 및 시안화 비닐 화합물의 공중합체는 아크릴계 단량체 40 내지 99.8 중량%, 방향족 비닐 화합물 0.1 내지 40 중량% 및 시안화 비닐 화합물 0.1 내지 20 중량%로 이루어질 수 있다. 상기 함량범위 내로 이루어지는 경우 상기 공중합체의 중합시 중합 안정성이 우수하며, 열가소성 수지 조성물의 고온에서 내변색성이 우수하고, 열가소성 수지 조성물을 이용한 성형품의 광택이 우수하다.The copolymer of the acrylic monomer, the aromatic vinyl compound and the vinyl cyanide compound may be composed of 40 to 99.8 wt% of the acrylic monomer, 0.1 to 40 wt% of the aromatic vinyl compound, and 0.1 to 20 wt% of the vinyl cyanide compound. When the amount is within the content range, the polymerization stability of the copolymer is excellent, the discoloration resistance is excellent at the high temperature of the thermoplastic resin composition, and the gloss of the molded article using the thermoplastic resin composition is excellent.
아크릴계 화합물(B) 중 아크릴계 중합체의 중량평균 분자량은 10,000 내지 200,000 g/mol이고, 바람직하게는 10,000 내지 150,000 g/mol이며, 더욱 바람직하게는 20,000 내지 120,000 g/mol이다. 상기 범위의 중량평균 분자량을 가질 경우 열가소성 수지 조성물의 유동성 및 내충격성의 우수한 물성 밸런스를 얻을 수 있다. 또한, 이러한 중량평균 분자량 범위 내에서 서로 다른 중량평균 분자량을 가진 적어도 2종의 아크릴계 중합체를 사용할 수 있다. 이와 같이 중량평균 분자량이 상이한 2종의 아크릴계 중합체를 사용할 경우 열가소성 수지 조성물의 유동성 및 내충격성을 조절할 수 있다.The weight average molecular weight of the acrylic polymer in the acrylic compound (B) is 10,000 to 200,000 g / mol, preferably 10,000 to 150,000 g / mol, and more preferably 20,000 to 120,000 g / mol. When the weight average molecular weight of the above range can be obtained excellent balance of physical properties of the flowability and impact resistance of the thermoplastic resin composition. In addition, at least two kinds of acrylic polymers having different weight average molecular weights within this weight average molecular weight range may be used. As such, when two kinds of acrylic polymers having different weight average molecular weights are used, the fluidity and impact resistance of the thermoplastic resin composition can be adjusted.
본 발명의 아크릴계 화합물(B)은 방향족 폴리아미드 수지(A), 아크릴계 화합물(B), 무기충진재(C) 및 백색안료(D)를 포함하는 기초 수지 조성물 100 중량%에 대하여, 5 내지 70 중량%를 포함한다. 아크릴계 화합물(B)의 함량이 5 중량% 미만인 경우 열가소성 수지 조성물의 고온 내변색성이 저하될 수 있고, 아크릴계 화합물(B)의 함량이 70 중량% 초과인 경우 열가소성 수지 조성물의 내열성 및 성형성이 저하될 수 있다.The acrylic compound (B) of the present invention is 5 to 70% by weight based on 100% by weight of the base resin composition containing an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D). Contains% When the content of the acrylic compound (B) is less than 5% by weight, the high temperature discoloration resistance of the thermoplastic resin composition may be lowered. When the content of the acrylic compound (B) is more than 70% by weight, the heat resistance and the moldability of the thermoplastic resin composition may be reduced. Can be degraded.
(C) 무기충진재 (C) inorganic filler
본 발명에서는 열가소성 수지 조성물의 기계적 특성, 내열성 및 치수안정성 등을 증가시키기 위하여 입자 형태가 다양한 무기충진재를 포함할 수 있다.In the present invention, in order to increase the mechanical properties, heat resistance and dimensional stability of the thermoplastic resin composition may include various inorganic fillers.
본 발명에서는 통상적으로 사용되는 무기충진재를 모두 사용할 수 있다. 그 구체적인 예로는, 탄소섬유, 유리섬유, 붕소섬유, 유리비드, 유리플레이크, 카본블랙, 활석, 클레이, 카올린, 탈크, 마이카, 탄산칼슘 및 이의 혼합물 등을 들 수 있고, 침상 무기충진재로서는 월라스토나이트, 티탄산칼륨 휘스카, 붕산알미늄 휘스카, 산화아연 휘스카, 칼슘 휘스카 및 이의 혼합물 등을 들 수 있다. 무기충진재(C)는 열가소성 수지와의 밀착력을 개선하기 위하여 적당한 유기물질로 표면을 코팅하여 사용할 수 있다.In the present invention, all of the commonly used inorganic fillers can be used. Specific examples thereof include carbon fiber, glass fiber, boron fiber, glass beads, glass flakes, carbon black, talc, clay, kaolin, talc, mica, calcium carbonate, and mixtures thereof. Nitrate, potassium titanate whisker, aluminum borate whisker, zinc oxide whisker, calcium whisker and mixtures thereof and the like. Inorganic filler (C) may be used by coating the surface with a suitable organic material in order to improve the adhesion with the thermoplastic resin.
무기충진재(C)를 열가소성 수지 조성물에 사용하는 경우, 열가소성 수지 조성물로부터 제조되는 성형품의 인장강도, 굴곡강도, 굴곡탄성률 등의 기계적 특성 및 열변형 온도 등의 내열 특성이 향상될 수 있다.When the inorganic filler (C) is used in the thermoplastic resin composition, mechanical properties such as tensile strength, flexural strength, flexural modulus, and heat resistance such as heat deformation temperature of the molded article manufactured from the thermoplastic resin composition may be improved.
특히, 열가소성 수지 조성물의 박막 성형과 같은 미세 성형 분야에서는 열가소성 수지 조성물의 유동성을 확보하는 것이 관건이다. 상기 무기충진재 중 열가소성 수지 조성물의 박막 성형성을 개선하기 위하여 월라스토나이트를 무기충진재로 사용할 수 있다. 두께 1 mm 이하의 박막 성형과 같은 미세 성형 분야에서 월라스토나이트를 사용하는 경우, 열가소성 수지 조성물의 우수한 내열성 및 기계적 물성을 유지하며, 성형성을 충분히 확보할 수 있다. 상기 월라스토나이트의 평균 길이는 0.1 내지 11 ㎛의 범위로 사용하는 것이 바람직하다. 상기 월라스토나이트의 겉보기 밀도(bulk density, tapped)는 0.1 내지 2 g/㎤, 바람직하게는 0.1 내지 1 g/㎤의 범위로 사용하는 것이 바람직하다. 월라스토나이트의 단면은 사각형 외에도 특수한 사용용도에 따라 단면의 변화를 줄 수 있다. 본 발명에서는 월라스토나이트의 형상은 어떠한 종류도 사용할 수 있다.In particular, in the field of fine molding such as thin film molding of the thermoplastic resin composition, it is important to secure the fluidity of the thermoplastic resin composition. In order to improve the thin film formability of the thermoplastic resin composition of the inorganic filler, wollastonite may be used as the inorganic filler. In the case of using wollastonite in the field of fine molding such as thin film molding having a thickness of 1 mm or less, the excellent heat resistance and mechanical properties of the thermoplastic resin composition can be maintained, and moldability can be sufficiently secured. The average length of the wollastonite is preferably used in the range of 0.1 to 11 ㎛. The bulk density (tapped) of the wollastonite is preferably used in the range of 0.1 to 2 g / cm 3, preferably 0.1 to 1 g / cm 3. The cross section of wollastonite can change the cross section depending on the special use besides the square. In the present invention, any kind of wollastonite may be used.
본 발명의 무기충진재(C)는 방향족 폴리아미드 수지(A), 아크릴계 화합물(B), 무기충진재(C) 및 백색안료(D)를 포함하는 기초 수지 조성물 100 중량%에 대하여, 5 내지 30 중량%를 포함한다. 무기충진재(C)의 함량이 5 중량% 미만인 경우 열가소성 수지 조성물의 충격강도와 같은 기계적 특성 및 내열 특성이 저하될 수 있고, 무기충진재(C)의 함량이 30 중량% 초과인 경우 열가소성 수지 조성물의 유동성이 저하되고, 열가소성 수지 조성물로부터 제조된 성형품의 외관이 나빠질 수 있다.Inorganic filler (C) of the present invention is 5 to 30% by weight based on 100% by weight of the base resin composition comprising an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D) Contains% When the content of the inorganic filler (C) is less than 5% by weight, mechanical and heat resistance properties such as impact strength of the thermoplastic resin composition may be lowered. When the content of the inorganic filler (C) is more than 30% by weight, The fluidity may be lowered and the appearance of the molded article manufactured from the thermoplastic resin composition may be deteriorated.
(D) 백색안료(D) white pigment
본 발명에서는 열가소성 수지 조성물의 충분한 반사율을 구현하기 위하여, 백색안료(D)를 필수 구성요소로서 사용하여야 한다.In the present invention, in order to realize sufficient reflectance of the thermoplastic resin composition, white pigment (D) should be used as an essential component.
사용하는 백색안료(D)로는 산화티탄, 산화아연, 황화아연, 연백, 황산아연, 황산바륨, 탄산칼슘, 산화알루미늄 등을 들 수 있다. 이들 백색안료는 단독 또는 2종 이상을 혼합하여 사용할 수 있다. 또한, 백색안료(D)는 실란 커플링제 또는 티탄 커플링제 등으로 처리하여 사용할 수도 있다. 예를 들면 비닐트리에톡시실란, 3-아미노프로필트리에톡시실란, 3-글리 시독시프로필트리에톡시실란 등의 실란계 화합물로 표면 처리될 수 있다.Examples of the white pigment (D) to be used include titanium oxide, zinc oxide, zinc sulfide, lead white, zinc sulfate, barium sulfate, calcium carbonate and aluminum oxide. These white pigments can be used individually or in mixture of 2 or more types. In addition, a white pigment (D) can also be used by processing with a silane coupling agent, a titanium coupling agent, etc. For example, it can surface-treat with silane type compounds, such as vinyl triethoxysilane, 3-aminopropyl triethoxysilane, and 3-glycidoxy propyl triethoxysilane.
본 발명에 사용되는 백색안료(D)로 이산화티탄이 바람직하다. 백색안료(D)로 이산화티탄을 사용함으로써 반사율, 은폐성이라는 광학특성이 향상된다. 이산화티탄은 일반적인 이산화티탄을 사용할 수도 있으며, 제조방법, 입경이 한정되는 것은 아니다.As a white pigment (D) used for this invention, titanium dioxide is preferable. By using titanium dioxide as the white pigment (D), optical characteristics such as reflectance and concealability are improved. As titanium dioxide, general titanium dioxide may be used, and the production method and particle size are not limited.
이산화티탄은 무기 표면처리제 또는 유기 표면처리제로 표면처리된 것을 사용하는 것이 보다 바람직하다. 무기 표면처리제로는 산화 알루미늄(알루미나, Al2O3), 이산화규소(실리카, SiO2), 이산화지르콘(지르코니아, ZrO2), 규산나트륨, 알루민산나트륨, 나트륨 규산알루미늄, 산화아연, 운모 등이 있다. 유기 표면처리제로는 폴리디메틸실록산, 트리메틸프로판(TMP), 펜타에리트리톨 등이 있다. 무기 또는 유기 표면처리제는 이산화티탄 100 중량부에 대해서 약 2 중량부 이하로 표면처리된다. 본 발명에서는 무기 표면처리제인 알루미나(Al2O3)가 이산화티탄 100 중량부에 대해서 2 중량부 미만으로 코팅된 이산화티탄이 바람직하다.As for titanium dioxide, it is more preferable to use what was surface-treated with the inorganic surface treating agent or the organic surface treating agent. Inorganic surface treatment agents include aluminum oxide (alumina, Al 2 O 3 ), silicon dioxide (silica, SiO 2 ), zirconium dioxide (zirconia, ZrO 2 ), sodium silicate, sodium aluminate, sodium aluminum silicate, zinc oxide, mica, etc. There is this. Organic surface treating agents include polydimethylsiloxane, trimethyl propane (TMP), pentaerythritol, and the like. The inorganic or organic surface treatment agent is surface treated to about 2 parts by weight or less based on 100 parts by weight of titanium dioxide. In the present invention, titanium dioxide coated with less than 2 parts by weight of alumina (Al 2 O 3 ), which is an inorganic surface treatment agent, with respect to 100 parts by weight of titanium dioxide is preferable.
알루미나로 표면처리된 이산화티탄은 이산화규소, 이산화지르콘, 규산나트륨, 알루민산나트륨, 나트륨 규산알루미늄, 운모 등의 무기 표면처리제나 폴리디메틸실록산, 트리메틸프로판(TMP), 펜타에리트리톨과 같은 유기 표면처리제로 더 개질하여 사용할 수 있다.Titanium dioxide surface-treated with alumina is inorganic surface treatment agent such as silicon dioxide, zirconium dioxide, sodium silicate, sodium aluminate, sodium aluminum silicate, mica, or organic surface treatment such as polydimethylsiloxane, trimethylpropane (TMP), pentaerythritol Zero further modifications can be used.
본 발명의 백색안료(D)는 방향족 폴리아미드 수지(A), 아크릴계 화합물(B), 무기충진재(C) 및 백색안료(D)를 포함하는 기초 수지 조성물 100 중량%에 대하여, 10 내지 50 중량%를 포함한다. 백색안료(D)의 함량이 10 중량% 미만인 경우 열가소성 수지 조성물의 내황변성 및 반사성이 저하될 수 있고, 백색안료(D)의 함량이 50 중량% 초과인 경우 열가소성 수지 조성물의 내충격성과 같은 기계적 물성이 저하될 수 있다.White pigment (D) of the present invention is 10 to 50% by weight based on 100% by weight of the base resin composition comprising an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D) Contains% When the content of the white pigment (D) is less than 10% by weight, the yellowing resistance and reflectivity of the thermoplastic resin composition may be lowered, and when the content of the white pigment (D) is more than 50% by weight, mechanical properties such as impact resistance of the thermoplastic resin composition This can be degraded.
(E) 광안정제(E) light stabilizer
본 발명의 열가소성 수지 조성물의 변색을 방지하고, 반사율의 저하를 억제하는 것을 목적으로 광안정제(E)를 사용할 수 있다. A light stabilizer (E) can be used for the purpose of preventing discoloration of the thermoplastic resin composition of this invention and suppressing a fall of a reflectance.
광안정제(E)로서는 벤조페논(benzophenone)계 화합물, 살리실레이트(salicylate)계 화합물, 벤조트리아졸(benzotriazole)계 화합물, 아크릴로니트릴(acrylonitrile)계 화합물, 그 밖의 공명구조 화합물 등의 자외선 흡수 효과가 있는 화합물, 힌더드 아민(hindered amine)계 화합물, 힌더드 페놀(hindered phenol)계 화합물 등의 라디칼(radical) 포착 능력이 있는 화합물, 또는 이들의 2 이상의 혼합물 등을 사용할 수 있다. 또한, 자외선 흡수 효과가 있는 화합물과 라디칼(radical) 포착능력이 있는 화합물을 병용하면 보다 높은 효과를 나타낼 수 있다.The light stabilizer (E) absorbs ultraviolet rays such as benzophenone compounds, salicylate compounds, benzotriazole compounds, acrylonitrile compounds, and other resonance structure compounds. A compound having a radical trapping ability such as an effective compound, a hindered amine compound, a hindered phenol compound, or a mixture of two or more thereof may be used. In addition, when a compound having an ultraviolet absorbing effect and a compound having a radical trapping ability are used in combination, a higher effect can be obtained.
본 발명의 광안정제(E)는 방향족 폴리아미드 수지(A), 아크릴계 화합물(B), 무기충진재(C) 및 백색안료(D)를 포함하는 기초 수지 조성물 100 중량부에 대하여, 0.01 내지 2 중량부, 바람직하게는 0.1 내지 2 중량부를 포함한다. 광안정제(E)의 함량이 0.01 중량부 미만인 경우 열가소성 수지 조성물의 내변색성 및 반사성이 저하될 수 있고, 2 중량부 초과인 경우 열가소성 수지 조성물의 고온 내변색성이 저하될 수 있다.The light stabilizer (E) of the present invention is 0.01 to 2 parts by weight based on 100 parts by weight of the base resin composition containing an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D). Parts, preferably 0.1 to 2 parts by weight. When the content of the light stabilizer (E) is less than 0.01 part by weight, the discoloration resistance and reflectivity of the thermoplastic resin composition may be lowered, and when it is more than 2 parts by weight, the high temperature discoloration resistance of the thermoplastic resin composition may be lowered.
(F) 소듐 포스페이트 염(F) sodium phosphate salt
본 발명의 소듐 포스페이스 염(F)은 열가소성 수지 조성물의 충분한 반사율을 구현하면서, 동시에 열변색 안정성, 가수분해 안정성 및 광 안정성을 확보하기 위하여 추가로 사용될 수 있다. The sodium space salt (F) of the present invention can be further used to realize sufficient reflectance of the thermoplastic resin composition while at the same time ensuring thermochromic stability, hydrolysis stability and light stability.
백색안료(D)와 소듐 포스페이트 염(F)을 동시에 적용하는 경우, 열가소성 수지 조성물의 충분한 백색도를 확보할 수 있을 뿐만 아니라, 열변색 안정성도 매우 우수해진다. 소듐 포스페이트 염은 그 자체로도 백색도가 높기 때문에, 이를 혼합하여도 열가소성 수지 조성물의 반사성을 충분히 확보할 수 있다. 뿐만 아니라, 이 경우 열가소성 수지 조성물이 열변색 안정성 및 가수분해 안정성이 뛰어난 소듐 포스페이트 염을 포함하게 되기 때문에 장시간 동안 고온/고습 조건에서 방치 후에도 색상 변성도 거의 일어나지 않으며, 반사율의 저하도 거의 일어나지 않는 열변색 안정성 및 가수분해 안정성을 확보할 수 있게 된다.When simultaneously applying the white pigment (D) and the sodium phosphate salt (F), not only can the whiteness of the thermoplastic resin composition be ensured, but also the thermochromic stability becomes very excellent. Since sodium phosphate salt has high whiteness in itself, even if it is mixed, the reflectivity of a thermoplastic resin composition can be ensured enough. In addition, in this case, since the thermoplastic resin composition includes a sodium phosphate salt having excellent thermochromic stability and hydrolysis stability, little color change occurs even after being left at a high temperature / high humidity condition for a long time, and heat of which the reflectance hardly decreases. It is possible to secure discoloration stability and hydrolysis stability.
또한, 소듐 포스페이트 염(F)은 열가소성 수지 조성물을 이용한 성형 작업 중 발생할 수 있는 산(acid)을 효과적으로 제거하여 본 발명의 열가소성 수지 조성물의 열변색 안정성 및 가수분해 안정성을 더욱 향상시키는 역할을 한다. In addition, sodium phosphate salt (F) serves to effectively remove the acid (acid) that may occur during the molding operation using the thermoplastic resin composition to further improve the thermochromic stability and hydrolysis stability of the thermoplastic resin composition of the present invention.
소듐 포스페이트 염(F)을 구체적으로 예시하면 인산 이수소 나트륨, 인산 일수소 나트륨, 인산 나트륨, 피로인산 나트륨, 산성 피로인산 나트륨 또는 이들의 혼합물 등이 있는데, 반드시 이에 제한 되는 것은 아니며, 소듐 포스페이트 염이라면 그 어떠한 것이라도 적절하게 선택되어 사용될 수 있다. Specific examples of the sodium phosphate salt (F) include, but are not limited to, sodium dihydrogen phosphate, sodium monohydrogen phosphate, sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate, or a mixture thereof. Anything may be selected and used appropriately.
소듐 포스페이트 염(F)은 일반적으로 제조방법, 입경이 한정되지 않으며, 열가소성 수지와의 상용성 및 열가소성 수지 매트릭스(matrix) 내에서 분산성을 향상시키기 위해 표면처리제로 표면 처리된 것을 사용할 수도 있다. Sodium phosphate salt (F) is generally not limited to the manufacturing method, the particle size, may be used that is surface-treated with a surface treatment agent to improve compatibility with the thermoplastic resin and dispersibility in the thermoplastic resin matrix (matrix).
표면처리제로는 실란(silane), 에폭시 실란(epoxy silane) 등의 실란 커플링제, 티탄 커플링제, 유기산, 폴리올(polyol), 실리콘 등의 유기물 등이 사용될 수 있다.As the surface treatment agent, silane coupling agents such as silane and epoxy silane, titanium coupling agents, organic acids such as organic acids, polyols, and silicones may be used.
본 발명의 소듐 포스페이트 염(F)은 방향족 폴리아미드 수지(A), 아크릴계 화합물(B), 무기충진재(C) 및 백색안료(D)를 포함하는 기초 수지 조성물 100 중량부에 대하여, 0.01 내지 2 중량부를 포함한다. 바람직하게는 0.1 내지 2 중량부가 포함된다. 소듐 포스페이트 염(F)의 함량이 0.01 중량부 미안인 경우 열가소성 수지 조성물의 반사성이 저하될 수 있고, 소듐 포스페이트 염(F)의 함량이 2 중량부 초과인 경우 열가소성 수지 조성물의 내충격성 및 내황변성이 저하될 수 있다.Sodium phosphate salt (F) of the present invention is 0.01 to 2 with respect to 100 parts by weight of the base resin composition containing an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D) It includes parts by weight. Preferably 0.1 to 2 parts by weight is included. When the content of sodium phosphate salt (F) is 0.01 parts by weight, the reflectivity of the thermoplastic resin composition may be reduced, and when the content of sodium phosphate salt (F) is more than 2 parts by weight, impact resistance and yellowing resistance of the thermoplastic resin composition This can be degraded.
(G) 첨가제(G) additive
본 발명의 열가소성 수지 조성물은 각각의 용도에 따라 형광증백제, 활제, 이형제, 핵제, 대전방지제, 안정제, 보강재, 무기물 첨가제, 안료, 염료 및 이들의 혼합물을 더 포함할 수 있으며, 반드시 이에 제한되는 것은 아니다.The thermoplastic resin composition of the present invention may further include a fluorescent brightener, a lubricant, a mold releasing agent, a nucleating agent, an antistatic agent, a stabilizer, a reinforcing agent, an inorganic additive, a pigment, a dye, and a mixture thereof according to each use, and the present invention is not limited thereto. It is not.
본 발명에서 첨가제(G)는 방향족 폴리아미드 수지(A), 아크릴계 화합물(B), 무기충진재(C) 및 백색안료(D)를 포함하는 기초 수지 조성물 100 중량부에 대하여, 0.01 내지 20 중량부가 사용될 수 있다.In the present invention, the additive (G) is 0.01 to 20 parts by weight based on 100 parts by weight of the base resin composition containing an aromatic polyamide resin (A), an acrylic compound (B), an inorganic filler (C) and a white pigment (D). Can be used.
형광증백제는 열가소성 수지 조성물의 반사율을 향상시키는 역할을 하는 것으로, 4-(벤조옥사졸-2-일)-4'-(5-메틸벤조옥사졸-2-일)스틸벤 또는 4,4'-비스(벤조옥사졸-2-일)스틸벤 등과 같은 스틸벤-비스벤조옥사졸 유도체가 사용될 수 있다.Fluorescent whitening agent serves to improve the reflectance of the thermoplastic resin composition, 4- (benzooxazol-2-yl) -4 '-(5-methylbenzooxazol-2-yl) stilbene or 4,4 Stilbene-bisbenzooxazole derivatives such as' -bis (benzooxazol-2-yl) stilbene and the like can be used.
이형제로는 불소 함유 중합체, 실리콘 오일, 스테아린산의 금속염, 몬탄산의 금속염, 몬탄산 에스테르 왁스 또는 폴리에틸렌 왁스가 사용될 수 있고, 핵제로는 탈크 또는 클레이가 사용될 수 있다.As the release agent, fluorine-containing polymers, silicone oils, metal salts of stearic acid, metal salts of montanic acid, montanic acid ester waxes or polyethylene waxes may be used, and talc or clay may be used as a nucleating agent.
본 발명에 따른 열가소성 수지 조성물은 수지 조성물을 제조하는 공지의 방법으로 제조할 수 있다. 예를 들면, 본 발명의 구성 성분과 기타 첨가제들을 동시에 혼합한 후, 압출기 내에서 용융 압출하여 펠렛 또는 칩 형태로 제조할 수 있다.The thermoplastic resin composition according to the present invention can be produced by a known method for producing a resin composition. For example, the components of the present invention and other additives may be mixed at the same time and then melt-extruded in an extruder to produce pellets or chips.
성형품Molded article
본 발명은 또한 상기 열가소성 수지 조성물로부터 제조된 성형품을 제공한다. 성형품을 성형하는 방법에는 특별한 제한이 없으며, 압출, 사출, 중공, 압축 혹은 캐스팅 성형방법 등이 적용될 수 있다. 이러한 성형은 본 발명이 속하는 분야에서 통상의 지식을 가진 자에 의해 용이하게 실시될 수 있다.The present invention also provides a molded article prepared from the thermoplastic resin composition. There is no particular limitation on the method of molding the molded article, and an extrusion, injection, hollow, compression or casting molding method may be applied. Such molding can be easily carried out by those skilled in the art.
본 발명의 열가소성 수지 조성물로부터 제조된 성형품은 색차계로 440 nm 파장에서 측정한 초기 반사율이 92% 이상이고, 온도 85 ℃, 상대습도 85%에서 150시간 방치 전/후 440 nm 파장에서 측정한 반사율 감소가 5% 미만이며, 온도 170 ℃에서 24시간 방치 전/후 측정한 황색도 변화(△YI)가 5 미만임을 특징으로 한다.The molded article prepared from the thermoplastic resin composition of the present invention has an initial reflectance of 92% or more measured with a color difference meter at a wavelength of 440 nm, and a reflectance decrease measured at a wavelength of 440 nm before / after 150 hours at a temperature of 85 ° C. and a relative humidity of 85%. Is less than 5%, and the yellowness change (ΔYI) measured before and after standing for 24 hours at a temperature of 170 ° C. is less than 5.
본 발명의 열가소성 수지 조성물로부터 제조된 성형품은 ASTM D256에 준하여 1/8 inch 두께 시편에 대하여 측정한 Izod 충격강도가 25 내지 40 kgf·cm/cm이고, ASTM D648에 준하여 18.6 kgf 하중 하에서 1/4 inch 두께 시편에 대하여 측정한 열변형 온도(HDT)가 200 내지 250 ℃임을 특징으로 한다.The molded article prepared from the thermoplastic resin composition of the present invention has an Izod impact strength of 25 to 40 kgf · cm / cm measured on a 1/8 inch thick specimen in accordance with ASTM D256, and a 1/4 under 18.6 kgf load in accordance with ASTM D648. It is characterized in that the heat deflection temperature (HDT) measured for the inch-thick specimen is 200 to 250 ℃.
본 발명의 열가소성 수지 조성물은 반사성, 내열성, 내충격성 및 고온에서 내변색성이 우수하기 때문에 여러 가지 제품의 성형에 바람직하게 적용될 수 있다. 특히, 본 발명의 열가소성 수지 조성물은 백색안료, 광안정제, 소듐 포스페이트 염을 동시에 적절한 함량으로 포함하여 내열성, 반사성 및 내충격성이 우수할 뿐만 아니라, 고온/고습 조건에서 장시간 방치 후에도 반사율 및 황변도가 저하되지 않는 등 내변색성이 우수하므로, 고온/고습의 환경에서 지속적으로 노출되는 LED 반사판의 재료로서 바람직하게 사용될 수 있다.Since the thermoplastic resin composition of the present invention is excellent in reflectivity, heat resistance, impact resistance and discoloration resistance at high temperature, it can be preferably applied to molding of various products. In particular, the thermoplastic resin composition of the present invention includes not only white pigments, light stabilizers, and sodium phosphate salts in suitable amounts at the same time, but also excellent in heat resistance, reflectivity and impact resistance, as well as reflectance and yellowing even after long time standing at high temperature / high humidity conditions. Since it is excellent in discoloration resistance, such as not falling, it can be used suitably as a material of the LED reflector which is continuously exposed in the environment of high temperature / high humidity.
본 발명의 열가소성 수지 조성물은 LED 반사판 뿐만 아니라, 그 외 다른 광선을 반사하는 용도라면 그 어디에라도 적용할 수 있다. 예를 들면 각종 전기전자 부품, 실내 조명, 실외 조명, 자동차 조명, 표시 기기, 헤드 라이트 등의 발광 장치용 반사판으로서 사용할 수 있다.The thermoplastic resin composition of the present invention can be applied not only to the LED reflecting plate but also to any other application for reflecting other light rays. For example, it can be used as a reflecting plate for light emitting devices, such as various electrical and electronic components, indoor lighting, outdoor lighting, automobile lighting, display equipment, and headlights.
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
본 발명의 실시예 및 비교실시예에서 사용된 방향족 폴리아미드 수지(A). 아크릴계 화합물(B), 무기충진재(C), 백색안료(D), 광안정제(E), 소듐 포스페이트 염(F)의 사양은 다음과 같다.Aromatic polyamide resin (A) used in Examples and Comparative Examples of the present invention. The specifications of the acrylic compound (B), inorganic filler (C), white pigment (D), light stabilizer (E), and sodium phosphate salt (F) are as follows.
(A) 방향족 폴리아미드 수지(A) Aromatic Polyamide Resin
(A-1) 폴리아미드 수지(PA10T)(A-1) polyamide resin (PA10T)
테레프탈산과 1,10-데칸 디아민과의 축중합에 의해 제조된 주사슬에 방향족 고리가 포함된 방향족 폴리아미드 수지인 PA10T를 사용하였다.PA10T, an aromatic polyamide resin containing an aromatic ring, was used in the main chain prepared by condensation polymerization of terephthalic acid and 1,10-decane diamine.
(A-2) 폴리아미드 수지(PA6T)(A-2) Polyamide Resin (PA6T)
테레프탈산과 헥사메틸렌 디아민과의 축중합에 의해 제조된 주사슬에 방향족 고리가 포함된 방향족 폴리아미드 수지인 PA6T를 사용하였다.PA6T, an aromatic polyamide resin containing an aromatic ring, was used in the main chain prepared by condensation polymerization of terephthalic acid and hexamethylene diamine.
(B) 아크릴계 화합물(B) Acrylic Compound
(B-1) 페닐메타아크릴레이트-메틸메타아크릴레이트 공중합체(B-1) Phenyl methacrylate-methyl methacrylate copolymer
페닐메타아크릴리에트 30 중량% 및 메틸메타아크릴레이트 70 중량%를 포함하고, 중량평균 분자량이 20,000 g/mol인 페닐메타아크릴레이트-메틸메타아크릴레이트 공중합체를 사용하였다.A phenylmethacrylate-methylmethacrylate copolymer having 30% by weight of phenylmethacrylate and 70% by weight of methylmethacrylate and having a weight average molecular weight of 20,000 g / mol was used.
(B-2) 폴리메틸메타아크릴레이트(B-2) polymethyl methacrylate
메틸메타아크릴레이트 단량체로부터 중합된 중량평균 분자량이 100,000 g/mol인 폴리메틸메타아크릴레이트를 사용하였다.Polymethylmethacrylate having a weight average molecular weight of 100,000 g / mol polymerized from the methylmethacrylate monomer was used.
(C) 무기충진재 (C) inorganic filler
무기충진재로 평균 길이가 2.2 ㎛이고, 겉보기 밀도가 0.77 g/㎤인 월라스토나이트로NYCO社의 NYAD 5000을 사용하였다.As an inorganic filler, NYCO NYAD 5000 was used as wollastonite with an average length of 2.2 μm and an apparent density of 0.77 g / cm 3.
(D) 백색안료 (D) white pigment
백색안료로 이산화티탄인 Kronos社의 KRONOS 2233을 사용하였다.Titanium dioxide, Kronos 2233 from titanium dioxide was used as a white pigment.
(E) 광안정제(E) light stabilizer
광안정제로 BASF社의 CHIMASSORB 944를 사용하였다.BASF CHIMASSORB 944 was used as a light stabilizer.
(F) 소듐 포스페이트 염(F) sodium phosphate salt
소듐 포스페이트 염으로 Innophos社의 산성 피로인산 나트륨(sodium acid pyrophosphate)을 사용하였다.Innophos sodium sodium pyrophosphate was used as the sodium phosphate salt.
실시예 1 내지 9 및 비교실시예 1 내지 5Examples 1-9 and Comparative Examples 1-5
하기 표 1의 함량에 따라 각 구성 성분을 첨가하고 240 내지 350 ℃로 가열된 이축 용융압출기 내에서 용융/혼련시켜 펠렛(pellet) 상태의 수지 조성물을 제조하였다. 이와 같이 얻어진 펠렛을 130 ℃의 온도에서 5시간 이상 건조시킨 다음, 240 내지 330 ℃로 가열된 스크류식 사출기를 이용하여 물성 평가용 시편을 제조하였다.Each component was added according to the content of Table 1 and melted / kneaded in a twin screw melt extruder heated to 240 to 350 ° C. to prepare a resin composition in a pellet state. The pellet thus obtained was dried at a temperature of 130 ° C. for at least 5 hours, and then a specimen for evaluation of physical properties was prepared using a screw injection machine heated to 240 to 330 ° C.
하기 표 1에서 (A), (B), (C) 및 (D)의 혼합비는 (A), (B), (C) 및 (D)의 전체 100 중량%에 대하여 중량%로 나타낸 것이고, (E) 및 (F)는 (A), (B), (C) 및 (D)의 기초 수지 조성물 100 중량부에 대하여 중량부로 나타낸 것이다.In the following Table 1, the mixing ratios of (A), (B), (C) and (D) are expressed in weight% relative to the total 100 weight% of (A), (B), (C) and (D), (E) and (F) are shown by weight part with respect to 100 weight part of base resin compositions of (A), (B), (C) and (D).
표 1
Figure PCTKR2013001723-appb-T000001
 Table 1
Figure PCTKR2013001723-appb-T000001
제조된 시편에 대하여 하기와 같은 방법으로 물성을 측정하였으며, 그 결과를 표 2에 나타내었다.The physical properties of the prepared specimens were measured by the following method, and the results are shown in Table 2.
(1) 내열성(HDT): ASTM D648에 준하여 1/4 inch 두께의 시편을 18.6 kgf의 하중으로 열변형 온도(HDT)를 측정하였다.(1) Heat resistance (HDT): In accordance with ASTM D648, the heat deflection temperature (HDT) was measured for a 1/4 inch thick specimen under a load of 18.6 kgf.
(2) 반사성(반사율): Konica Minolta社 3600D CIE Lab. 색차계로 440 nm 파장에서의 초기 반사율(SCI, specular component included)을 측정하고, 온도 85 ℃, 상대습도 85%에서 150시간 방치 후 다시 반사율을 측정하여, 반사율의 감소를 평가하였다.(2) Reflectivity (reflectivity): Konica Minolta 3600D CIE Lab. The initial reflectance (SCI, specular component included) at 440 nm wavelength was measured with a color difference meter, and the reflectance was measured again after 150 hours at 85 ° C. and 85% relative humidity to evaluate the decrease in reflectance.
(3) 내황변성(황색도): Konica Minolta社 3600D CIE Lab. 색차계로 초기 황색도(yellow index, YI)를 측정하고, 온도 170 ℃에서 24시간 방치 후 다시 황색도를 측정하여, 황색도의 변화를 평가하였다.(3) Yellowing resistance (yellowness): Konica Minolta 3600D CIE Lab. The initial yellowness index (YI) was measured with a color difference meter, and the yellowness was measured again after standing at a temperature of 170 ° C. for 24 hours to evaluate the change in yellowness.
(4) 내충격성(Izod 충격강도): ASTM D256에 준하여 1/8 inch 두께의 unnotched 시편에 대해 Izod 충격강도를 측정하였다.(4) Impact resistance (Izod impact strength): Izod impact strength was measured for unnotched specimens of 1/8 inch thickness according to ASTM D256.
표 2
Figure PCTKR2013001723-appb-T000002
 TABLE 2
Figure PCTKR2013001723-appb-T000002
상기 표 2의 결과로부터, 본 발명의 조성에 따른 실시예 1 내지 9의 열가소성 수지 조성물은 내열성, 내충격성을 저하시키지 않으면서, 항온/항습 평가에서 반사율 유지 특성 및 항온 평가에서 황색도 유지 특성이 뛰어나 고온 내변색성이 우수함을 알 수 있다.From the results of Table 2, the thermoplastic resin compositions of Examples 1 to 9 according to the composition of the present invention have the yellowness retention characteristics in the constant temperature / humidity evaluation and the reflectance retention characteristics and constant temperature evaluation without deteriorating heat resistance and impact resistance. It can be seen that it is excellent in high temperature discoloration resistance.
반면, 비교실시예 2와 같이 아크릴계 화합물(B)을 사용하지 않거나, 비교실시예 3과 같이 아크릴계 화합물(B)을 본 발명의 범위 밖으로 소량 사용한 경우, 우수한 황색도 유지 특성을 확보할 수 없어 고온 내변색성이 저하된 것을 알 수 있다. 또한, 무기충진재(C)를 사용하지 않은 비교실시예 1은 내열성이 저하된 것을 알 수 있다.On the other hand, when the acrylic compound (B) is not used as in Comparative Example 2, or when the acrylic compound (B) is used in a small amount outside the scope of the present invention as in Comparative Example 3, excellent yellowness retention characteristics cannot be secured, so that It turns out that discoloration resistance fell. In addition, it can be seen that Comparative Example 1, in which the inorganic filler (C) is not used, has reduced heat resistance.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (18)

  1. (A) 방향족 폴리아미드 수지;(A) aromatic polyamide resin;
    (B) 아크릴계 화합물;(B) acrylic compounds;
    (C) 무기충진재;(C) inorganic fillers;
    (D) 백색안료;(D) white pigments;
    (E) 광안정제; 및(E) light stabilizers; And
    (F) 소듐 포스페이트 염;(F) sodium phosphate salts;
    을 포함하는 것을 특징으로 하는 열가소성 수지 조성물.Thermoplastic resin composition comprising a.
  2. 제1항에 있어서, 상기 방향족 폴리아미드 수지(A) 10 내지 70 중량%; 상기 아크릴계 화합물(B) 5 내지 70 중량%; 상기 무기충진재(C) 5 내지 30 중량%; 및 상기 백색안료(D) 10 내지 50 중량%;를 포함하는 기초 수지 조성물 100 중량부에 대하여, 상기 광안정제(E) 0.01 내지 2 중량부; 및 상기 소듐 포스페이스 염(F) 0.01 내지 2 중량부;를 포함하는 것을 특징으로 하는 열가소성 수지 조성물.10 to 70% by weight of the aromatic polyamide resin (A); 5 to 70% by weight of the acrylic compound (B); 5 to 30% by weight of the inorganic filler (C); 10 to 50% by weight of the white pigment (D); 0.01 to 2 parts by weight of the light stabilizer (E); And 0.01 to 2 parts by weight of the sodium foam salt (F); thermoplastic resin composition comprising a.
  3. 제1항에 있어서, 상기 방향족 폴리아미드 수지(A)는 방향족 디카르복실산이 10 내지 100 몰%가 포함된 디카르복실산과 C4 내지 C20의 지방족 또는 지환족 디아민을 포함하는 단량체들의 축중합에 의하여 제조된 것을 특징으로 하는 열가소성 수지 조성물.The method of claim 1, wherein the aromatic polyamide resin (A) is a polycondensation polymerization of monomers containing dicarboxylic acid containing 10 to 100 mol% aromatic dicarboxylic acid and C 4 to C 20 aliphatic or alicyclic diamine Thermoplastic resin composition, characterized in that prepared by.
  4. 제1항에 있어서, 상기 방향족 폴리아미드 수지(A)는 하기 화학식 3으로 표시되는 반복단위를 포함하는 것을 특징으로 하는 열가소성 수지 조성물:The thermoplastic resin composition of claim 1, wherein the aromatic polyamide resin (A) comprises a repeating unit represented by the following Chemical Formula 3:
    [화학식 3][Formula 3]
    Figure PCTKR2013001723-appb-I000002
    Figure PCTKR2013001723-appb-I000002
    상기 식에서, m은 4 내지 12, n은 50 내지 500의 정수임.Wherein m is an integer from 4 to 12, n is from 50 to 500.
  5. 제1항에 있어서, 상기 아크릴계 화합물(B)은 선형 구조의 아크릴계 단량체 또는 중합체를 포함하는 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition of claim 1, wherein the acrylic compound (B) comprises an acrylic monomer or a polymer having a linear structure.
  6. 제5항에 있어서, 상기 아크릴계 화합물(B)은 (메타)아크릴산 알킬에스테르, (메타)아크릴산 아릴에스테르, (메타)아크릴산 사이클로알킬 에스테르, (메타)아크릴산 또는 이들의 혼합물을 포함하는 것을 특징으로 하는 열가소성 수지 조성물.The acrylic compound (B) comprises (meth) acrylic acid alkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid or a mixture thereof. Thermoplastic resin composition.
  7. 제6항에 있어서, 상기 아크릴계 화합물(B)은 폴리(메타)아크릴산 알킬에스테르 또는 이의 공중합체, 폴리 (메타)아크릴산 아릴에스테르 또는 이의 공중합체, 폴리(메타)아크릴산 사이클로알킬 에스테르 또는 이의 공중합체, 폴리(메타)아크릴산 또는 이의 공중합체, 또는 이들의 혼합물을 포함하는 것을 특징으로 하는 열가소성 수지 조성물.The method of claim 6, wherein the acrylic compound (B) is a poly (meth) acrylic acid alkyl ester or copolymer thereof, poly (meth) acrylic acid aryl ester or copolymer thereof, poly (meth) acrylic acid cycloalkyl ester or copolymer thereof, A thermoplastic resin composition comprising poly (meth) acrylic acid or a copolymer thereof, or a mixture thereof.
  8. 제5항에 있어서, 상기 아크릴계 단량체 또는 중합체는 상기 아크릴계 화합물(B) 100 중량%에 대하여 40 내지 100 중량%로 포함되는 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to claim 5, wherein the acrylic monomer or polymer is included in an amount of 40 to 100% by weight based on 100% by weight of the acrylic compound (B).
  9. 제5항에 있어서, 상기 아크릴계 화합물(B)은 아크릴계 단량체와 방향족 비닐 화합물, 시안화 비닐 화합물, 헤테로 고리 화합물 또는 이들의 혼합물의 공중합체를 더 포함하는 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition according to claim 5, wherein the acrylic compound (B) further comprises a copolymer of an acrylic monomer, an aromatic vinyl compound, a vinyl cyanide compound, a heterocyclic compound, or a mixture thereof.
  10. 제1항에 있어서, 상기 무기충진재(C)는 탄소섬유, 유리섬유, 붕소섬유, 유리비드, 유리플레이크, 카본블랙, 활석, 클레이, 카올린, 탈크, 마이카, 탄산칼슘, 월라스토나이트, 티탄산칼륨 휘스카, 붕산알미늄 휘스카, 산화아연 휘스카, 칼슘 휘스카 및 이들의 혼합물로 이루어진 군으로부터 선택된 하나 이상인 것을 특징으로 하는 열가소성 수지 조성물.The method of claim 1, wherein the inorganic filler (C) is carbon fiber, glass fiber, boron fiber, glass beads, glass flakes, carbon black, talc, clay, kaolin, talc, mica, calcium carbonate, wollastonite, potassium titanate At least one selected from the group consisting of whiskers, aluminum borate whiskers, zinc oxide whiskers, calcium whiskers and mixtures thereof.
  11. 제1항에 있어서, 상기 무기충진재(C)는 월라스토나이트이고, 상기 월라스토나이트는 평균 길이가 0.1 내지 11 ㎛인 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin composition of claim 1, wherein the inorganic filler (C) is wollastonite, and the wollastonite has an average length of 0.1 to 11 µm.
  12. 제1항에 있어서, 상기 백색안료(D)는 산화티탄, 산화아연, 황화아연, 연백, 황산아연, 황산바륨, 탄산칼슘, 산화알루미늄 및 이들의 혼합물로 이루어진 군으로부터 선택된 하나 이상인 것을 특징으로 하는 열가소성 수지 조성물.The method of claim 1, wherein the white pigment (D) is at least one selected from the group consisting of titanium oxide, zinc oxide, zinc sulfide, lead white, zinc sulfate, barium sulfate, calcium carbonate, aluminum oxide and mixtures thereof. Thermoplastic resin composition.
  13. 제1항에 있어서, 상기 광안정제(E)는 벤조페논계 화합물, 살리실레이트계 화합물, 벤조트리아졸계 화합물, 아크릴로니트릴계 화합물, 힌더드아민계 화합물, 힌더드 페놀계 화합물 및 이들의 혼합물로 이루어진 군으로부터 선택된 하나 이상인 것을 특징으로 하는 열가소성 수지 조성물.According to claim 1, wherein the light stabilizer (E) is a benzophenone compound, salicylate compound, benzotriazole compound, acrylonitrile compound, hindered amine compound, hindered phenol compound and mixtures thereof Thermoplastic resin composition, characterized in that at least one selected from the group consisting of.
  14. 제1항에 있어서, 상기 소듐 포스페이트 염(F)은 인산 일수소 나트륨, 인산 이수소 나트륨, 인산 나트륨, 피로인산 나트륨, 산성 피로인산 나트륨 및 이들의 혼합물로 이루어진 군으로부터 선택된 하나 이상인 것을 특징으로 하는 열가소성 수지 조성물.The sodium phosphate salt (F) is at least one selected from the group consisting of sodium monohydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, sodium pyrophosphate, acidic sodium pyrophosphate and mixtures thereof. Thermoplastic resin composition.
  15. 제1항에 있어서, 형광증백제, 활제, 이형제, 핵제, 대전방지제, 안정제, 보강재, 무기물 첨가제, 안료, 염료 및 이들의 혼합물로 이루어진 군으로부터 선택되는 첨가제를 더 포함하는 것을 특징으로 하는 열가소성 수지 조성물.The thermoplastic resin of claim 1, further comprising an additive selected from the group consisting of fluorescent brighteners, lubricants, mold release agents, nucleating agents, antistatic agents, stabilizers, reinforcing agents, inorganic additives, pigments, dyes, and mixtures thereof. Composition.
  16. 제1항 내지 제15항 중 어느 한 항의 열가소성 수지 조성물로부터 제조된 성형품.A molded article prepared from the thermoplastic resin composition according to any one of claims 1 to 15.
  17. 제16항에 있어서, 상기 성형품은 색차계로 440 nm 파장에서 측정한 초기 반사율이 92% 이상이고, 온도 85 ℃, 상대습도 85%에서 150시간 방치 전/후 440 nm 파장에서 측정한 반사율 감소가 5% 미만이며, 온도 170 ℃에서 24시간 방치 전/후 측정한 황색도 변화(△YI)가 5 미만인 것을 특징으로 하는 성형품.The method of claim 16, wherein the molded article is measured by the color difference meter at an initial reflectance of 92% or more, the reflectance decrease measured at 440 nm wavelength before and after 150 hours at 85 ℃, 85% relative humidity of 5 It is less than%, the molded article characterized by the yellowness change (△ YI) measured before / after standing for 24 hours at a temperature of 170 ℃ less than 5.
  18. 제16항에 있어서, 상기 성형품은 ASTM D256에 준하여 1/8 inch 두께 시편에 대하여 측정한 Izod 충격강도가 25 내지 40 kgf·cm/cm이고, ASTM D648에 준하여 18.6 kgf 하중 하에서 1/4 inch 두께 시편에 대하여 측정한 열변형 온도(HDT)가 200 내지 250 ℃인 것을 특징으로 하는 성형품.The method according to claim 16, wherein the molded article has an Izod impact strength of 25 to 40 kgf cm / cm measured on a 1/8 inch thick specimen in accordance with ASTM D256, 1/4 inch thickness under an 18.6 kgf load in accordance with ASTM D648 Molded article characterized in that the heat deflection temperature (HDT) measured for the specimen is 200 to 250 ℃.
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