WO2016133056A1 - Composition de résine de polyester perméable à la lumière infrarouge - Google Patents

Composition de résine de polyester perméable à la lumière infrarouge Download PDF

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WO2016133056A1
WO2016133056A1 PCT/JP2016/054328 JP2016054328W WO2016133056A1 WO 2016133056 A1 WO2016133056 A1 WO 2016133056A1 JP 2016054328 W JP2016054328 W JP 2016054328W WO 2016133056 A1 WO2016133056 A1 WO 2016133056A1
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polyester resin
resin composition
mass
carboxylic acid
acid
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PCT/JP2016/054328
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English (en)
Japanese (ja)
Inventor
卓也 下拂
知英 中川
安井　淳一
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東洋紡株式会社
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Priority to JP2016512136A priority Critical patent/JPWO2016133056A1/ja
Publication of WO2016133056A1 publication Critical patent/WO2016133056A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a polyester resin composition suitable for use as a design member (particularly a lamp member) having excellent infrared light transmittance, good heat resistance, and low gas properties.
  • Polybutylene terephthalate resin is widely used as an injection-molded product in the fields of automobile parts, mechanical parts, electrical / communication parts, etc. by utilizing its excellent injection moldability, mechanical properties, heat resistance, electrical properties, chemical resistance, etc. It's being used. Furthermore, it is excellent in mold transferability, and can be suitably used for lamp members for automotive extension applications that require particularly good appearance. In addition, it is necessary to highly control the heat resistance of the resin and the suppression of gas generation (lowmonyy) during molding.
  • LED lights are mounted on headlamps of luxury cars and the like, and lamp designs have begun to be renewed.
  • the reflector type light reflected from the light source is reflected by the reflector
  • the projector type light source light is condensed and irradiated on the front lens.
  • the sunlight collection is such that the condensing part becomes very hot and scratches are caused.
  • Patent Documents 1 to 3 disclose polybutylene terephthalate or a resin comprising polybutylene terephthalate and a polybutylene terephthalate copolymer, polycarbonate resin, styrene acrylonitrile resin, 1,4-cyclohexanediene.
  • a resin composition comprising an amorphous resin such as a polyester resin containing a methanol component is disclosed.
  • these technologies are useful for increasing the infrared light transmittance of polybutylene terephthalate resin, but the thermal deformation temperature is remarkably lowered by the addition of amorphous resin. It is difficult to use.
  • Patent Document 4 discloses a polyethylene terephthalate resin composition containing a pigment that does not contain carbon black but is blackened by color matching. It is disclosed. According to the present invention, the use of a non-carbon black pigment can reduce the temperature corresponding to the amount of heat stored due to the infrared light absorption of carbon black, but its temperature rise inhibiting effect is small and greatly improved. There is room.
  • JP 2004-315805 A Japanese Patent No. 5034217 JP 2008-106217 A JP 2014-125588 A Special table 2014-512420 gazette
  • an object of the present invention is to provide a polyester resin composition suitable for use as a design member (especially a lamp member) having excellent infrared light transmittance, good heat resistance, and low gas properties. is there.
  • the present invention has the following configuration.
  • the average value of the transmittance at a wavelength of 800 to 1100 nm of a 2 mm-thick flat plate obtained from the polyester resin composition is 20% or more and 75% or less
  • the thermal deformation temperature (0.45 MPa) [2]
  • the polyester resin (A) contains the polybutylene terephthalate resin (a) and the polyethylene terephthalate resin (b) in a mass ratio of 100: 0 to 50:50 [ 1] The polyester resin composition described in 1].
  • the metal constituting the organic carboxylic acid alkali metal salt (B) having 3 to 40 carbon atoms is one or more selected from lithium, sodium and potassium [1] Or the polyester resin composition as described in [2].
  • the organic carboxylic acid constituting the alkali metal salt of organic carboxylic acid having 3 to 40 carbon atoms (B) is an aliphatic carboxylic acid having 3 to 20 carbon atoms, [1] to [3 ]
  • the transmittance at a wavelength of 300 to 700 nm of a 2 mm-thick flat plate obtained from the polyester resin composition containing the colorant (D) is substantially 0% [1] to [4]
  • [6] The polyester resin composition according to [5], including a colorant (D), and the polyester resin composition satisfies the following requirement (3).
  • Color-L represents the hue L * value by the LIE * L * a * b * system of the CIE color difference system of the polyester resin composition.
  • Color-L represents the hue L * value by the LIE * L * a * b * system of the CIE color difference system of the polyester resin composition.
  • the infrared light transmittance is dramatically increased while maintaining high crystallinity. Therefore, good heat resistance (high heat distortion temperature) can be realized without adding a reinforcing filler such as talc, and both high infrared light transmittance and excellent heat resistance can be achieved. Furthermore, since a resin molded body in which gas generation is also highly controlled can be obtained, it is excellent in fogging resistance and it is possible to reduce mold contamination during injection molding.
  • the polyester resin (A) that can be used in the present invention is preferably a polyester resin having a dicarboxylic acid component and a diol component as constituent units.
  • the dicarboxylic acid component those having an aromatic dicarboxylic acid as a main component are preferable.
  • the main component is usually 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more with respect to all dicarboxylic acid units.
  • aromatic dicarboxylic acids aliphatic dicarboxylic acids can be used.
  • Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2, Fragrances such as 7-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, 4,4′-biphenyl ether dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid, anthracene dicarboxylic acid Among these, terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid are preferable.
  • aliphatic dicarboxylic acid examples include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecanedioic acid, dimer acid, and cyclohexanedicarboxylic acid, which usually have 2 to 40 carbon atoms.
  • examples include chain or alicyclic dicarboxylic acids.
  • the above dicarboxylic acid components can be used alone or in admixture of two or more.
  • a hydroxycarboxylic acid component or a lactone component may be copolymerized. The amount used is preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less, based on all monomer components.
  • diol component examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 3-methyl-1,5.
  • -Pentanediol 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,9-nonanediol
  • Examples include 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol and the like. Of these, ethylene glycol, 1,3-propanediol, and 1,4-butanediol are preferable.
  • polyester resins (A) include polybutylene terephthalate, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene naphthalate, and polyethylene naphthalate.
  • the polyester resin (A) preferably has an intrinsic viscosity (IV) of 0.36 to 1.60 dl / g when an o-chlorophenol solution is measured at 25 ° C., and is 0.52 to 1.25 dl. / G is more suitable, more preferred is 0.58 to 1.12 dl / g, and most preferred is 0.62 to 1.02 dl / g. It is.
  • the mechanical properties and moldability of the polyester resin composition of the present invention are improved.
  • polytrimethylene terephthalate resin (c) and polybutylene naphthalate resin (d) as a polyester resin (A).
  • the polytrimethylene terephthalate resin (c) can be used as an alternative to the polyethylene terephthalate resin (b), and the polybutylene naphthalate resin (d) can be used as an alternative to the polybutylene terephthalate resin (a). is there.
  • the polybutylene terephthalate resin (a) that can be used in the present invention is a polycondensation reaction mainly comprising terephthalic acid or an ester-forming derivative thereof and 1,4-butanediol or an ester-forming derivative thereof. It is a polymer obtained by a general polymerization method.
  • the polymer is preferably a polymer having a butylene terephthalate repeating unit of 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and most preferably 100 mol%.
  • Other copolymer components may be included in a range not impairing the characteristics, for example, about 20% by mass or less.
  • copolymers examples include polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene (terephthalate / naphthalate), poly (butylene) / Ethylene) terephthalate, etc., may be used alone or in combination of two or more.
  • the polybutylene terephthalate resin (a) that can be used in the present invention preferably has an intrinsic viscosity (IV) of 0.36 to 1.60 dl / g when an o-chlorophenol solution is measured at 25 ° C. More preferably in the range of 0.52 to 1.25 dl / g, more preferably in the range of 0.58 to 1.12 dl / g, and 0.62 to 1.02 dl / g. Those in the g range are most preferred.
  • the intrinsic viscosity of (a) is 0.36 to 1.60 dl / g, the mechanical properties and moldability of the polyester resin composition of the present invention are improved.
  • the polybutylene naphthalate resin (d) that can be used in the present invention is the same as the polybutylene terephthalate resin (a).
  • the polyethylene terephthalate resin (b) that can be used in the present invention is a conventional polymerization method such as a polycondensation reaction mainly comprising terephthalic acid or an ester-forming derivative thereof and ethylene glycol or an ester-forming derivative thereof.
  • the resulting polymer is preferably a polymer having an ethylene terephthalate repeating unit of 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and most preferably 100 mol%.
  • Other copolymer components may be included in a range not impairing the characteristics, for example, about 20% by mass or less.
  • copolymers examples include polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sebacate), polyethylene (terephthalate / decanedicarboxylate), polyethylene (terephthalate / naphthalate), poly (ethylene) / Cyclohexanedimethyl) / terephthalate, poly (butylene / ethylene) terephthalate, and the like, and may be used alone or in combination of two or more.
  • the polyethylene terephthalate resin (b) the molding shrinkage of the resin composition can be controlled.
  • the polyethylene terephthalate resin (b) that can be used in the present invention preferably has an intrinsic viscosity (IV) of 0.36 to 1.60 dl / g when an o-chlorophenol solution is measured at 25 ° C. More preferably in the range of 0.45 to 1.35 dl / g, more preferably in the range of 0.50 to 1.20 dl / g, and 0.55 to 1.05 dl / g. Those in the range are most preferable.
  • the intrinsic viscosity of (b) is 0.36 to 1.60 dl / g, the mechanical properties and moldability of the polyester resin composition of the present invention are improved.
  • the polytrimethylene terephthalate resin (c) that can be used in the present invention is the same as the polyethylene terephthalate resin (b).
  • the total amount of the polybutylene terephthalate resin (a) and the polyethylene terephthalate resin (b) in the polyester resin (A) is preferably 80% by mass or more, more preferably 90% by mass or more, and 95% by mass or more. Is more preferable, and may be 100% by mass.
  • polybutylene terephthalate resin (a) means “at least one of polybutylene terephthalate resin (a) and polybutylene naphthalate resin (d)”, “polyethylene terephthalate resin (b)” , “At least one of polyethylene terephthalate resin (b) and polytrimethylene terephthalate resin (c)”.
  • the polyester resin composition of the present invention contains 0.1 to 1 part by mass of an organic metal carboxylic acid alkali metal salt (B) having 3 to 40 carbon atoms with respect to 100 parts by mass of the polyester resin (A).
  • the organic carboxylic acid alkali metal salt (B) is less than 0.1 part by mass, the infrared light transmittance of the polyester resin composition tends to decrease.
  • the organic carboxylic acid alkali metal salt (B) is blended in an amount exceeding 1 part by mass, the polyester resin composition is significantly decomposed by the catalytic action of the alkali metal salt, resulting in a decrease in molecular weight and mechanical strength.
  • the blending amount of the organic carboxylic acid alkali metal salt (B) is preferably 0.1 to 0.7 parts by mass, and 0.15 to 0.5 parts by mass with respect to 100 parts by mass of the polyester resin (A). It is more preferable.
  • the organic carboxylic acid alkali metal salt (B) having 3 to 40 carbon atoms used in the present invention is an alkali metal salt of an aliphatic, alicyclic or aromatic carboxylic acid having 3 to 40 carbon atoms.
  • an alkali metal sodium, potassium, and lithium are preferable.
  • An aliphatic carboxylic acid is a compound in which a linear or branched aliphatic group has a carboxyl group, and an unsaturated group, an alicyclic group, an aromatic group or a hydroxyl group, a phosphate ester group is part of the bond. It may have other substituents such as.
  • aliphatic carboxylic acids propionic acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, mytilic acid, palmitic acid, margaric acid, stearic acid, oleic acid, linoleic acid, Montanic acid and the like are preferable, and among alkali metal salts, sodium salt is preferable in terms of solubility in polyester resin and good crystal nucleation.
  • the organic carboxylic acid constituting the organic carboxylic acid alkali metal salt (B) having 3 to 40 carbon atoms is an aliphatic carboxylic acid having 3 to 20 carbon atoms from the viewpoint of melting property and compatibility with the polyester resin.
  • An aliphatic carboxylic acid having 6 to 20 carbon atoms is more preferable.
  • the aliphatic carboxylic acid metal salt having less than 14 carbon atoms is preferable in that the infrared light transmittance can be improved with a small amount.
  • the alkali metal carboxylic acid metal salt (B) acts on the polyester resin (A) as a crystal nucleating agent to form microcrystals with a uniform size, thereby increasing the infrared light transmittance. Further, the alkali metal salt of organic carboxylic acid (B) changes the carboxyl group of the polyester resin (A) to an alkali metal base by an ion exchange reaction, lowers the mobility of the molecular chain terminal, and inhibits further crystallization, It is considered that the organic carboxylic acid is liberated as the ion exchange reaction proceeds.
  • the organic carboxylic acid alkali metal salt (B) can effectively improve the infrared light transmittance with a small amount of blending compared to the alkali metal salt other than the organic carboxylic acid. This is because the organic carboxylic acid alkali metal salt (B) has a relatively small molecular weight, so when the same part by mass is added, the number of molecules increases and crystallization tends to occur, and the molecular size is relatively small. Therefore, this is considered to be due to the fact that the crystal size of the polyester resin (A) generated using this as a crystal nucleus is small (that is, the crystal is difficult to grow and microcrystallizes).
  • Two or more of the above organic carboxylic acid alkali metal salts (B) may be used in combination.
  • Use of a compound having 3 to 14 carbon atoms and a compound having 14 or more carbon atoms is preferred in that the solubility of those having 3 to 14 carbon atoms is improved and the infrared light transmittance is easily improved.
  • the polyester resin composition of the present invention contains 0.05 to 3 parts by mass of the polycarbodiimide compound (C) with respect to 100 parts by mass of the polyester resin (A).
  • the polycarbodiimide compound (C) within this range, it is possible to efficiently exhibit the thickening effect and the trapping effect of the gasifying component such as the organic carboxylic acid to be liberated.
  • the melt viscosity is increased due to the thickening effect and the shear stress is increased, whereby the dispersion of the alkali metal salt of the organic carboxylic acid (B) can be promoted.
  • the growth of crystals is suppressed by the thickening effect, and it is possible to promote the microcrystallization with the organic metal carboxylate (B). Furthermore, excellent low gas properties can be realized by the trapping effect of gasifying components such as free organic carboxylic acids and free hydroxyl group-containing compounds. If the polycarbodiimide compound (C) is more than 3 parts by mass, gelation may be caused by reaction with the polyester resin (A), or infrared light transmittance may be reduced due to compatibility problems.
  • the blending amount of the polycarbodiimide compound (C) is preferably 0.07 parts by mass, more preferably 0.08 parts by mass with respect to 100 parts by mass of the polyester resin (A). It is more preferably 1 part by mass, particularly preferably 0.15 part by mass, and the upper limit is preferably 2 parts by mass, more preferably 1 part by mass, and 0.5 parts by mass. More preferably.
  • the polycarbodiimide compound (C) can have a carboxylic acid reactive group and a hydroxyl group reactive group in one molecule.
  • a compound having a carboxylic acid reactive group and a hydroxyl group reactive group in one molecule is a free acid or a free hydroxyl group-containing compound produced by decomposition of an organic carboxylic acid alkali metal salt (B) or a fatty acid ester compound, and a subsequent heat treatment. It can capture the free acid and free hydroxyl group-containing compound generated during the process and use at high temperature, and can effectively prevent volatilization. Since free acids and free hydroxyl group-containing compounds greatly affect the generation of gas, their capture is effective in preventing volatilization. In particular, free carboxylic acid volatilizes at a relatively low temperature, and the volatiles crystallize, which often causes fogging. Therefore, capturing the free carboxylic acid is extremely important.
  • Examples of the functional group that reacts with the carboxylic acid include a glycidyl group, an oxazoline group, an oxetane group, and a carbodiimide group.
  • general glycidyl group-containing compounds, oxazoline group-containing compounds, and oxetane group-containing compounds do not react quickly, and it may be difficult to coexist with a functional group that reacts with a hydroxyl group. Since it is intense, it is often difficult to use it in applications requiring fogging resistance.
  • carbodiimide compounds have a faster reaction than glycidyl groups, oxazoline groups, and oxetane groups, and are very preferably used for capturing free carboxylic acids.
  • the functional group that reacts with a hydroxyl group is different from the functional group that reacts with a carboxylic acid, and examples thereof include an isocyanate group and an acid anhydride group, and an isocyanate group is particularly preferred from the viewpoint of reactivity.
  • the compound having a carboxylic acid group-reactive group and a hydroxyl group-reactive group in one molecule is most preferably a compound having a carbodiimide group and an isocyanate group in one molecule.
  • the merit of containing a carboxylic acid group-reactive group and a hydroxyl group-reactive group in one molecule is that these functional groups can easily react with either a thermoplastic resin or a free acid or a free hydroxyl group-containing compound, and have a large molecular weight. It is that the volatilization of the fatty acid ester decomposition product can be significantly reduced by connecting the plastic resin and the decomposition product with a reactive compound. Therefore, in the case of the thermoplastic polyester resin containing a carboxylic acid as in the present invention, effects such as hydrolysis inhibition can be imparted, and effects such as improved processability as a resin composition can be exhibited.
  • Polycarbodiimide is a compound having two or more —N ⁇ C ⁇ N— structures in one molecule, and a known one prepared by decarbonation of a diisocyanate compound can be used (US Pat. No. 2,941,956, (See Japanese Patent Publication No. 47-3279, J. Org. Chem., 28, 2069-2075 (1963), Chemical Review 1981, Vol. 81, No. 4, 619-621).
  • diisocyanate compound examples include aliphatic or alicyclic isocyanate compounds such as hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, and methylcyclohexane diisocyanate, 4,4-diphenylmethane diisocyanate, 4,4- Diphenyldimethylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, tetramethylxylylene Range isocyanate, 1,3,5-triisopropylphenylene-2,4-diisocyanate, etc.
  • Family isocyanate compounds may be
  • the polycarbodiimide compound (C) may have a branched structure, and a functional group other than a carbodiimide group or an isocyanate group may be introduced by copolymerization. Further, a part or all of the terminal isocyanate may be blocked.
  • monoisocyanate compounds such as phenyl isocyanate, tris isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate, -OH group, -COOH group, -SH group, -NH-R (R is hydrogen)
  • R is hydrogen
  • the merit of blocking part or all of the terminal isocyanate is that the reaction in the compound can be easily controlled, and the degree of polymerization and melt viscosity can be controlled.
  • a certain amount or more of a polycarbodiimide compound in which the terminal isocyanate is not blocked is added to the polyester resin (A)
  • the melt viscosity may be remarkably increased due to thickening, and the addition amount may be limited.
  • the amount of polycarbodiimide compound added is limited, the expected effect may not be obtained.
  • it can be solved by using a polycarbodiimide compound in which a terminal isocyanate is blocked. Even if all of the terminal isocyanates are blocked, the effect of capturing the free carboxylic acid due to the high reactivity of the carbodiimide group is high, so that a sufficiently high low gas property can be obtained.
  • the Nisshinbo Carbodilite series has an aliphatic or alicyclic structure and is preferably used.
  • the average transmittance of a 2 mm thick flat plate obtained from the polyester resin composition at a wavelength of 800 to 1100 nm is 20% or more and 75% or less. is there. Details of the transmittance measurement are as described in the Examples section, but using a 2 mm thick flat plate obtained by injection molding the polyester resin composition at a mold temperature of 60 ° C., a spectrophotometer was used. Measured. The average value is a value obtained by dividing the sum of transmittance at each wavelength by the number of measurements in the range of 800 to 1100 nm. The number of measurements depends on the sampling pitch.
  • the sampling pitch is 1 nm
  • transmittance data is obtained every 1 nm, such as 800, 801, 802,..., 1098, 1099, 1100 nm, and the number of measurements is 301. Therefore, in this case, the average value of the transmittance at a wavelength of 800 to 1100 nm is obtained by (the sum of the transmittance at each wavelength / 301).
  • the average value of the transmittance at a wavelength of 800 to 1100 nm is in this range, even if sunlight is collected, it is difficult to reach a high temperature.
  • a feature of the polyester composition of the present invention is that the infrared light transmittance is remarkably improved while maintaining high crystallinity.
  • the average value of transmittance at a wavelength of 800 to 1100 nm is preferably 25% or more, and more preferably 70% or less.
  • the thermal deformation temperature at a load of 0.45 MPa is 150 ° C. or higher.
  • the heat distortion temperature is measured as described in the Examples section. When the heat distortion temperature is less than 150 ° C., the heat resistance is insufficient, and in particular, it may not be used for applications requiring heat resistance. When the heat distortion temperature is 150 ° C. or higher, it can be said that the polyester resin composition satisfies the heat resistance as a lamp member resin.
  • the heat distortion temperature is preferably 155 ° C. or higher. In that case, the heat resistance as a lamp member resin is more highly satisfied, and 160 ° C. or higher is more preferable.
  • a technique for adding an inorganic filler such as talc is known as a technique for increasing the heat distortion temperature.
  • high heat resistance heat distortion temperature
  • This is considered to be realized by the effect of the alkali metal salt of organic carboxylic acid (B) because it is possible to form microcrystals of uniform size while maintaining or increasing the crystallinity of the resin composition.
  • the haze value of the glass plate after the fogging test can be 5% or less. According to the present invention, gas generation can be effectively suppressed and excellent fogging resistance can be achieved. When the amount of gas generated is large and the haze value of the glass plate after the fogging test (160 ° C.) exceeds 5%, there is a practical problem of fogging as various lamp parts. In addition, the mold is likely to be contaminated during injection molding, which may adversely affect quality and productivity.
  • the fogging test can be performed by the following method. Cut out a small piece of about 40 mm x 40 mm from an injection molded product (thickness 2 mm), put a total of 10 g in a glass tube (for example, ⁇ 65 x 80 mm) with an aluminum foil covered, and place it on a hot plate. set. Further, the glass tube is covered with a slide glass (for example, 78 mm ⁇ 76 mm ⁇ thickness 1 mm) so that there is no gap between the glass tube, and then heat treated at 160 ° C. for 24 hours. Deposits due to decomposition products sublimated from the resin composition are deposited). The haze value of the slide glass is measured using a haze meter or the like.
  • the polyester resin composition of the present invention can contain a colorant (D).
  • a pigment is used as the colorant, the infrared transmittance is remarkably lowered. Therefore, it is preferable to use an infrared light transmitting dye.
  • the infrared light transmitting dye known dyes can be used, and one kind or a mixture of two or more kinds of dyes may be used.
  • the dye may be added directly to the resin at the time of compounding, or may be added as a master batch. From the viewpoint of dispersibility and handling properties, it is preferable to add them in a master batch.
  • the color is preferably black from the viewpoint of design.
  • the dye that can be added to the polyester resin composition examples include dyes such as quinoline compounds, anthraquinone compounds, and perinone compounds. These have good heat resistance and are hardly thermally decomposed during compounding or injection molding of the polyester resin composition.
  • the molecular weight per molecule of the infrared light transmitting dye is preferably 350 or more, more preferably 380 or more, and further preferably 400 or more.
  • the melting point is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, and further preferably 200 ° C. or higher. It is sufficient that either the molecular weight or the melting point satisfy this range, and it is particularly preferable that both the molecular weight and the melting point satisfy this range.
  • the molecular weight and melting point of each dye alone preferably satisfy the above ranges.
  • the molecular weight and the melting point satisfy the above ranges, there are cases in which the dye is also volatilized due to the vaporization of the gasification component due to the high interaction with the gasification component contained in the resin. is there.
  • anthraquinone compounds and perinone compounds can be preferably used from the viewpoint of fogging properties.
  • the colorant (D) is contained, the content thereof is preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of the polyester resin (A).
  • the content of the colorant (D) is more preferably 0.1 to 2 parts by mass, and further preferably 0.2 to 1 part by mass.
  • the content as a colorant is usually about 5 to 20% by mass (especially in the case of dyes), although it depends on the type of base resin and colorant used. Often.
  • the hue of the master batch pellet is the hue L * value (Color-) according to the L * a * b * system of the CIE color difference system.
  • L is preferably 22 or less
  • hue a * value (Color-a) is from ⁇ 1.5 to 1.5
  • hue b * value (Color-b) is preferably from ⁇ 1.5 to 1.5.
  • Color of the masterbatch pellets is more preferably, a hue L * value according to the L * a * b * system of CIE color difference system (Color-L) is 21 or less, hue a * value (Color-a) is -1 1 or less, hue b * value (Color-b) is ⁇ 1 or more and 1 or less (both measured values by SCE method).
  • the transmittance at a wavelength of 300 to 700 nm of a 2 mm-thick flat plate obtained from the polyester resin composition is preferably substantially 0%.
  • the transmittance measurement at this wavelength is the same as described above. “Substantially” means that noise during measurement is not taken into consideration. Usually, when it is 0 ⁇ 0.05%, it can be regarded as substantially 0%. In the present invention, the fact that the transmittance at a wavelength of 300 to 700 nm is in the range of 0 ⁇ 0.05% is substantially 0%.
  • the transmittance at a wavelength of 300 to 700 nm is substantially 0% because the visible light hiding property is high and the design property is high.
  • the transmittance at a wavelength of 300 to 700 nm exceeds 0% (substantially 0%), the visible light concealing property is not sufficient, and the design property is low.
  • the polyester resin composition of the present invention containing a colorant (D) has a hue L * value (Color-L) of CIE color difference L * a * b * of 7 or less (SCE method) Measured value).
  • Color-L ⁇ 7 (I) When the L * value is 7 or less, the polyester resin composition of the present invention can have sufficient blackness, and can exhibit sufficient blackness even in a molded product obtained by melt molding or the like. Therefore, it is excellent in design property.
  • the hue L * value is preferably 6 or less, more preferably 5 or less. When the hue L * value is higher than 7, the blackness is insufficient and the design property is low.
  • the polyester resin composition of the present invention may contain an inorganic filler (E) as long as the characteristics of the present invention are not impaired.
  • An inorganic filler (E) is not specifically limited, A well-known thing can be used.
  • the inorganic filler (E) may be subjected to a surface treatment in order to improve compatibility and dispersibility with the polyester resin composition.
  • the average particle size of the inorganic filler (E) is preferably 3.0 ⁇ m or less.
  • 1 mass part or less is preferable with respect to 100 mass parts of polyester resins (A), and, as for content of an inorganic filler (E), 0.8 mass part or less is more preferable, and 0.5 mass part or less is further more preferable.
  • the amount exceeds 1 part by mass, coarse crystals may be generated using the inorganic filler as a crystal nucleating agent, and the infrared transmittance may be significantly reduced.
  • a technique of adding an inorganic filler such as talc is generally known as a technique for increasing the heat distortion temperature.
  • the polyester resin composition of the present invention does not contain an inorganic filler such as talc.
  • the polyester resin composition of the present invention may contain a release agent as long as the characteristics of the present invention are not impaired.
  • the content of the release agent is preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polyester resin (A). If the release agent is less than 0.1 parts by mass, a sufficient release effect cannot be obtained, and there may be problems such as defective release and release wrinkles.
  • the mold release agent itself becomes a gas and bleeds out to contaminate the mold, and adheres to the lens cover, mirror, etc. in a temperature environment in the range of 100 ° C to 200 ° C. There is a problem of generating (fogging). When the release agent exceeds 3 parts by mass, these problems become significant.
  • the type of release agent is not particularly limited as long as it can be used for polyester.
  • long chain fatty acids or esters thereof, metal salts, amide compounds, polyethylene wax, silicon, polyethylene oxide and the like can be mentioned.
  • the long chain fatty acid preferably has 12 or more carbon atoms, and examples thereof include stearic acid, 12-hydroxystearic acid, behenic acid, and montanic acid. Partial or total carboxylic acid is esterified with monoglycol or polyglycol. Or a metal salt may be formed.
  • the amide compound include ethylene bisterephthalamide and methylene bisstearyl amide. These release agents may be used alone or as a mixture.
  • As the release agent there is a compound overlapping with the above component (B). When such a compound is used as the release agent, the total amount of the component (B) and the amount of the release agent is as described above (B ) It must be within the range of acceptable contents of components.
  • the polyester resin composition of the present invention can contain various additives in a known range as long as the characteristics of the present invention are not impaired, if necessary.
  • known additives include heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, plasticizers, modifiers, antistatic agents, flame retardants and the like.
  • the polyester resin composition of the present invention preferably occupies 85% by mass or more in total of the components (A), (B), (C), and (D) (the component (D) is an optional component), 90 It is more preferable to occupy 95% by mass or more, and it is even more preferable to occupy 95% by mass or more.
  • the polyester resin composition of the present invention can be produced by mixing the above-described components and various stabilizers as necessary, and melt-kneading. Any method known to those skilled in the art can be used as the melt-kneading method, and a single screw extruder, a twin screw extruder, a pressure kneader, a Banbury mixer, or the like can be used. Among these, it is preferable to use a twin screw extruder. As general melt kneading conditions, in a twin screw extruder, the cylinder temperature is 230 to 270 ° C., and the kneading time is 2 to 15 minutes.
  • the method for molding the polyester resin composition of the present invention is not particularly limited, and known methods such as injection molding, extrusion molding, and blow molding can be used. Among these, an injection molding method is preferably used from the viewpoint of versatility.
  • the molded article of the polyester resin composition of the present invention can directly form (evaporate) a light reflecting metal layer on at least a part of the surface.
  • the vapor deposition method is not particularly limited, and a known method can be used.
  • the molded product molded using the polyester resin composition of the present invention can be suitably used as a design member (particularly a lamp member).
  • a design member particularly a lamp member.
  • it can be used as a member for automobile lamps (head lamps, etc.), light reflectors (extensions, reflectors, housings, etc.), lighting equipment, electrical / electronic parts, household goods, etc.
  • the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
  • the measured value described in the Example is measured by the following method.
  • a transmittance of a wavelength of 300 to 1500 nm is obtained with a sampling pitch of 1.0 nm and a slit width (12). Measurements were made to calculate the average transmittance (sum of transmittance at each wavelength / 301) at wavelengths of 800 to 1100 nm. When the colorant was used, the transmittance at a wavelength of 300 to 700 nm was separately measured.
  • MFR Melt flow rate
  • the hue of the flat plate of the polyester resin composition was measured by the following method. Using an injection molding machine EC-100N (manufactured by Toshiba Machine Co., Ltd.), a flat plate molded product having a thickness of 100 mm ⁇ 100 mm ⁇ 2 mm was injection molded using a mold having a mirror surface polished on # 6000 file on one side. Molding was performed at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C.
  • the hue L * value (CIE color difference system) on the mirror surface side of the molded plate is measured according to JIS Z 8722 and JIS Z 8781-4. did. Measurements were taken with a D65 light source, 10 ° field of view, 0 ° -d method, and SCE method. The hue of the infrared light transmissive dye masterbatch pellet was measured by the following method.
  • Aliphatic carboxylic acid alkali metal salt (B); (B-1) Sodium caprylate (manufactured by Nitto Kasei Kogyo Co., Ltd., melting point 220 ° C.) (B-2) Sodium stearate (manufactured by NOF Corporation, melting point 230 ° C.)
  • B-3 ADK STAB NA-11 (not an alkali metal carboxylate, aromatic nucleating agent, manufactured by ADEKA, melting point ⁇ 400 ° C.)
  • B-4) ADK STAB NA-21 (not an alkali metal carboxylate, aromatic nucleating agent, manufactured by ADEKA, melting point ⁇ 210 ° C.)
  • Inorganic fillers Talc (average particle size: 2.5 ⁇ m [laser diffraction method]): Microace SG-95 (manufactured by Nippon Talc Co., Ltd.) Catalog values are used for the average particle size.
  • Triglycerin flubehenate Poem TR-FB (manufactured by Riken Vitamin) Stabilizers
  • Antioxidant Irganox 1010 (BASF)
  • Example 1 to 12 Comparative Examples 1 to 10
  • Example 8 Comparative Examples 2, 3 and 4 are 260 ° C.
  • the strand was cooled with water and pelletized.
  • Each of the obtained pellets was dried at 130 ° C. for 4 hours and used for each of the above-described evaluation tests. The results are shown in Tables 1 and 2.
  • molded articles obtained from the polyester resin compositions of Examples 1 to 8 and 12 of the present invention have an infrared light transmittance of 20% or more and a heat distortion temperature of 150 ° C. or more, which is excellent. It can be seen that it has the characteristics. In all cases, the haze value of the glass plate after the fogging test was as good as 5% or less. It turns out that Example 9, 10 has provided the visible light hiding property which was excellent by addition of a black coloring agent. The physical properties were the same as before the colorant addition, and all were good. Furthermore, the haze value of the glass plate after the fogging test was also good at 5% or less.
  • Example 11 using the purple dye, the infrared light transmittance and other physical properties were good, but the hue L * exceeded 7 and the blackness was insufficient.
  • Comparative Example 1 since there was no addition of an organic metal carboxylic acid alkali metal salt or an inorganic filler, there was no problem in infrared light transmission and haze, but the heat distortion temperature was low.
  • Comparative Examples 2 and 3 were at a level to which an amorphous resin was added, and high infrared light transmittance was obtained, but the heat distortion temperature was lower than that of Comparative Example 1, and the haze of the glass plate after the fogging test was obtained. The value became high.
  • Comparative Example 8 not containing the polycarbodiimide compound (C), compared to Examples 2, 3 and 4, the infrared light transmittance was lowered and fogging was confirmed, and the heat distortion temperature was also low. Moreover, although it seems that dispersion
  • the polyester resin composition of the present invention is excellent in infrared light transmission and has good heat resistance and low gas properties, it is a design member (particularly for lamp members in which scratches due to sunlight collection are a problem) ) Is a polyester resin composition suitable for use as an industrial utility value.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Non-Portable Lighting Devices Or Systems Thereof (AREA)

Abstract

La présente invention concerne une composition de résine de polyester qui satisfait aux conditions (1) et (2) ci-dessous et qui contient de 0,1 à 1 partie en masse d'un sel de métal alcalin d'acide organocarboxylique en C3 à C40 et (B) de 0,05 à 3 parties en masse d'un composé polycarbodiimide (C) pour 100 parties en masse d'une résine de polyester (A), ladite composition de résine de polyester présentant une excellente perméabilité à la lumière infrarouge ainsi qu'une bonne résistance à la chaleur et un faible dégagement gazeux, et étant appropriée pour être utilisée comme élément de conception (en particulier, un élément lampe). (1) La valeur moyenne de la transmittance à une longueur d'onde de 800 à 1100 nm d'une plaque de 2 mm d'épaisseur obtenue à partir de cette composition de résine de polyester est de 20 à 75 %. (2) La température de déformation thermique (0,45 MPa) est supérieure ou égale à 150 °C.
PCT/JP2016/054328 2015-02-16 2016-02-15 Composition de résine de polyester perméable à la lumière infrarouge WO2016133056A1 (fr)

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WO2018143479A1 (fr) * 2017-02-06 2018-08-09 ウィンテックポリマー株式会社 Procédé de production d'une composition de résine polyester aromatique thermoplastique
CN109306154A (zh) * 2017-07-28 2019-02-05 现代摩比斯株式会社 聚酯树脂组合物及由其制造的制品
KR20200123444A (ko) * 2018-02-23 2020-10-29 닛신보 케미칼 가부시키가이샤 수지 조성물, 수지 재료 및 수지 가교체
US20200385413A1 (en) * 2018-02-23 2020-12-10 Nisshinbo Chemical Inc. Metal alkoxide, and aqueous resin crosslinking composition and aqueous resin composition which use same

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WO2018143479A1 (fr) * 2017-02-06 2018-08-09 ウィンテックポリマー株式会社 Procédé de production d'une composition de résine polyester aromatique thermoplastique
JPWO2018143479A1 (ja) * 2017-02-06 2019-02-07 ウィンテックポリマー株式会社 熱可塑性芳香族ポリエステル樹脂組成物の製造方法
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CN109306154B (zh) * 2017-07-28 2021-07-23 现代摩比斯株式会社 聚酯树脂组合物及由其制造的制品
KR20200123444A (ko) * 2018-02-23 2020-10-29 닛신보 케미칼 가부시키가이샤 수지 조성물, 수지 재료 및 수지 가교체
US20200385413A1 (en) * 2018-02-23 2020-12-10 Nisshinbo Chemical Inc. Metal alkoxide, and aqueous resin crosslinking composition and aqueous resin composition which use same
US11685753B2 (en) * 2018-02-23 2023-06-27 Nisshinbo Chemical Inc. Metal alkoxide, and aqueous resin crosslinking composition and aqueous resin composition which use same
KR102706797B1 (ko) * 2018-02-23 2024-09-19 닛신보 케미칼 가부시키가이샤 수지 조성물, 수지 재료 및 수지 가교체

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