WO2017038547A1 - Composition de résine de polycarbonate aromatique et produit moulé associé - Google Patents

Composition de résine de polycarbonate aromatique et produit moulé associé Download PDF

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Publication number
WO2017038547A1
WO2017038547A1 PCT/JP2016/074466 JP2016074466W WO2017038547A1 WO 2017038547 A1 WO2017038547 A1 WO 2017038547A1 JP 2016074466 W JP2016074466 W JP 2016074466W WO 2017038547 A1 WO2017038547 A1 WO 2017038547A1
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WIPO (PCT)
Prior art keywords
polycarbonate resin
aromatic polycarbonate
resin composition
stabilizer
spiro ring
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PCT/JP2016/074466
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English (en)
Japanese (ja)
Inventor
誠 江川
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三菱エンジニアリングプラスチックス株式会社
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Priority claimed from JP2016145507A external-priority patent/JP6183513B2/ja
Application filed by 三菱エンジニアリングプラスチックス株式会社 filed Critical 三菱エンジニアリングプラスチックス株式会社
Publication of WO2017038547A1 publication Critical patent/WO2017038547A1/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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • C08K5/1575—Six-membered rings
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/527—Cyclic esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to an aromatic polycarbonate resin composition. Specifically, the present invention relates to an aromatic polycarbonate resin composition having improved residence heat stability. The present invention also relates to a molded article formed by molding this aromatic polycarbonate resin composition.
  • Aromatic polycarbonate resins are used in a wide range of applications such as electrical equipment, communication equipment, precision machinery, and automobile parts because they are excellent in impact resistance, heat distortion resistance, rigidity, dimensional stability, transparency, and the like.
  • Aromatic polycarbonate resin deteriorates by receiving heat during the molding process, causing problems such as molecular weight reduction and yellowing due to decomposition of the resin. Due to the decrease in the molecular weight of the aromatic polycarbonate resin, the mechanical properties such as the excellent impact resistance inherent in the aromatic polycarbonate resin are impaired. Yellowing becomes a serious problem that impairs commercial value in applications using the inherent transparency of aromatic polycarbonate resin.
  • the production plan (molding cycle) can be secured if a long holding time from filling the aromatic polycarbonate resin composition into the cylinder of the injection molding machine to injecting the molten resin can be secured. ) Can be increased, and an unexpected trouble can be dealt with with a margin. Therefore, the residence heat stability of the resin composition is a very important improvement item in industrial production.
  • Patent Document 1 describes that yellowing is suppressed by blending a phosphite-based stabilizer having a spiro ring skeleton as a thermal stabilizer.
  • An object of the present invention is to provide an aromatic polycarbonate resin composition excellent in residence heat stability and suppressed in molecular weight reduction and yellowing due to residence under high temperature conditions, and a molded product thereof.
  • the present inventor has found that the above problem can be solved by using a phenolic stabilizer having a spiro ring skeleton and a phosphite stabilizer having a spiro ring skeleton in combination.
  • the gist of the present invention is as follows.
  • R 10A and R 10B each independently represent an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.
  • the total content of the agent (B-1) and the phosphite stabilizer (B-2) having a spiro ring skeleton is 0.01 to 0.15 mass relative to 100 mass parts of the aromatic polycarbonate resin (A). Part of an aromatic polycarbonate resin composition.
  • the viscosity average molecular weight of the aromatic polycarbonate resin (A) contained in the aromatic polycarbonate resin composition pellet is Mv (0)
  • the aromatic polycarbonate resin composition When the viscosity average molecular weight of the aromatic polycarbonate resin (A) contained in the molded article obtained by holding the pellet at 340 ° C. for 20 minutes and then injection molding is Mv (20), it is calculated by the following formula (2).
  • ⁇ Mv Mv (0) ⁇ Mv (20) (2)
  • the aromatic polycarbonate resin composition of the present invention is excellent in residence heat stability and has almost no problem of molecular weight reduction or yellowing due to residence under high temperature conditions.
  • the degree of freedom of the molding cycle can be increased, and the molding can be efficiently performed flexibly according to the situation of the production line. Can be done.
  • the molded article of the aromatic polycarbonate resin composition of the present invention is useful for a wide range of applications such as electrical equipment, communication equipment, precision machinery, automobile parts and the like.
  • the aromatic polycarbonate resin composition of the present invention has excellent residence heat stability, and even when the residence time in the molding machine is long during molding, there are few problems of molecular weight reduction and yellowing due to resin decomposition, and impact resistance.
  • a molded product having excellent mechanical properties such as the above and a hue can be obtained.
  • the molded product formed by molding the aromatic polycarbonate resin composition of the present invention is particularly suitable in the fields of mechanical properties such as impact resistance, transparency, and hue, lens cover, lighting cover, etc. used.
  • the molded article made of the aromatic polycarbonate resin composition of the present invention is particularly suitably used as an automotive lighting cover.
  • the aromatic polycarbonate resin composition of the present invention comprises an aromatic polycarbonate resin (A) and a phenolic stabilizer having a spiro ring skeleton as a stabilizer (B) with respect to 100 parts by mass of the aromatic polycarbonate resin (A). (B-1) 0.005 to 0.1 parts by mass and a phosphite stabilizer (B-2) having a spiro ring skeleton (0.002 to 0.1 parts by mass).
  • the aromatic polycarbonate resin (A) is an aromatic polycarbonate polymer obtained by reacting an aromatic hydroxy compound with a diester of phosgene or carbonic acid.
  • the aromatic polycarbonate polymer may have a branch.
  • the method for producing the aromatic polycarbonate resin is not particularly limited, and may be a conventional method such as a phosgene method (interfacial polymerization method) or a melting method (transesterification method).
  • aromatic dihydroxy compound examples include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxy-3-methylphenyl).
  • Propane 2,2-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy) -3,5-dibromophenyl) propane, 4,4-bis (4-hydroxyphenyl) heptane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxybiphenyl, 3,3 ', 5 , 5′-tetramethyl-4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) Yl) sulfide bis (4-hydroxyphenyl) ether, bis (4- hydroxyphenyl) ketone.
  • 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is particularly preferable.
  • aromatic dihydroxy compound one kind may be used alone, or two or more kinds may be mixed and used.
  • the aromatic polycarbonate resin (A) in addition to the aromatic dihydroxy compound, a small amount of polyhydric phenol having 3 or more hydroxy groups in the molecule may be added. In this case, the aromatic polycarbonate resin (A) has a branch.
  • 1,1,1-tris (4-hydroxylphenyl) ethane or 1,3,5-tris (4-hydroxyphenyl) benzene is preferable.
  • the amount of polyhydric phenol used is preferably 0.01 to 10 mol%, more preferably 0.1 to 2 mol%, based on the aromatic dihydroxy compound (100 mol%).
  • a carbonic acid diester is used as a monomer instead of phosgene.
  • Representative examples of carbonic acid diesters include substituted diaryl carbonates typified by diphenyl carbonate, ditolyl carbonate and the like; dialkyl carbonates typified by dimethyl carbonate, diethyl carbonate, di-tert-butyl carbonate and the like. These carbonic acid diesters can be used alone or in combination of two or more. Among these, diphenyl carbonate and substituted diphenyl carbonate are preferable.
  • the carbonic acid diester may preferably be substituted with dicarboxylic acid or dicarboxylic acid ester in an amount of 50 mol% or less, more preferably 30 mol% or less.
  • Representative dicarboxylic acids or dicarboxylic acid esters include terephthalic acid, isophthalic acid, diphenyl terephthalate, and diphenyl isophthalate.
  • a catalyst When producing an aromatic polycarbonate resin by a transesterification method, a catalyst is usually used. There is no limitation on the catalyst species. As the catalyst, a basic compound such as an alkali metal compound, an alkaline earth metal compound, a basic boron compound, a basic phosphorus compound, a basic ammonium compound, or an amine compound is generally used. Of these, alkali metal compounds and / or alkaline earth metal compounds are particularly preferred. These may be used alone or in combination of two or more. In the transesterification method, the catalyst is generally deactivated with p-toluenesulfonic acid ester or the like.
  • the aromatic polycarbonate resin (A) can be copolymerized with a polymer or oligomer having a siloxane structure for the purpose of imparting flame retardancy and the like.
  • the viscosity average molecular weight of the aromatic polycarbonate resin (A) is preferably 15,000 to 30,000.
  • the viscosity average molecular weight of the aromatic polycarbonate resin (A) is less than 15,000, the obtained molded article has insufficient mechanical strength, and it may not be possible to obtain a product having sufficient mechanical strength.
  • the viscosity average molecular weight of the aromatic polycarbonate resin (A) exceeds 30,000, the melt viscosity of the aromatic polycarbonate resin (A) increases, and thus the molded product is produced by injection molding the aromatic polycarbonate resin composition. In particular, excellent fluidity cannot be obtained.
  • the viscosity average molecular weight of the aromatic polycarbonate resin (A) is more preferably 17,000 to 28,000, and further preferably 18,000 to 25,000.
  • the viscosity average molecular weight of the aromatic polycarbonate resin (A) is calculated from the solution viscosity measured at a temperature of 20 ° C. using methylene chloride as a solvent.
  • the aromatic polycarbonate resin (A) may be a mixture of two or more aromatic polycarbonate resins having different viscosity average molecular weights.
  • the aromatic polycarbonate resin (A) may be prepared by mixing an aromatic polycarbonate resin having a viscosity average molecular weight outside the above range to be within the range of the viscosity average molecular weight.
  • the aromatic polycarbonate resin composition of the present invention includes, as the stabilizer (B), a phenolic stabilizer (B-1) having a spiro ring skeleton (hereinafter sometimes referred to as “component (B-1)”). And a phosphite stabilizer (B-2) having a spiro ring skeleton (hereinafter sometimes referred to as “component (B-2)”).
  • the phenol stabilizer (B-1) having a spiro ring skeleton is not particularly limited as long as it is a phenol compound having a spiro ring skeleton.
  • the phenol-based stabilizer (B-1) having a spiro ring skeleton has a 2,4,8,10-tetraoxaspiro [5.5] undecane ring represented by the following formula (Ia) as a spiro ring Are preferred, and those represented by the following general formula (I) are particularly preferred.
  • R 1A , R 1B , R 3A , R 3B , R 4A and R 4B each independently represent a hydrogen atom or an alkyl group.
  • R 5A and R 5B each independently represent an alkylene group.
  • R 1A , R 1B , R 2A and R 2B are preferably each independently a linear or branched lower alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group. It is.
  • R 3A , R 3B , R 4A and R 4B are preferably each independently a linear or branched alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or a t-butyl group.
  • R 5A and R 5B are preferably each independently a lower alkylene group having 1 to 4 carbon atoms, and more preferably an ethylene group.
  • the alkylene group of R 5A and R 5B may further have an alkyl group as a substituent.
  • R 1A R 1B
  • R 2A R 2B
  • R 3A R 3B
  • R 4A R 4B
  • R 5A R 5B and symmetrical with respect to the central carbon atom of the spiro ring It is preferable that it is a compound of these.
  • phenol-based stabilizer (B-1) having a spiro ring skeleton examples include 3,9-bis [2- ⁇ 3- (3-tert-butyl) represented by the following structural formula (I-1). -4-hydroxy-5-methylphenyl) propionyloxy ⁇ 1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane.
  • the component (B-1) may be used alone or in combination of two or more.
  • the phosphite stabilizer (B-2) having a spiro ring skeleton is not particularly limited as long as it is a phosphite compound having a spiro ring skeleton.
  • the phosphite stabilizer (B-2) having a spiro ring skeleton those represented by the following general formula (II) are preferable.
  • R 10A and R 10B each independently represent an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms.
  • the alkyl groups represented by R 10A and R 10B are preferably each independently a linear or branched alkyl group having 1 to 10 carbon atoms.
  • R 10A and R 10B are aryl groups, aryl groups represented by any of the following general formulas (II-a), (II-b), or (II-c) are preferable.
  • R A represents an alkyl group having 1 to 10 carbon atoms.
  • R B represents an alkyl group having 1 to 10 carbon atoms.
  • the phosphite stabilizer (II-1) having a spiro ring skeleton represented by the general formula (II) may be a compound represented by the following general formula (II-1).
  • R 11 to R 18 each independently represents a hydrogen atom or an alkyl group.
  • R 19 to R 22 each independently represents an alkyl group, an aryl group or an aralkyl group.
  • a to d each independently represent an integer of 0 to 3.
  • R 11 to R 18 are each independently preferably an alkyl group having 1 to 5 carbon atoms, and preferably a methyl group. a to d are preferably 0.
  • phosphite stabilizer (B-2) having a spiro ring skeleton bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diester represented by the following structural formula (II-A) Phosphite and bis (2,4-dicumylphenyl) pentaerythritol diphosphite represented by the following structural formula (II-B) are preferable.
  • the component (B-2) may be used alone or in combination of two or more.
  • the content of the component (B-1) is 0.005 to 0.1 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
  • the content of the component (B-1) is less than 0.005 parts by mass, a sufficient effect of improving the staying heat stability cannot be obtained.
  • the content of the component (B-1) exceeds 0.1 parts by mass, the amount of gas during molding increases or transfer defects due to mold deposits occur, so the light transmittance of the resulting molded product decreases. There is a fear.
  • the content of the component (B-1) is preferably 0.008 to 0.08 parts by mass, more preferably 0.01 to 0.05 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). is there.
  • the content of the component (B-2) is 0.005 to 0.1 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A).
  • the content of the component (B-2) is less than 0.005 parts by mass, it is not possible to obtain a sufficient improvement effect of the residence heat stability. If the content of the component (B-2) exceeds 0.1 parts by mass, the amount of gas at the time of molding increases or transfer defects due to mold deposits occur, so the light transmittance of the resulting molded product decreases. There is a fear.
  • the content of the component (B-2) is preferably 0.008 to 0.08 parts by mass, more preferably 0.01 to 0.05 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). is there.
  • the component (B-1) and the component (B-2) are preferably used in a well-balanced manner in order to more reliably obtain the effect of improving the residence heat stability by using them together.
  • the total content of the component (B-1) and the component (B-2) in the aromatic polycarbonate resin composition of the present invention is 0.01 to 0.00 per 100 parts by mass of the aromatic polycarbonate resin (A).
  • the amount is preferably 15 parts by mass, more preferably 0.02 to 0.12 parts by mass, and still more preferably 0.03 to 0.1 parts by mass.
  • the aromatic polycarbonate resin composition of the present invention may contain a fatty acid ester (C) as a releasing agent in addition to the aromatic polycarbonate resin (A) and the stabilizer (B).
  • Fatty acid ester (C) is a condensation compound of aliphatic carboxylic acid and alcohol.
  • Examples of the aliphatic carboxylic acid constituting the fatty acid ester (C) include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid and tricarboxylic acid.
  • Aliphatic carboxylic acids also include alicyclic carboxylic acids.
  • the aliphatic carboxylic acid is preferably a monocarboxylic acid or dicarboxylic acid having 6 to 36 carbon atoms, and more preferably an aliphatic saturated monocarboxylic acid having 6 to 36 carbon atoms.
  • aliphatic carboxylic acid examples include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melissic acid, tetratriacontanoic acid, montanic acid , Glutaric acid, adipic acid and azelaic acid.
  • Examples of the alcohol constituting the fatty acid ester (C) include saturated or unsaturated monohydric alcohols and polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom, a chlorine atom, a bromine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Aliphatic alcohols also include alicyclic alcohols.
  • Examples of the alcohol include octanol, decanol, dodecanol, tetradecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc.
  • fatty acid ester (C) examples include beeswax (mixture containing myristyl palmitate as a main component), hydrogenated oil, butyl stearate, behenyl behenate, octyldodecyl behenate, stearyl stearate, glycerin monopalmitate, glycerin monopalmitate Stearate, glycerol monooleate, glycerol distearate, glycerol tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, pentaerythritol tetrastearate, etc. .
  • the fatty acid ester (C) may be used alone or in combination of two or more.
  • the aromatic polycarbonate resin composition of the present invention contains the fatty acid ester (C), the content thereof is 0.03 to 0.3 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). preferable.
  • content of fatty acid ester (C) is less than 0.03 mass part, there exists a tendency for the mold release property of the obtained molded article to become inadequate.
  • the content of the fatty acid ester (C) exceeds 0.3 parts by mass, the amount of gas at the time of molding increases or transfer defects due to mold deposits occur, so the light transmittance of the obtained molded product decreases. There is a fear.
  • the content of the fatty acid ester (C) is more preferably 0.06 to 0.25 parts by mass, still more preferably 0.08 to 0.2 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate resin (A). is there.
  • the aromatic polycarbonate resin composition of the present invention may preferably contain an ultraviolet absorber (D). By containing the ultraviolet absorbent (D), the weather resistance of the aromatic polycarbonate resin composition of the present invention can be improved.
  • Examples of the ultraviolet absorber (D) include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds, etc.
  • Organic ultraviolet absorbers and the like can be mentioned. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorber, the transparency and mechanical properties of the aromatic polycarbonate resin composition of the present invention are improved.
  • benzotriazole compound examples include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis ( ⁇ , ⁇ -dimethylbenzyl) phenyl].
  • 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzo Triazol-2-yl) phenol] is preferred.
  • 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole is particularly preferred.
  • benzotriazole compound examples include “Seesorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704” and “Seesorb 709” manufactured by Sipro Kasei Co., Ltd. “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583”, Chemipro Chemical Co., Ltd.
  • benzophenone compound examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxybenzophenone, 2 -Hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4 ' -Dimethoxybenzophenone and the like.
  • benzophenone compound examples include “Seasorb 100”, “Seasorb 101”, “Seasorb 101S”, “Seasorb 102”, “Seasorb 103” manufactured by Sipro Kasei Co., Ltd., “Biosorb 100”, “Biosorb” manufactured by Kyodo Yakuhin Co., Ltd.
  • salicylate compound examples include phenyl salicylate and 4-tert-butylphenyl salicylate.
  • Specific examples of the salicylate compound include “Seasorb 201” and “Seasorb 202” manufactured by Sipro Kasei Co., Ltd., “Chemisorb 21” and “Chemisorb 22” manufactured by Chempro Chemical.
  • Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like.
  • Specific examples of the cyanoacrylate compound include “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Yakuhin Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35” manufactured by BASF Corporation, Ubinur N-539 ”and the like.
  • oxanilide compound examples include 2-ethoxy-2'-ethyloxalinic acid bisalinide and the like.
  • oxalinide compound examples include “Sanduboa VSU” manufactured by Clariant.
  • malonic acid ester compound 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable.
  • Specific examples of the malonic acid ester compound include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by Ciba Specialty Chemicals, and the like.
  • the ultraviolet absorber (D) may be used alone or in combination of two or more.
  • the aromatic polycarbonate resin composition of the present invention contains the ultraviolet absorber (D)
  • the content is usually 0.001 to 3 parts by mass, preferably 100 parts by mass of the aromatic polycarbonate resin (A). Is 0.01 to 1 part by mass, more preferably 0.05 to 0.5 part by mass.
  • content of a ultraviolet absorber (D) is less than the said minimum, a weather-resistant improvement effect may become inadequate.
  • the content of the ultraviolet absorber (D) exceeds the above upper limit value, mold deposits and the like are generated, which may cause mold contamination.
  • an antioxidant In the aromatic polycarbonate resin composition of the present invention, an antioxidant, a release agent, a fluorescent whitening agent, a dye / pigment, a flame retardant, an impact resistance improver, as optional components, as long as the object of the present invention is not impaired.
  • An antistatic agent, a lubricant, a plasticizer, a compatibilizer, a filler and the like may be blended.
  • the method for producing the aromatic polycarbonate resin composition of the present invention is not particularly limited.
  • Examples of the method for producing the aromatic polycarbonate resin composition of the present invention include a method in which the components are mixed or divided and mixed and melt-kneaded at an arbitrary stage until the final molded product is molded.
  • a blending method of each component for example, a method using a tumbler, a Henschel mixer or the like, a method of quantitatively feeding to an extruder hopper with a feeder and mixing, and the like can be mentioned.
  • melt kneading method examples include a method using a single screw kneading extruder, a twin screw kneading extruder, a kneader, a Banbury mixer, and the like.
  • molding method of aromatic polycarbonate resin composition There is no restriction
  • the molding method include an injection molding method, a compression molding method, and an injection compression molding method, and an injection molding method is preferable.
  • the molded article of the aromatic polycarbonate resin composition of the present invention is useful for a wide range of applications such as electrical equipment, communication equipment, precision machinery, and automobile parts.
  • the aromatic polycarbonate resin composition of the present invention has excellent residence heat stability, and even when the residence time in the molding machine is long during molding, there are few problems of molecular weight reduction and yellowing due to resin decomposition, and impact resistance.
  • a molded product having excellent mechanical properties such as the above and a hue can be obtained.
  • the molded product formed by molding the aromatic polycarbonate resin composition of the present invention is particularly suitable in the fields of mechanical properties such as impact resistance, transparency, and hue, lens cover, lighting cover, etc. used.
  • the molded article made of the aromatic polycarbonate resin composition of the present invention is particularly suitably used as an automotive lighting cover.
  • the aromatic polycarbonate resin composition of the present invention is excellent in residence heat stability, and yellowing during the heat residence process is suppressed.
  • the aromatic polycarbonate resin composition of the present invention has a YI value measured on a molded article having a thickness of 2 mm obtained by injection molding after holding the pellet of the aromatic polycarbonate resin composition of the present invention at 340 ° C. for 5 minutes.
  • YI (20) the YI value measured for a molded article having a thickness of 2 mm obtained by injection molding after holding the pellet of the aromatic polycarbonate resin composition at 340 ° C. for 20 minutes.
  • the YI value increase amount ⁇ YI calculated by the equation (1) is preferably excellent in heat-resistant yellowing such that it is preferably 0.3 or less. This ⁇ YI is more preferably 0.2 or less, and still more preferably 0.1 or less.
  • ⁇ YI YI (20) ⁇ YI (5) (1)
  • the YI value of the molded product is measured by the method described in the section of Examples described later.
  • the aromatic polycarbonate resin composition of the present invention is excellent in residence heat stability and has a small decrease in molecular weight due to decomposition of the resin during the heat residence process.
  • the viscosity average molecular weight of the aromatic polycarbonate resin (A) contained in the aromatic polycarbonate resin composition pellets of the present invention is Mv (0), and the pellets are held at 340 ° C. for 20 minutes and then molded by injection molding.
  • the decrease in viscosity average molecular weight ⁇ Mv calculated by the following formula (2) is preferably 1000 or less. It is excellent. This ⁇ Mv is more preferably 900 or less, and still more preferably 700 or less.
  • ⁇ Mv Mv (0) ⁇ Mv (20) (2)
  • the viscosity average molecular weight of the aromatic polycarbonate resin (A) is measured by the method described in the Examples section below.
  • Aromatic polycarbonate resin (A) Aromatic polycarbonate resin manufactured by Mitsubishi Engineering Plastics: Bisphenol A type aromatic polycarbonate resin manufactured by interfacial polymerization (viscosity average molecular weight 21,500)
  • ADEKA STAB AO-60 pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl] propionate represented by the following structural formula (in Tables 1 and 2, “AO— 60 ”)
  • ADEKA STAB PEP-36 manufactured by ADEKA: bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite represented by the structural formula (II-A) (in Tables 1 and 2) , Described as “PEP-36”.
  • DEKA STAB PEP-36 bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite represented by the structural formula (II-A) (in Tables 1 and 2) , Described as “PEP-36”.
  • Doverphos S-9228 manufactured by Properties & Characteristics: bis (2,4-dicumylphenyl) pentaerythritol diphosphite represented by the structural formula (II-B) (in Tables 1 and 2, “S-9228” and (Describe)
  • ADEKA STAB 2112 Tris (2,4-di-tert-butylphenyl) phosphite represented by the following structural formula (indicated as “2112” in Tables 1 and 2)
  • VPG861 Pentaerythritol tetrastearate
  • the intrinsic viscosity ([ ⁇ ]) is a value calculated from the following equation by measuring the specific viscosity ( ⁇ sp ) at each solution concentration (C) (g / dl).
  • the aromatic polycarbonate resin composition of the present invention has excellent residence heat stability and suppresses molecular weight reduction and yellowing during the thermal residence process.
  • Comparative Examples 1 to 3 in which both the phenol-based stabilizer and the phosphite-based stabilizer do not satisfy the provisions of the present invention, or one of the phenol-based stabilizer and the phosphite-based stabilizer is defined by the present invention.
  • Comparative Examples 4 to 6 which do not satisfy the above, Comparative Example 7 using only one of the phenolic stabilizer (B-1) having a spiro ring skeleton and the phosphite stabilizer (B-2) having a spiro ring skeleton In ⁇ 9, the thermal stability of residence is inferior, and there are problems of molecular weight reduction and yellowing during the thermal residence process.

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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)

Abstract

L'invention concerne une composition de résine de polycarbonate aromatique qui présente une excellente stabilité à une exposition à la chaleur prolongée, et dans laquelle une réduction de la masse moléculaire et un jaunissement lié à une exposition prolongée à des conditions de température élevée ont été supprimés. L'invention concerne une composition de résine de polycarbonate aromatique comprenant une résine de polycarbonate aromatique (A), et comme agent stabilisant (B), par rapport à 100 parties en masse de ladite résine de polycarbonate aromatique (A), de 0,005 à 0,1 partie en masse d'un agent stabilisant phénolique (B-1) présentant un squelette spiranique, et de 0,005 à 0,1 partie en masse d'un agent stabilisant phosphite (B-2) présentant un squelette spiranique.
PCT/JP2016/074466 2015-09-04 2016-08-23 Composition de résine de polycarbonate aromatique et produit moulé associé WO2017038547A1 (fr)

Applications Claiming Priority (4)

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JP2015174770 2015-09-04
JP2015-174770 2015-09-04
JP2016145507A JP6183513B2 (ja) 2015-09-04 2016-07-25 芳香族ポリカーボネート樹脂組成物及びその成形品
JP2016-145507 2016-07-25

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62141066A (ja) * 1985-12-13 1987-06-24 Adeka Argus Chem Co Ltd 安定化された合成高分子材料組成物
WO2008133342A1 (fr) * 2007-04-25 2008-11-06 Teijin Limited Composition de résine de polycarbonate
JP2010523742A (ja) * 2007-04-05 2010-07-15 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト ポリカーボネート成形組成物
JP2011157545A (ja) * 2010-01-07 2011-08-18 Mitsubishi Chemicals Corp ポリカーボネート樹脂組成物及びその成形品
JP2013049847A (ja) * 2011-08-03 2013-03-14 Mitsubishi Chemicals Corp 自動車内装品
JP2015093912A (ja) * 2013-11-11 2015-05-18 出光興産株式会社 ポリカーボネート樹脂組成物

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62141066A (ja) * 1985-12-13 1987-06-24 Adeka Argus Chem Co Ltd 安定化された合成高分子材料組成物
JP2010523742A (ja) * 2007-04-05 2010-07-15 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト ポリカーボネート成形組成物
WO2008133342A1 (fr) * 2007-04-25 2008-11-06 Teijin Limited Composition de résine de polycarbonate
JP2011157545A (ja) * 2010-01-07 2011-08-18 Mitsubishi Chemicals Corp ポリカーボネート樹脂組成物及びその成形品
JP2013049847A (ja) * 2011-08-03 2013-03-14 Mitsubishi Chemicals Corp 自動車内装品
JP2015093912A (ja) * 2013-11-11 2015-05-18 出光興産株式会社 ポリカーボネート樹脂組成物

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