JP4787505B2 - Aromatic polycarbonate resin composition and molded article thereof - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition and a molded article thereof.

  Molded products made of aromatic polycarbonate resin are excellent in transparency, impact resistance, heat resistance, dimensional stability, self-extinguishing properties (flame retardant), etc., so electrical / electronic / OA equipment, optical components It is used in a wide range of fields such as precision machinery, automobiles, security / medical care, building materials, and miscellaneous goods. However, since the aromatic polycarbonate resin is usually amorphous, it has the problems of (i) high molding processing temperature, poor melt fluidity, and (ii) poor chemical resistance.

  In addition, as an aromatic polycarbonate resin composition that improves rigidity, flame retardancy, or antistatic property without impairing the excellent properties of a molded article made of an aromatic polycarbonate resin, an inorganic filler such as glass fiber is used. Reinforced aromatic polycarbonate-based resin composition (for example, Patent Document 1), a flame-retardant aromatic polycarbonate-based resin composition (for example, Patent Document 2) to which a flame retardant such as a silicone compound or organic sulfonate is added, An antistatic aromatic polycarbonate resin composition (for example, Patent Document 3) to which an antistatic agent such as a metal salt of benzenesulfonic acid or a phosphonium salt is added has been proposed. However, these aromatic polycarbonate resin compositions also have the problems (i) and (ii).

  In recent years, moldings of aromatic polycarbonate resin compositions have become larger, thinner, more complicated in shape and higher in performance, and are also made of aromatic polycarbonate resins with increasing interest in environmental issues. A resin modifier that improves the melt fluidity of an aromatic polycarbonate resin composition and improves injection moldability without impairing the excellent properties of the molded article, and an aromatic polycarbonate resin composition using the resin modifier It has been demanded.

  Improve the melt fluidity of the aromatic polycarbonate resin composition without impairing the properties (transparency, heat resistance, rigidity, flame retardancy, antistatic property, etc.) of the molded article made of the aromatic polycarbonate resin composition As a method, (1) a method of lowering the molecular weight of an aromatic polycarbonate resin itself, which is a matrix resin, is well known. Also, (2) a method for improving melt flowability by polymer alloying an aromatic polycarbonate resin and a specific styrene resin (for example, Patent Documents 4 and 5), (3) an aromatic polycarbonate resin and A method (for example, Patent Document 6) for improving the melt fluidity by polymer alloying a specific methacrylate resin has been proposed. For the purpose of further improving the melt fluidity of the aromatic polycarbonate resin composition, (4) a method of adding a polyester oligomer (for example, Patent Document 7), (5) a method of adding an oligomer of a polycarbonate (Patent Document 8). ), (6) A method of adding a low molecular weight styrene copolymer (for example, Patent Documents 9 to 11) has been proposed.

However, these conventional methods have the following problems although the melt fluidity is improved to some extent.
In the method (1), although the melt fluidity is greatly improved, a decrease in molecular weight more than necessary impairs the heat resistance, chemical resistance, and impact resistance of a molded product made of an aromatic polycarbonate resin. Therefore, there is a limit to improving the melt fluidity of the aromatic polycarbonate resin composition by reducing the molecular weight of the aromatic polycarbonate resin while maintaining the excellent characteristics of the molded product.

  In the methods (2) and (3), the balance between the peel resistance of the molded product and the melt fluidity of the aromatic polycarbonate resin composition is still insufficient. Specifically, although the method (2) is excellent in the melt fluidity of the aromatic polycarbonate resin composition, the compatibility is still inadequate, so that the surface of the molded product is easily peeled off, and the appearance and mechanical properties are excellent. Decrease significantly. The method (3) is excellent in the compatibility of the aromatic polycarbonate resin composition and the molded article has good transparency, but the effect of improving the melt fluidity of the aromatic polycarbonate resin composition is small. Therefore, in order to improve the melt fluidity, it is necessary to increase the blending amount of the methacrylate resin, and the melt flow of the aromatic polycarbonate resin composition while maintaining the heat resistance, impact resistance, etc. of the molded product. There is a limit to improving the performance.

Although the methods (4) and (5) are effective in improving the melt fluidity of the aromatic polycarbonate resin composition, there is a problem that the heat resistance and impact resistance of the molded product are remarkably lowered.
In the method (6), the melt flowability of the aromatic polycarbonate resin composition can be improved by adding a small amount of the low molecular weight styrene copolymer while maintaining the heat resistance of the molded product to some extent. Compatibility is still insufficient. For this reason, surface layer peeling easily occurs in the molded product, and accordingly, there remains a problem that impact strength, practically important weld appearance, and surface impact are not sufficient.

As described above, none of the conventional methods has been improved in terms of improving the melt fluidity of the aromatic polycarbonate resin-based composition without impairing the excellent properties of the molded article made of the aromatic polycarbonate resin-based composition. Insufficient.
In addition, there are the following problems in order to increase the size, weight, and thickness of a molded article made of an aromatic polycarbonate resin composition by a conventional method.
For example, in the method (1), although the melt viscosity is lowered and the melt fluidity is greatly improved, as the molecular weight is lowered, mechanical properties such as heat resistance and impact resistance are lowered, and further chemical resistance is also improved. There are problems that are spoiled.
JP-A-8-143760 JP 2000-226527 A JP 2003-64249 A Japanese Patent Publication No.59-42024 JP-A-62-138514 Japanese Patent No. 2622152 Japanese Patent Publication No.54-37977 Japanese Patent Laid-Open No. 3-24501 Japanese Patent Publication No.52-784 Japanese Patent Laid-Open No. 11-181197 JP 2000-239477 A

  The object of the present invention is to improve the melt fluidity (moldability) and chemical resistance without impairing the transparency and heat resistance (in addition, rigidity, flame retardancy, antistatic property, etc.) of the obtained molded product. An object of the present invention is to provide an aromatic polycarbonate resin composition and a molded article excellent in transparency, heat resistance and chemical resistance (further, rigidity, flame retardancy, antistatic property, etc.).

The aromatic polycarbonate resin composition of the present invention is an aromatic polycarbonate resin composition in which an aromatic polycarbonate resin (A), a fluidity improver (B), and a stabilizer (C) are blended. The fluidity improver (B) is an aromatic vinyl monomer (b1) 0.5-99.5% by mass, and the monomer (b2) 0.5-99 represented by the following formula (I): And a monomer mixture consisting of 0 to 40% by mass of the other monomer (b3) [provided that the total of the monomers (b1) to (b3) is 100% by mass. ] Is a polymer obtained by polymerizing].

(In formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is an optionally substituted phenyl group.)

The aromatic polycarbonate resin composition of the present invention may further contain an inorganic filler (D).
The aromatic polycarbonate resin composition of the present invention may further contain a flame retardant (E).
The aromatic polycarbonate resin composition of the present invention may further contain an antistatic agent (F).
The molded product of the present invention is formed by molding the aromatic polycarbonate resin composition of the present invention.

The aromatic polycarbonate resin composition of the present invention has a melt fluidity as compared with the conventional one without impairing the transparency and heat resistance (in addition, rigidity, flame retardancy, antistatic properties, etc.) of the molded product obtained. Excellent in moldability and chemical resistance.
The molded article of the present invention is excellent in transparency, heat resistance and chemical resistance (further, rigidity, flame retardancy, antistatic property, etc.).

[Aromatic polycarbonate resin (A)]
The aromatic polycarbonate resin (A) is an aromatic polycarbonate polymer or copolymer obtained by reacting an aromatic hydroxy compound with a carbonic acid diester such as diphenyl carbonate or phosgene. The aromatic polycarbonate resin (A) may be branched. In the case of the branched aromatic polycarbonate resin (A), an aromatic dihydroxy compound and an aromatic polyhydroxy compound are used in combination as the aromatic hydroxy compound.

  As aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4,4 -Dihydroxy diphenyl etc. are mentioned. Of these, bisphenol A is preferred. Furthermore, for the purpose of enhancing the flame retardancy, these aromatic dihydroxy compounds may have a structure substituted with a tetraalkylphosphonium sulfonate, a bromine atom, or a group having a siloxane structure.

  Examples of the aromatic polyhydroxy compound include phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2, 4,6-dimethyl-2,4,6-tri (4 -Hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenylheptene-3,1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1- Examples include tri (4-hydroxyphenyl) ethane, etc. The amount of the aromatic polyhydroxy compound used to obtain the branched aromatic polycarbonate resin (A) is based on the aromatic dihydroxy compound (100 mol%). Preferably, it is 0.01-10 mol%, More preferably, it is 0.1-2 mol%.

  A monovalent aromatic hydroxy compound or a monovalent aromatic hydroxy compound derivative such as a chloroformate thereof may be used for the purpose of adjusting the molecular weight of the aromatic polycarbonate resin (A), adjusting the end group, and the like. Examples of monovalent aromatic hydroxy compounds and derivatives thereof include phenol, m-cresol, p-cresol, p-propylphenol, p-tert-butylphenol, p-long chain alkyl-substituted phenols, and derivatives thereof. It is done. The amount of these monovalent aromatic hydroxy compounds and / or derivatives thereof used is usually 0.1 to 10 mol%, preferably 1 to 8 mol%, based on the aromatic dihydroxy compound (100 mol%). .

The aromatic polycarbonate resin (A) has a dicarboxylic acid or dicarboxylic acid chloride for the purpose of copolymerizing a polymer or oligomer having a siloxane structure for the purpose of enhancing flame retardancy or improving the melt fluidity during molding. Derivatives such as these may be copolymerized.
The molecular weight of the aromatic polycarbonate resin (A) is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 14,000 to 40,000, more preferably 16,000 to 30,000, and 18,000. ˜26000 is particularly preferred. Two or more aromatic polycarbonate resins (A) may be mixed and used.

  As the resin material containing the aromatic polycarbonate resin (A), an aromatic polycarbonate polymer alloy obtained by combining the aromatic polycarbonate resin (A) with other resins and / or elastomers described later may be used.

[Other resins and elastomers]
The aromatic polycarbonate resin composition of the present invention has excellent transparency, impact resistance, heat resistance, dimensional stability, self-extinguishing properties (flame retardant), etc. inherent to the aromatic polycarbonate resin (A). Other resins and / or elastomers may be blended as necessary within a range that is not impaired, specifically, within a range of 50 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin (A).

  Other resins include polystyrene (PSt), styrene random copolymers (acrylonitrile-styrene resin (AS resin), etc.), alternating copolymers of styrene and maleic anhydride, and graft copolymers (acrylonitrile-butadiene-). Styrene resins such as styrene resin (ABS resin), acrylonitrile-ethylene propylene rubber-styrene resin (AES resin), acrylonitrile-acrylate-styrene resin (AAS resin), high impact polystyrene (HIPS), etc .; polyethylene terephthalate (PET) , Polyesters such as polybutylene terephthalate (PBT) and copolymers thereof; acrylic resins such as polymethyl methacrylate (PMMA) and copolymers having methyl methacrylate units; polypropylene (PP) and polyethylene (PE), olefin resins such as ethylene- (meth) acrylic acid copolymer; polyurethane; silicone resin; syndiotactic PS; polyamide such as 6-nylon and 6,6-nylon; polyarylate; polyphenylene sulfide; Examples include various general-purpose resins or engineering plastics such as ether ketone; polysulfone; polyethersulfone polyamideimide; polyacetal.

  As the elastomer, isobutylene-isoprene rubber; polyester-based elastomer; styrene-butadiene rubber, polystyrene-polybutadiene-polystyrene (SBS), polystyrene-poly (ethylene-butylene) -polystyrene (SEBS), polystyrene-polyisoprene-polystyrene (SIS). Styrene elastomers such as polystyrene-poly (ethylene-propylene) -polystyrene (SEPS); polyolefin elastomers such as ethylene-propylene rubber; polyamide elastomers; acrylic elastomers; diene rubbers, acrylic rubbers, silicone rubbers, etc. Containing methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-styrene resin (MAS tree) ) Impact modifiers such as core-shell type represented by like.

[Flowability improver (B)]
The fluidity improver (B) is an aromatic vinyl monomer (b1) 0.5 to 99.5% by mass, and a monomer (b2) 0.5 to 99.5 represented by the following formula (I). And a monomer mixture composed of 0 to 40% by mass of the other monomer (b3) [provided that the total of the monomers (b1) to (b3) is 100% by mass. ] Is a polymer obtained by polymerizing.

(In formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is an optionally substituted phenyl group.)
The fluidity improver (B) is a fragrance that exhibits phase separation behavior with the aromatic polycarbonate resin (A) during melt molding and has a good level of peel resistance in the use temperature range of the molded product. Because it exhibits compatibility (affinity) with the aromatic polycarbonate resin (A), it does not impair the properties (heat resistance, impact resistance, etc.) of the aromatic polycarbonate resin (A), and has an unprecedented melt fluidity. (Formability) and chemical resistance are improved.

  The fluidity improver (B) includes a mixing ratio (% by mass) of each monomer in the monomer mixture before polymerization, and a content (% by mass) of each monomer constituent unit in the polymer after polymerization. ) Is preferably the same. In order to obtain such a polymer, the polymerization rate of the monomer mixture is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 97% by mass or more. . When the polymerization rate is 90% by mass or more, the mixing ratio (% by mass) of each monomer in the monomer mixture before polymerization and the content (mass of each monomer constituent unit in the polymer after polymerization) %) Is almost the same. When the polymerization rate is less than 90% by mass, the mixing ratio (% by mass) of each monomer in the monomer mixture and the content (mass of monomer constituent units contained in the polymer after polymerization) %) May be different.

  Examples of the aromatic vinyl monomer (b1) include styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, p-methoxystyrene, o-methoxystyrene, 2,4-dimethylstyrene, Examples include chlorostyrene, bromostyrene, vinyl toluene, vinyl naphthalene, vinyl anthracene and the like. These may be used alone or in combination of two or more. Of these, styrene, α-methylstyrene, and pt-butylstyrene are preferable.

Content of an aromatic vinyl monomer (b1) is 0.5-99.5 mass% in a monomer mixture (100 mass%). When the content of the aromatic vinyl monomer (b1) is within this range, the fluidity improver (B) exhibits an excellent effect of improving melt fluidity and chemical resistance.
When the content of the aromatic vinyl monomer (b1) exceeds 99.5% by mass, the compatibility with the aromatic polycarbonate resin (A) becomes insufficient, and as a result, the molded product causes delamination, and the appearance And may damage the mechanical properties. If the content of the aromatic vinyl monomer (b1) is less than 0.5% by mass, the compatibility with the aromatic polycarbonate resin (A) becomes too good, so that the phase separation behavior is fully exhibited during melting. It cannot be done, and the effect of improving the melt fluidity tends to decrease and the effect of improving the chemical resistance tends to decrease.

  Considering the balance between appearance and mechanical properties, melt fluidity and chemical resistance, the content of the aromatic vinyl monomer (b1) is preferably 98% by mass or less, more preferably 96% by mass or less, and 93 The mass% or less is further preferable, and 90 mass% or less is particularly preferable. Moreover, 10 mass% or more is preferable, as for content of an aromatic vinyl monomer (b1), 20 mass% or more is more preferable, 50 mass% or more is further more preferable, and 70 mass% or more is especially preferable.

  As the monomer (b2) represented by the formula (I), phenyl (meth) acrylate, 4-t-butylphenyl (meth) acrylate, bromophenyl (meth) acrylate, dibromo (meth) acrylate Examples include phenyl, 2,4,6-tribromophenyl (meth) acrylate, monochlorophenyl (meth) acrylate, dichlorophenyl (meth) acrylate, trichlorophenyl (meth) acrylate, and the like. These may be used alone or in combination of two or more. Of these, phenyl (meth) acrylate is particularly preferred. In the present invention, “(meth) acrylic acid” means acrylic acid and / or methacrylic acid.

Content of a monomer (b2) is 0.5-99.5 mass% in a monomer mixture (100 mass%). If content of a monomer (b2) exists in this range, a fluidity improver (B) will express the improvement effect of the outstanding compatibility (peeling resistance).
When the content of the monomer (b2) is less than 0.5% by mass, the compatibility with the aromatic polycarbonate resin (A) becomes insufficient, and as a result, the molded product causes delamination, and the appearance and machine The characteristics may be impaired. When the content of the monomer (b2) exceeds 99.5% by mass, the compatibility with the aromatic polycarbonate resin (A) becomes too good, so that the phase separation behavior can be sufficiently exhibited during melting. However, the effect of improving the melt fluidity tends to decrease and the effect of improving the chemical resistance tends to decrease.

  Considering the balance between appearance and mechanical properties, melt fluidity and chemical resistance, the content of the monomer (b2) is preferably 90% by mass or less, more preferably 80% by mass or less, and 50% by mass or less. Is more preferable, and 30% by mass or less is particularly preferable. Moreover, 2 mass% or more is preferable, as for content of a monomer (b2), 4 mass% or more is more preferable, 7 mass% or more is further more preferable, and 10 mass% or more is especially preferable.

  The polymer constituting the fluidity improver (B) can be copolymerized with the aromatic vinyl monomer (b1) and the monomer (b2) as required, as long as the above-mentioned properties are not impaired. The monomer (b3) may be contained in an amount of 0 to 40% by mass.

  The other monomer (b3) is an α, β-unsaturated monomer. Such monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as (meth) acrylic acid cyclohexyl, (meth) acrylic acid benzyl, (meth) acrylic acid t-butyl, (meth) acrylic acid isobornyl, (meth) acrylic acid t-butylcyclohexyl; Reactive functional groups such as (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, 2-methacryloyloxyethyl phthalate, allyl (meth) acrylate, 1,3-butylene dimethacrylate (Meth) acrylic acid ester having vinyl benzoate, vinyl acetate, Water maleate, N- phenylmaleimide, cyclohexylmaleimide, divinylbenzene and the like. These may be used alone or in combination of two or more.

  Content of another monomer (b3) is 0-40 mass% in a monomer mixture (100 mass%). When the content of the monomer (b3) exceeds 40% by mass, the effect of improving the melt fluidity and chemical resistance of the aromatic polycarbonate resin composition tends to be lowered. The content of the other monomer (b3) is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less.

Since the fluidity improver (B) is excellent in compatibility with the aromatic polycarbonate resin (A), the transparency of the molded product made of the aromatic polycarbonate resin composition containing the fluid polycarbonate resin is improved. The polymer constituting the fluidity improver (B) is a two-component system of an aromatic vinyl monomer (b1) and a monomer (b2) represented by the formula (I), and the content thereof is further increased. By making it within a specific range, it becomes possible to express extremely high transparency.
As a polymer which expresses extremely high transparency, a polymer comprising 0.5 to 40% by mass of an aromatic vinyl monomer (b1) and 60 to 99.5% by mass of a monomer (b2) ( B1) (total amount of both is 100% by mass), aromatic vinyl monomer (b1) 60-99.5% by mass and monomer (b2) 0.5-40% by mass There are two combinations (B2) (the total amount of both is 100% by mass).

  The mass average molecular weight of the polymer constituting the fluidity improver (B) is preferably 5,000 to 200,000. If the mass average molecular weight is less than 5,000, relatively low molecular weight substances are increased, which may reduce various properties such as heat resistance and rigidity. In addition, there is a possibility that problems such as smoke generation at the time of melt molding, mist, mechanical dirt, appearance defects of molded products such as fish eyes and silver may increase. When a molded article having good transparency at high temperature (molded article having a low haze temperature dependency) is required, the polymer should have a higher mass average molecular weight. Therefore, the weight average molecular weight of the polymer is preferably 10,000 or more, more preferably 15,000 or more, further preferably 30000 or more, and particularly preferably 40000 or more.

  Moreover, when the mass average molecular weight of the polymer exceeds 200,000, the melt viscosity of the aromatic polycarbonate resin composition becomes high, and there is a possibility that sufficient effect of improving melt fluidity cannot be obtained. In the case where it is desired to improve only the chemical resistance, there is no particular problem even if the mass average molecular weight of the polymer exceeds 200,000. If a significant effect of improving melt fluidity is required, the polymer should have a lower mass average molecular weight. Therefore, the weight average molecular weight of the polymer is preferably 170000 or less, more preferably 150,000 or less, further preferably 120,000 or less, and particularly preferably 100,000 or less.

  The molecular weight distribution of the polymer constituting the fluidity improver (B), that is, the mass average molecular weight (Mw) / number average molecular weight (Mn) is preferably smaller. The molecular weight distribution is preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less. If the molecular weight distribution exceeds 4.0, the melt viscosity of the aromatic polycarbonate resin composition also increases, and there is a possibility that sufficient effect of improving melt fluidity cannot be obtained.

  Examples of the method for producing the polymer constituting the fluidity improver (B) include an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method. Among these, the suspension polymerization method and the emulsion polymerization method are preferable because the recovery method is easy. In the case of the emulsion polymerization method, residual salts in the polymer may cause thermal decomposition of the aromatic polycarbonate resin. Therefore, at the time of emulsion polymerization, a carboxylate emulsifier or the like is used, and the polymer is recovered by acid precipitation coagulation or the like, or a nonionic anionic emulsifier such as a phosphate ester is used, and the polymer is calcium acetate salt or the like. It is preferable to recover by salting out coagulation using

  What is necessary is just to determine the compounding quantity of a fluid improvement agent (B) suitably according to a desired physical property. In order to obtain an effective effect of improving melt fluidity without deteriorating the properties (transparency, heat resistance, impact resistance, etc.) of the aromatic polycarbonate resin (A), the blending of the fluidity improver (B) The amount is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A) and other resins and / or elastomers. If the blending amount of the fluidity improver (B) is less than 0.1 parts by mass, a sufficient effect of improving melt fluidity may not be obtained. If the blending amount of the fluidity improver (B) exceeds 30 parts by mass, the excellent mechanical properties of the aromatic polycarbonate resin (A) may be impaired. The blending amount of the fluidity improver (B) is preferably 1 part by mass or more and more preferably 2 parts by mass or more with respect to a total of 100 parts by mass of the aromatic polycarbonate resin (A) and other resins and / or elastomers. It is preferably 3 parts by mass or more. Further, the blending amount of the fluidity improver (B) is preferably 25 parts by mass or less, and 15 parts by mass or less with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A) and other resins and / or elastomers. Is more preferable, and 10 parts by mass or less is particularly preferable.

[Stabilizer (C)]
The stabilizer (C) is an ultraviolet absorber, a light stabilizer, an antioxidant, or a heat stabilizer. These may be used alone or in combination of two or more.

  An ultraviolet absorber improves the weather resistance and light resistance of the molded article which consists of an aromatic polycarbonate-type resin composition of this invention. Examples of the UV absorber include various UV absorbers such as a benzotriazole UV absorber, a benzophenone UV absorber, a salicylate UV absorber, a cyanoacrylate UV absorber, and a nickel UV absorber. Of these, benzophenone ultraviolet absorbers and benzotriazole ultraviolet absorbers having high heat resistance are preferred.

  Examples of benzophenone-based ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2-hydroxy-4- Methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydroxy-2- Methoxyphenyl) meta , 2-hydroxy -4-n-dodecyloxy benzoin phenone, 2-hydroxy-4-methoxy-2'-carboxy benzophenone. These may be used alone or in combination of two or more.

  Examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′-methylenebis [4- (1,1,3 , 3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy -3,5-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy 3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3-benzoxazine-4 -One), 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole and the like. These may be used alone or in combination of two or more.

  The compounding amount of the ultraviolet absorber is 0.01 to 2 parts by mass with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A) and other resin and / or elastomer and the fluidity improver (B). preferable.

A light stabilizer improves the weather resistance and light resistance of the molded article which consists of an aromatic polycarbonate-type resin composition of this invention.
Examples of the light stabilizer include hindered amine light stabilizers (HALS). The light stabilizer is preferably used in combination with an ultraviolet absorber.
The blending amount of the light stabilizer is 0.01 to 2 parts by mass with respect to a total of 100 parts by mass of the aromatic polycarbonate resin (A) and other resin and / or elastomer and the fluidity improver (B). preferable.

Antioxidants prevent deterioration due to heat, particularly during the preparation, molding and use of the resin composition.
Antioxidants include known antioxidants, for example, phenolic antioxidants such as hindered phenols; phosphorus antioxidants such as phosphite antioxidants and phosphonite antioxidants; sulfur such as thioethers And system antioxidants. Of these, the combined use of a phenolic antioxidant having low volatility and good oil resistance and a phosphorus antioxidant that improves the initial color during molding is preferred.

  Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol-bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4,6- Lis (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5- Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 3,9-bis {1,1-dimethyl-2- And [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane.

  The compounding quantity of antioxidant is 0.001-0.05 mass with respect to a total of 100 mass parts of aromatic polycarbonate-type resin (A), another resin and / or elastomer, and a fluid improvement agent (B). Part is preferred.

The heat stabilizer prevents deterioration due to heat particularly during the preparation, molding and use of the resin composition.
Examples of the heat stabilizer include phosphoric acid derivatives such as phosphoric acid ester, phosphorous acid, phosphonous acid, phosphonic acid, and esters thereof.

  Examples of the heat stabilizer include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl) -4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphos Ite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl Phosphate, dioctyl phosphate, diisopropyl phosphate, tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4 ′ -Biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) 4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4, 4′-biphenylenediphosphonite, tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4 ′ -Biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenyl Rangephosphonite, bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite, benzenephosphone Examples thereof include dimethyl acid, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

Of these, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, bis (2,4- Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred. These may be used alone or in combination of two or more.
The blending amount of the heat stabilizer is 0.001 to 0.15 mass relative to 100 mass parts in total of the aromatic polycarbonate resin (A) and other resin and / or elastomer and the fluidity improver (B). Part is preferable, and 0.002 to 0.07 part by mass is more preferable.

[Inorganic filler (D)]
Examples of the inorganic filler (D) include glass fiber, glass milled fiber, glass flake, glass bead, carbon fiber, silica, alumina, titanium oxide, calcium sulfate powder, gypsum, gypsum whisker, barium sulfate, talc, mica. , Layered compounds such as clay, wollastonite, calcium silicate, carbon black, graphite, iron powder, copper powder, molybdenum disulfide, silicon carbide, silicon carbide fiber, brass fiber, stainless steel fiber, potassium titanate fiber whisker, An aromatic polyamide fiber etc. are mentioned. Of these, commercially available glass fibers called milled fibers, cut fibers, glass powders, etc., fibrous reinforcing agents such as pitch-based and PAN-based carbon fibers, and layered compounds are preferred. These may be used alone or in combination of two or more. Moreover, what performed various surface treatments to the fibrous reinforcing agent or the layered compound may be used.

The glass fiber is preferably a glass fiber having an average fiber diameter of 5 to 15 μm and an average fiber length of 2 to 5 mm. The carbon fiber may be either PAN-based or pitch-based, and is preferably carbon fiber having an average fiber diameter of 6 to 9 μm and an average fiber length of 3 to 8 mm.
Moreover, as an inorganic filler (D) which does not impair the outstanding transparency of the molded article which consists of an aromatic polycarbonate-type resin composition, the difference of refractive index with an aromatic polycarbonate-type resin (A) is 0.015 or less. Particularly preferred are glass fibers or layered silicates having a cation exchange capacity of 50 to 200 meq / 100 g.

The difference is 0.015 or less of the glass fiber having a refractive index of an aromatic polycarbonate-based resin (A), the exception of B ₂ O _3, F ₂ components from the composition components constituting the E glass, MgO, TiO _2, ZnO The ratio of components such as is increased. Examples of such glass fibers include ECR glass (refractive index: 1.579) manufactured by Asahi Fiber Glass Co., Ltd.
The layered silicate having a cation exchange capacity of 50 to 200 meq / 100 g is composed of a combination of a SiO ₄ tetrahedral sheet structure composed of SiO ₂ chains and an octahedral sheet structure containing Al, Mg, Li and the like. It is a silicate (silicate) or clay mineral (clay) in which exchangeable cations are coordinated between the layers. Examples of the silicate (silicate) or clay mineral (clay) include smectite minerals, vermiculite, halloysite, and swellable mica.

Examples of smectite minerals include montmorillonite, hectorite, fluorine hectorite, saponite, beidellite, and stevensite. Examples of the swellable mica include swellable synthetic mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, and Li-type tetrasilicon fluorine mica.
These layered silicates may be either natural products or synthetic products. The synthetic product is produced by, for example, hydrothermal synthesis, melt synthesis, or solid reaction. Among the layered silicates, from the viewpoint of cation exchange capacity, etc., swelled fluorine such as smectite clay minerals such as montmorillonite and hectorite, Li type fluorine teniolite, Na type fluorine teniolite, Na type tetrasilicon fluorine mica Mica is preferable, and montmorillonite obtained by purifying bentonite or synthetic fluorine mica is more preferable in terms of purity and the like. Of these, synthetic fluorine mica that can provide good mechanical properties and thermal stability is particularly preferable.

  The compounding quantity of an inorganic filler (D) is 1-100 mass parts with respect to a total of 100 mass parts of aromatic polycarbonate-type resin (A), another resin, and / or an elastomer, and a fluid improvement agent (B). Is preferred. If the blending amount of the inorganic filler (D) is less than 1 part by mass, the intended strength, rigidity and heat resistance may not be obtained. When the compounding quantity of an inorganic filler (D) exceeds 100 mass parts, the melt fluidity | liquidity of an aromatic polycarbonate-type resin composition will fall, and melt molding may become extremely difficult. The blending amount of the inorganic filler (D) is 5 to 80 parts by mass with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A) and other resin and / or elastomer and the fluidity improver (B). Is more preferable, and 20-50 mass parts is especially preferable. The blending amount of the inorganic filler (D) is determined in consideration of the required properties such as strength, rigidity, heat resistance of the molded product, fluidity of the aromatic polycarbonate resin composition, and the type of the inorganic filler (D). It is determined by comprehensive judgment based on the kind and amount of the group polycarbonate resin (A), the kind and amount of the fluidity improver (B), and the like.

[Flame Retardant (E)]
Flame retardants (E) include halogenated flame retardants such as brominated flame retardants such as tetrabromobisphenol A and decabromodiphenyl oxide, and chlorinated flame retardants such as chlorinated paraffin and chlorinated polyethylene; non-halogen phosphate esters Phosphorus flame retardants (monophosphate / condensation), halogen-containing phosphate ester flame retardants (monophosphate / condensation), inorganic phosphate flame retardants, red phosphorus flame retardants and other phosphorus flame retardants; antimony trioxide, Examples thereof include inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide; organic salt flame retardants, silicone flame retardants and the like. These may be used alone or in combination of two or more.

  Preferred flame retardants (E) include halogenated bisphenol A, halogenated polycarbonate oligomers, halogenated bisphenol A polycarbonate flame retardants, halogenated compounds such as brominated epoxy compounds, and flame retardant aids such as antimony oxide. Combined halogen flame retardants; Organic salt flame retardants; Phosphorus flame retardants such as aromatic phosphate ester flame retardants, halogenated aromatic phosphate ester flame retardants; Branched phenyl silicone compounds and phenyl silicone resins And silicone flame retardants such as organopolysiloxanes. These may be used alone or in combination of two or more.

Examples of the polycarbonate-type flame retardant of halogenated bisphenol A include a polycarbonate-type flame retardant of tetrabromobisphenol A, a copolymer polycarbonate-type flame retardant of tetrabromobisphenol A and bisphenol A, and the like.
Organic salt flame retardants include dipotassium diphenylsulfone-3,3′-disulfonate, potassium diphenylsulfone-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,5-trichlorobenzenesulfone. Potassium phosphate, potassium bis (2,6-dibromo-4-cumylphenyl) phosphate, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphate) imide, bis ( 2,4,6-tribromophenyl) potassium phosphate, potassium bis (2,4-dibromophenyl) phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, perfluoro Potassium butanesulfonate, sodium lauryl sulfate Or potassium, sodium hexadecyl sulfate or potassium.

Examples of the halogenated aromatic phosphate ester type flame retardant include tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate, and the like. .
Aromatic phosphate ester flame retardants include triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,6-xylyl) resorcin diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate, tetrakis (2,6-xylyl) -4,4′-biphenol diphosphate, tetraphenylresorcin diphosphate, tetraphenylhydroquinone diphosphate, tetraphenyl-4,4′-biphenol diphosphate, the aromatic ring source is resorcin and phenol Aromatic polyphosphates containing no phenolic OH groups, aromatic ring sources resorcinol and phenol, aromatic polyphosphates containing phenolic OH groups, aromatic ring sources hydroquinone and phenol Aromatic polyphosphates that do not contain a phenolic OH group, aromatic polyphosphates whose aromatic ring source is hydroquinone and phenol and that contain a phenolic OH group (the “aromatic polyphosphate” shown below contains a phenolic OH group) Aromatic polyphosphates and aromatic polyphosphates not containing), aromatic polyphosphates whose aromatic ring source is bisphenol A and phenol, aromatic whose aromatic ring source is tetrabromobisphenol A and phenol Polyphosphates, aromatic polyphosphates where the aromatic ring source is resorcin and 2,6-xylenol, aromatic polyphosphates where the aromatic ring source is hydroquinone and 2,6-xylenol, aromatic ring sources are bisphenol A and 2,6- Ki Examples include aromatic polyphosphates that are silenol, aromatic polyphosphates whose aromatic ring source is tetrabromobisphenol A and 2,6-xylenol, and the like.

  The blending amount of the flame retardant (E) is 0.01 to 30 mass with respect to a total of 100 mass parts of the aromatic polycarbonate resin (A) and other resin and / or elastomer and the fluidity improver (B). Part is preferable, 0.02 to 25 parts by mass is more preferable, and 0.05 to 20 parts by mass is particularly preferable. If the blending amount of the flame retardant (E) is less than 0.01 parts by mass, the target flame retardancy may not be obtained. If the blending amount of the flame retardant (E) exceeds 30 parts by mass, the heat resistance and impact resistance of the molded product may be lowered. The blending amount of the flame retardant (E) is determined in consideration of the flame retardant required characteristics of the molded product, the kind of the flame retardant, the kind and amount of the aromatic polycarbonate resin (A), the kind of the fluidity improver (B) and It is determined by comprehensive judgment based on the amount.

[Antistatic agent ( F )]
Antistatic agents ( F ) include various anionic, cationic, amphoteric and nonionic surfactants such as alkyl metal salts of sulfonic acids, phosphonium salts of sulfonic acids, and ammonium salts; polyethylene oxides, polyether esters Polyether type polymer antistatic agent such as amide, polyether amide imide, ethylene oxide / shrimp halohydrin copolymer, methoxypolyethylene glycol (meth) acrylate copolymer; fatty acid ester compound, carbon, graphite, metal powder, etc. It is done. These may be used alone or in combination of two or more.

Of these, sulfonic acid metal salts such as sodium alkyl sulfonate and sodium alkylbenzene sulfonate; phosphonium sulfonates such as alkyl sulfonic acid phosphonium salt and alkyl benzene sulfonic acid phosphonium salt because of high heat resistance and good transparency. Preferred are salts; polyether ester copolymers having a sulfonate group.
Examples of the sulfonic acid metal salt and phosphonium salt include sodium benzenesulfonate, calcium benzenesulfonate, magnesium benzenesulfonate, barium benzenesulfonate, phosphonium dodecylbenzenesulfonate, and tetrabutylphosphonium dodecylbenzenesulfonate. .

The compounding quantity of antistatic agent ( F ) is 0.01-5 with respect to a total of 100 mass parts of aromatic polycarbonate-type resin (A), another resin, and / or an elastomer, and a fluid improvement agent (B). Mass parts are preferred, 0.05 to 3.0 parts by mass are more preferred, and 0.5 to 2.5 parts by mass are particularly preferred. When the blending amount of the antistatic agent ( F ) is less than 0.01 parts by mass, a sufficient antistatic effect cannot be obtained. When the blending amount of the antistatic agent ( F ) exceeds 5.0 parts by mass, the mechanical properties of the molded article made of the aromatic polycarbonate resin composition are inferior, and the transparency and appearance may be deteriorated. The blending amount of the antistatic agent ( F ) is determined in consideration of the required characteristics of the molded product, the kind of the antistatic agent, the kind and amount of the aromatic polycarbonate resin (A), the kind of the flow improver (B) and It is determined by comprehensive judgment based on the amount .

[Other additives]
A release agent may be added to the aromatic polycarbonate resin composition of the present invention within a range that does not impair the object of the present invention in order to further improve the releasability from the mold during melt molding. Examples of the release agent include fatty acid esters, polyorganosiloxane, paraffin wax, beeswax and the like. The amount of the release agent added is 0.001 to 0.5 mass with respect to a total of 100 mass parts of the aromatic polycarbonate resin (A) and other resin and / or elastomer and the fluidity improver (B). Part is preferred.

  You may add a bluing agent to the aromatic polycarbonate-type resin composition of this invention in the range which does not impair the objective of invention. The bluing agent is effective for eliminating the yellowishness of the molded product made of the aromatic polycarbonate resin composition. In the case of molded products with weather resistance, since a certain amount of UV absorber is used, the molded product tends to have a yellowish tint depending on the action or color of the UV absorber, and in particular, it is naturally transparent to molded products such as sheets. The addition of a bluing agent is very effective for imparting a feeling.

Examples of the bluing agent include Macrolex Violet B from Bayer and Triazole Blue RLS from Sand.
The addition amount of the bluing agent is preferably 0.05 to 2 ppm with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A) and other resin and / or elastomer and the fluidity improver (B), 0.5 to 1.5 ppm is more preferable. If the amount of the bluing agent is too large, the blueness of the molded product may become strong and the luminous transparency may be lowered.

  A non-drip agent may be added to the aromatic polycarbonate resin composition of the present invention for the purpose of preventing melt dripping during combustion. Examples of the non-drip agent include fluoroolefin resins mainly composed of a fluoroolefin resin. The fluoroolefin resin is a polymer, copolymer, or composite containing a fluoroethylene structure. Examples of the fluoroolefin resin include a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, a copolymer of tetrafluoroethylene and an ethylene monomer not containing fluorine, and tetrafluoroethylene. Examples thereof include a composite of a polymer and a vinyl resin such as an acrylic resin. Of these, polytetrafluoroethylene (PTFE) is preferred. The mass average molecular weight of polytetrafluoroethylene is preferably 500,000 or more, particularly preferably 500,000 to 10,000,000. Any known polytetrafluoroethylene can be used.

Among polytetrafluoroethylenes, those having fibril-forming ability are preferable because they can impart higher melt dripping prevention properties. Examples of the polytetrafluoroethylene having fibril forming ability include those classified as type 3 in the ASTM standard. Examples of polytetrafluoroethylene classified as type 3 include Teflon (registered trademark) 6-J (manufactured by Mitsui DuPont Fluorochemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201 (Daikin Industries). CD1, CD076 (manufactured by Asahi IC Fluoropolymers Co., Ltd.) and the like.
Examples of polytetrafluoroethylene other than those classified as type 3 include Algoflon F5 (manufactured by Montefluos Co., Ltd.), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries, Ltd.), and the like. These polytetrafluoroethylenes may be used alone or in combination of two or more.

  The added amount of the non-drip agent is 0.05 to 5 parts by mass with respect to 100 parts by mass in total of the aromatic polycarbonate resin (A) and other resin and / or elastomer and the fluidity improver (B). Preferably, 0.1 to 2 parts by mass is more preferable. When the addition amount of the non-drip agent is less than 0.05 parts by mass, the melt resistance in the target flame retardancy may not be sufficient. Even if the added amount of the non-drip agent exceeds 5 parts by mass, the effect commensurate with this is not improved, and the impact resistance and appearance of the molded product may be adversely affected. The amount of the non-drip agent added depends on the degree of flame retardancy required for the molded product, for example, UL94 V-0, V-1, V-2, etc. May be determined as appropriate.

[Aromatic polycarbonate resin composition]
The aromatic polycarbonate resin composition of the present invention includes, for example, an aromatic polycarbonate resin (A), a fluidity improver (B), and a stabilizer (C), and other resins, elastomers, and inorganic fillers as necessary. Mixing agent (D), flame retardant (E), antistatic agent (F), and other additives with a tumbler, V-type blender, super mixer, nauter mixer, Banbury mixer, kneading roll, extruder, etc. Can be prepared.

  The blending of various additives may be carried out in one step or in two or more steps. As a method to be carried out in two stages, for example, after various additives are blended in advance, this is blended with the aromatic polycarbonate resin (A) and the fluidity improver (B); A part of the resin-based resin (A) and various additives and fluidity improver (B) are blended, that is, the various additives are diluted with the aromatic polycarbonate-based resin (A) to obtain a master batch of various additives. Then, the method of blending this masterbatch and aromatic polycarbonate resin (A) is mentioned.

The aromatic polycarbonate resin composition of the present invention can provide a molded product particularly excellent in transparency. More specifically, it is possible to provide a molded product having transparency in which the haze of the molded product having a thickness of 2 mm is in the range of 0.1 to 5%. Moreover, when the above-mentioned polymer (B1) or polymer (B2) is used as the fluidity improver (B), the haze of the molded product having a thickness of 3 mm is excellent in the range of 0.1 to 2%. It is possible to provide a molded product having high transparency.
In addition, the aromatic polycarbonate resin composition of the present invention can provide a molded product in which transparency is maintained within a practical temperature range (room temperature to high temperature). High temperature here is the range of 60-100 degreeC.

〔Molding〕
The molded product of the present invention is the injection molding method, the extrusion molding method, the compression molding method, the blow molding method, the casting after the aromatic polycarbonate resin composition of the present invention as it is or after being once pelletized with a melt extruder. It can be obtained by molding by a known method such as a molding method. In particular, the aromatic polycarbonate resin composition of the present invention is useful as a raw material for injection molded products.

  In the aromatic polycarbonate resin composition of the present invention described above, it is melted compared to the conventional one without impairing the transparency, heat resistance, rigidity, flame retardancy, antistatic property, etc. of the obtained molded product. Excellent fluidity (formability) and chemical resistance. In particular, the chemical resistance of the resulting molded product and the melt flowability (moldability) of the resin composition are remarkably excellent, so that demands for electrical / electronic / OA equipment, optical parts, and precision machinery have been increasing in recent years. It is suitable for various large / thin-wall injection molded products for automobiles, safety / medical use, building materials, miscellaneous goods, and injection molded products requiring chemical resistance.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the following description, “parts” and “%” mean “parts by mass” and “% by mass” unless otherwise specified.

(Production Example 1)
Production of fluidity improver (B-1):
In a separable flask equipped with a condenser and a stirrer, anionic emulsifier ("Latemul ASK", manufactured by Kao Corporation) (solid content 28%) 1.0 part (solid content), 295 parts distilled water, Heated to 80 ° C. in a water bath under nitrogen atmosphere. Then, in a separable flask, 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.3 part of Rongalite were added in 5 parts of distilled water. A mixture of 5 parts, phenyl methacrylate 12.5 parts, t-butyl hydroperoxide 0.2 parts and n-octyl mercaptan 0.5 parts was added dropwise over 180 minutes. Thereafter, the mixture was stirred at 80 ° C. for 60 minutes to obtain a polymer emulsion (polymerization rate: 98%).

  While stirring, 300 parts of an aqueous solution in which sulfuric acid was dissolved at a ratio of 0.7% was heated to 70 ° C., and the polymer emulsion obtained therein was gradually added dropwise to solidify the polymer. The precipitate was separated and washed, and then dried at 75 ° C. for 24 hours to obtain a polymer (fluidity improver (B-1)). The weight average molecular weight (Mw) was 49000, and the molecular weight distribution (Mw / Mn) was 2.1.

(Production Example 2)
Production of fluidity improver (B-2):
A polymer (fluidity improver (B-2)) was obtained by the same method as in Production Example 1 except that the amount of n-octyl mercaptan was changed from 0.5 part to 0.2 part (polymerization rate was 98%). The weight average molecular weight (Mw) was 97000, and the molecular weight distribution (Mw / Mn) was 2.0.

(Production Example 3)
Production of fluidity improver (B-3):
A polymer (flowability improver (B-3) was prepared in the same manner as in Production Example 1 except that 25 parts of styrene, 75 parts of phenyl methacrylate, and the amount of n-octyl mercaptan were changed from 0.5 part to 2 parts. )) Was obtained (polymerization rate 99%). The weight average molecular weight (Mw) was 27000, and the molecular weight distribution (Mw / Mn) was 1.9.

(Production Example 4)
Production of fluidity improver (B-4):
A separable flask equipped with a condenser and a stirrer was charged with 0.4 parts of calcium phosphate and 150 parts of distilled water, then 87.5 parts of styrene, 12.5 parts of phenyl methacrylate, 2,2′-azobis (isobutyrate). (Ronitrile) 1 part and a mixture in which 0.7 part of α-methylstyrene dimer was dissolved were added and stirred for a while, followed by nitrogen bubbling for 30 minutes. The mixture was stirred at 80 ° C. for 4 hours under a nitrogen atmosphere, and further stirred at 90 ° C. for 1 hour. The precipitate was separated and washed, and then dried at 75 ° C. for 24 hours to obtain a polymer (flowability improver (B-4)) (polymerization rate was 98%). The weight average molecular weight (Mw) was 47000, and the molecular weight distribution (Mw / Mn) was 2.0.

(Production Example 5)
Production of fluidity improver (B′-5):
87.5 parts of styrene, 12.5 parts of phenyl methacrylate, 96 parts of styrene, 4 parts of n-butyl acrylate, 1 part of 2,2′-azobis (isobutyronitrile), α-methylstyrene A polymer (flowability improver (B′-5)) was obtained in the same manner as in Production Example 4 except that 0.7 part of dimer was changed to 1.2 part of benzoyl peroxide (the polymerization rate was 97). %). The mass average molecular weight (Mw) was 150,000, and the molecular weight distribution (Mw / Mn) was 3.3.

  Table 1 shows the charged amount (parts) of each component, the polymerization mode, the polymerization rate, the mass average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) of the obtained polymer in Production Examples 1 to 5. In the table, St is styrene, PhMA is phenyl methacrylate, BA is n-butyl acrylate, AIBN is 2,2'-azobis (isobutyronitrile), and BPO is benzoyl peroxide. Moreover, the polymerization rate was computed by the mass conversion of the solid substance of the obtained polymer. Moreover, the mass average molecular weight (Mw) and the number average molecular weight (Mn) were measured by GPC method (eluent: chloroform).

(Examples 1-5, Comparative Examples 1-3)
The following were prepared as aromatic polycarbonate resins.
PC1: Aromatic polycarbonate resin, “Panlite L1225WS”, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 21,000.
PC2: Aromatic polycarbonate resin, “Panlite L1225ZL”, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 18,000.

A fluidity improver and an aromatic polycarbonate resin were mixed in the formulation shown in Table 2 (100 parts in total), and an ultraviolet absorber (“Tinuvin 329”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.3 Part, 0.1 part of antioxidant ("Irganox 1076", manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.1 part of heat stabilizer ("Adeka Stub 2112", manufactured by Asahi Denka Kogyo Co., Ltd.) The mixture was supplied to a twin screw extruder (model name “TEM-35”, manufactured by Toshiba Machine Co., Ltd.) and melt kneaded at 280 ° C. to obtain an aromatic polycarbonate resin composition.
About the obtained aromatic polycarbonate-type resin composition, the below-mentioned (1)-(5) evaluation was performed. The results are shown in Table 2.

(Evaluation methods)
(1) Melt fluidity:
The spiral flow length (SFL) of the aromatic polycarbonate resin composition was evaluated using an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.). The molding temperature was 280 ° C., the mold temperature was 80 ° C., and the injection pressure was 98 MPa. The thickness of the molded product was 2 mm and the width was 15 mm.

(2) Chemical resistance:
Using an aromatic polycarbonate resin composition, a 2 mm thick, 15 cm square flat plate was produced by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.), and this was cut to a thickness of 2 mm. A molded product of 15 cm × 2.5 cm was obtained. After the test piece was annealed at 120 ° C. for 2 hours, a cantilever test was performed, and the breaking time of the test piece by chemical application was measured. The measurement was performed at a test temperature: 23 ° C., a load: 20 MPa, and a solvent: toluene / isooctane = 1/1 vol ratio.

(3) Surface peelability (peeling resistance):
The protruding pin mark of the molded product obtained in (2) was cut with a cutter, and the peeled state was visually observed. The evaluation criteria are as follows.
○: Good without peeling.
X: Surface layer peeling is seen.

(4) Deflection temperature under load (heat resistance):
Using the aromatic polycarbonate resin composition, a molded article having a thickness of ¼ inch was molded by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.). The deflection temperature under load of the molded product was measured according to ASTM D648. The annealing treatment was performed at 120 ° C. for 1 hour, and the load was 1.82 MPa.

(5) Transparency:
Using the aromatic polycarbonate resin composition, a 3 mm thick, 5 cm square flat molded product was molded by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.).
The total light transmittance and haze of the molded product were measured at 23 ° C. and 100 ° C. in accordance with ASTM D1003.

As is clear from the results in Table 2, the aromatic polycarbonate-based resin compositions obtained in Examples 1 to 5 were melt flowable and resistant without impairing the heat resistance, peel resistance, and transparency of the molded product. The chemical property was remarkably improved and the balance of physical properties was excellent.
On the other hand, since the aromatic polycarbonate resin composition obtained in Comparative Example 1 has insufficient compatibility, good peeling resistance could not be obtained, and improvement in melt fluidity and chemical resistance could not be obtained. .
Further, the aromatic polycarbonate resin compositions obtained in Comparative Examples 2 and 3 did not contain the fluidity improver (B), and sufficient fluidity and chemical resistance were not obtained.

(Examples 6-7, Comparative Examples 4-5)
The following were prepared as a resin material containing an aromatic polycarbonate resin.
PC3: Aromatic polycarbonate resin ("Iupilon S-2000F", manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 25,000), styrene-acrylonitrile resin ("SR 30B", manufactured by MG ABS Co., Ltd.) ) In a 95/5 mass ratio.
PC4: Aromatic polycarbonate resin ("Iupilon S-2000F", manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 25,000) and polyester elastomer ("Perprene P-40" manufactured by Toyobo Co., Ltd.) And 95/5 mass ratio.

A resin material containing a fluidity improver and an aromatic polycarbonate resin is mixed in the composition shown in Table 3 (100 parts in total), and further an ultraviolet absorber (“Tinuvin 329”, manufactured by Ciba Specialty Chemicals Co., Ltd.). 0.3 parts, antioxidant ("Irganox 1076", manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1 part, heat stabilizer ("Adeka Stub 2112", manufactured by Asahi Denka Kogyo Co., Ltd.) 0. 1 part was added, and it supplied to the twin-screw extruder (model name "TEM-35", Toshiba Machine Co., Ltd. product), melt-kneaded at 280 degreeC, and obtained the aromatic polycarbonate-type resin composition.
About the obtained aromatic polycarbonate-type resin, evaluation of above-mentioned (1)-(4) and evaluation of the below-mentioned (6) were performed. The results are shown in Table 3.

(Evaluation methods)
(6) Transparency:
Using the aromatic polycarbonate resin composition, a flat molded product having a thickness of 2 mm and 5 cm × 10 cm was molded by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.). The transparency of the molded product was visually evaluated according to the following criteria.
○: Excellent transparency.
Δ: Transparent.
X: No transparency.

As is apparent from the results in Table 3, the aromatic polycarbonate resin compositions obtained in Examples 6 and 7 were melt flowable and resistant without impairing the heat resistance, peel resistance, and transparency of the molded product. The chemical property was remarkably improved and the balance of physical properties was excellent.
On the other hand, the aromatic polycarbonate resin compositions obtained in Comparative Examples 4 and 5 did not contain the fluidity improver (B), and sufficient fluidity and chemical resistance were not obtained.

(Examples 8-9, Comparative Examples 6-7)
The following were prepared as aromatic polycarbonate resins and inorganic fillers.
PC5: aromatic polycarbonate resin, “Taflon FN1700”, manufactured by Idemitsu Petrochemical Co., Ltd., viscosity average molecular weight 17,000, refractive index 1.585.
Glass fiber 1: “CS03MAFT737K25”, manufactured by Asahi Fiber Glass Co., Ltd., refractive index 1.545, average fiber length 3 mm, average fiber diameter 13 μm, sizing agent: urethane sizing agent.
Glass fiber 2: “ECR glass fiber”, manufactured by Asahi Fiber Glass Co., Ltd., refractive index 1.579, average fiber length 3 mm, average fiber diameter 13 μm, sizing agent: urethane sizing agent.

The fluidity improver, the aromatic polycarbonate resin, and the glass fiber are mixed in the formulation shown in Table 4 (100 parts in total of the fluidity improver and the aromatic polycarbonate resin), and further an ultraviolet absorber (“Tinuvin 329”). ”, 0.3 part of Ciba Specialty Chemicals Co., Ltd., 0.1 part of antioxidant (“ Irganox 1076 ”, Ciba Specialty Chemicals Co., Ltd.), heat stabilizer (“ Adeka Stub 2112: Asahi Denka Kogyo Co., Ltd. (0.1 part) is added and supplied to a twin screw extruder (model name “TEM-35”, manufactured by Toshiba Machine Co., Ltd.) equipped with a side feeder and melt-kneaded at 290 ° C. An aromatic polycarbonate resin composition was obtained.
About the obtained aromatic polycarbonate-type resin, below-mentioned (7) and above-mentioned (2)-(4), (6) evaluation was performed. The results are shown in Table 4.

(Evaluation methods)
(7) Melt fluidity:
The spiral flow length (SFL) of the aromatic polycarbonate resin composition was evaluated using an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.). The molding temperature was 290 ° C., the mold temperature was 80 ° C., and the injection pressure was 98 MPa. The thickness of the molded product was 2 mm and the width was 15 mm.

As is clear from the results in Table 4, the aromatic polycarbonate resin compositions obtained in Examples 8 and 9 were melt flowable and resistant without impairing the heat resistance, peel resistance, and transparency of the molded product. The chemical property was remarkably improved and the balance of physical properties was excellent.
On the other hand, the aromatic polycarbonate resin compositions obtained in Comparative Examples 6 and 7 did not contain the fluidity improver (B), and sufficient fluidity and chemical resistance were not obtained.

(Examples 10-11, Comparative Examples 8-9)
The following were prepared as an aromatic polycarbonate resin, a resin material containing the same, and a flame retardant.
PC5: Aromatic polycarbonate resin, “Taflon FN1700”, manufactured by Idemitsu Petrochemical Co., Ltd., viscosity average molecular weight 17,000.
PC6: Aromatic polycarbonate resin (“Taflon FN1700”, manufactured by Idemitsu Petrochemical Co., Ltd., viscosity average molecular weight 17,000), acrylonitrile-butadiene-styrene resin (“UX 050”, manufactured by UMG ABS Co., Ltd.) ) And styrene-acrylonitrile resin (“SR 30B”, manufactured by UMG ABS Co., Ltd.) at a mass ratio of 80/10/10.
Flame retardant 1: “Megafac F114”, potassium perfluorobutane sulfonate, manufactured by Dainippon Ink & Chemicals, Inc.
Flame retardant 2: “PX-200”, a condensed phosphate ester flame retardant, manufactured by Daihachi Chemical Industry Co., Ltd.

Formulation of fluidity improver, aromatic polycarbonate resin or resin material containing the same, and flame retardant shown in Table 5 (total 100 parts of fluidity improver and aromatic polycarbonate resin or resin material containing the same) In addition, 0.3 parts of an ultraviolet absorber (“Tinuvin 329”, manufactured by Ciba Specialty Chemicals Co., Ltd.), an antioxidant (“Irganox 1076”, manufactured by Ciba Specialty Chemicals Co., Ltd.) 0 0.1 part, heat stabilizer ("Adeka Stub 2112", manufactured by Asahi Denka Kogyo Co., Ltd.) 0.1 part, non-drip agent ("Teflon (registered trademark) CD-1", manufactured by Asahi IC Fluoropolymers Co., Ltd.) ) Mix 0.3 parts, supply to twin screw extruder (model name “TEM-35”, manufactured by Toshiba Machine Co., Ltd.), melt knead at 280 ° C., aromatic polycarbonate resin It was obtained Narubutsu.
About the obtained aromatic polycarbonate-type resin composition, evaluation of above-mentioned (1)-(4), (6) and below-mentioned (8) was performed. The results are shown in Table 5.

(Evaluation methods)
(8) Flame retardancy:
Using an aromatic polycarbonate resin composition, a test piece having a thickness of 1/8 inch was obtained by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.). The flame retardancy of the five molded articles obtained was tested in the test methods shown in Breitin 94 of Underwriters Laboratories, Inc., and the combustion test UL94 / V-0, V-1, and V-2 for material classification. Based on the evaluation. The criteria for each V grade for UL94 are outlined below.
V-0: The average flame holding time after removing the ignition flame is 5 seconds or less, and all the samples do not drop the fine flame that ignites the absorbent cotton.
V-1: The average flame holding time after removing the ignition flame is 25 seconds or less, and all the samples do not drop the fine flame that ignites the absorbent cotton.
V-2: The average flame holding time after removing the ignition flame is 25 seconds or less, and these samples drop the particulate flame that ignites absorbent cotton.
UL94 also states that if all test bars do not pass a particular V grade, they must not be classified into that grade. If this condition is not met, the five test bars are given the grade of the one with the worst performance. For example, if one test bar is classified as V-2, the grade for all five test bars is V-2.

As is clear from the results in Table 5, the aromatic polycarbonate resin compositions obtained in Examples 10 and 11 were melted without impairing the heat resistance, peel resistance, flame retardancy, and transparency of the molded product. The fluidity and chemical resistance were remarkably improved, and the physical property balance was excellent.
On the other hand, the aromatic polycarbonate resin compositions obtained in Comparative Examples 8 and 9 did not contain the fluidity improver (B), and sufficient fluidity and chemical resistance were not obtained.

(Example 12, Comparative Example 10)
The following were prepared as an aromatic polycarbonate resin and an antistatic agent.
PC1: Aromatic polycarbonate resin (“Panlite L1225WS”, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 21,000.
Antistatic agent: Tetrabutylphosphonium salt of dodecylbenzenesulfonate, manufactured by Kao Corporation.

A fluidity improver, an aromatic polycarbonate resin, and an antistatic agent are mixed in the composition shown in Table 6 (100 parts in total of the fluidity improver and the aromatic polycarbonate resin), and further an ultraviolet absorber ("Tinuvin"). 329 ", manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.3 parts, antioxidant (" Irganox 1076 ", manufactured by Ciba Specialty Chemicals Co., Ltd.) 0.1 parts, thermal stabilizer (" ADK STAB 2112 ") ”, 0.1 part of Asahi Denka Kogyo Co., Ltd.), mixed and supplied to a twin screw extruder (model name“ TEM-35 ”, manufactured by Toshiba Machine Co., Ltd.), melted and kneaded at 280 ° C. A polycarbonate resin composition was obtained.
About the obtained aromatic polycarbonate-type resin composition, evaluation of above-mentioned (1)-(5) and below-mentioned (9) was performed. The results are shown in Table 6.

(Evaluation methods)
(9) Antistatic property:
Using the aromatic polycarbonate resin composition, a 3 mm thick, 5 cm square flat molded product was molded by an injection molding machine (“IS-100”, manufactured by Toshiba Machine Co., Ltd.). The specific resistance of the molded plate surface was measured by SM-8210 limit insulation meter manufactured by Toa Denpa Kogyo Co., Ltd.

As is apparent from the results in Table 6, the aromatic polycarbonate resin composition obtained in Example 12 is melt flowable and chemical resistant without impairing heat resistance, peel resistance, antistatic properties, and transparency. The property was remarkably improved and the balance of physical properties was very excellent.
On the other hand, the aromatic polycarbonate resin composition obtained in Comparative Example 10 did not contain the fluidity improver (B), and sufficient fluidity and chemical resistance could not be obtained.

The aromatic polycarbonate resin composition of the present invention is remarkably excellent in chemical resistance and melt flowability (moldability), so that there has been a growing demand in recent years for large-sized, thin-walled electric / electronic / OA equipment, optical components. It is suitable for various injection-molded products for industrial use, precision machinery, automobiles, safety / medical use, building materials and general goods, and is extremely useful industrially.

Claims (5)

An aromatic polycarbonate-based resin (A), the flowability improver (B), and a stabilizer (C) an aromatic polycarbonate resin composition containing,
The fluidity improver (B) is an aromatic vinyl monomer (b1) 0.5 to 99.5% by mass, a monomer (b2) represented by the following formula (I) 0.5 to 99.99. A monomer mixture comprising 5% by mass and other monomers (b3) 0 to 40% by mass [wherein the total of the monomers (b1) to (b3) is 100% by mass. An aromatic polycarbonate-based resin composition, which is a polymer obtained by polymerizing].

(In formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is an optionally substituted phenyl group.)   The aromatic polycarbonate resin composition according to claim 1, further comprising an inorganic filler (D).   The aromatic polycarbonate resin composition according to claim 1 or 2, further comprising a flame retardant (E).   Furthermore, the aromatic polycarbonate-type resin composition as described in any one of Claim 1 thru | or 3 containing an antistatic agent (F). A molded article formed by molding the aromatic polycarbonate resin composition according to any one of claims 1 to 4.