JP2006306958A - Flow improver for aromatic polycarbonate resin, aromatic polycarbonate resin composition, and molded article thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flow improver for an aromatic polycarbonate resin for improving melt flowability (moldability) of a resin composition and chemical resistance of a molded article without impairing high-temperature transparency, heat resistance, and the like of the molded article, and to provide an aromatic polycarbonate resin composition comprising the same and a molded article thereof. <P>SOLUTION: A monomer mixture comprising 0.5-99.5 mass% of an aromatic vinyl monomer (a1), 0.5-99.5 mass% of a monomer (a2) represented by the formula (I): CH<SB>2</SB>=C(-R<SP>1</SP>)-COOR<SP>2</SP>(wherein R<SP>1</SP>is a hydrogen atom or a methyl group; and R<SP>2</SP>is a phenyl group which may have a substituent), and 0-40 mass% of another monomer (a3) is polymerized to form a polymer having a glass transition temperature of 110°C or higher and a mass average molecular weight of 5,000-200,000. The polymer is used as the flow improver for an aromatic polycarbonate resin. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a fluidity improver for an aromatic polycarbonate resin, an aromatic polycarbonate resin composition containing the same, and a molded article thereof.

  Molded products made of aromatic polycarbonate resin have excellent mechanical strength, heat resistance, electrical characteristics, dimensional stability, etc., so OA (office automation) equipment, information / communication equipment, electronic / electric equipment, home electrification It is used in a wide range of fields such as equipment, automobiles, and architecture. 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 recent years, moldings of aromatic polycarbonate resins have become larger, thinner, more complicated in shape and higher in performance, and molded from aromatic polycarbonate resins as interest in environmental issues has increased. There is a need for a resin modifier that improves the melt fluidity of an aromatic polycarbonate resin composition without impairing the excellent properties of the product, and improves the injection moldability, and an aromatic polycarbonate resin composition using the same. It has been.

  As a method for improving the melt fluidity of the aromatic polycarbonate resin composition without impairing the properties (transparency, heat resistance, etc.) of the molded article made of the aromatic polycarbonate resin composition, (1) matrix resin A method for reducing the molecular weight of an aromatic polycarbonate resin itself is well known. Also, (2) a method for improving melt fluidity by polymer alloying an aromatic polycarbonate resin and a specific styrene resin (for example, Patent Documents 1 and 2), (3) an aromatic polycarbonate resin A method (for example, Patent Document 3) for improving 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 4), (5) a method of adding an oligomer of a polycarbonate (for example, Patent Document) 5), (6) A method of adding a low molecular weight styrene copolymer (for example, Patent Documents 6 to 8) 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, and the transparency of the molded product at high temperatures (high temperature transparency) It 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. In addition to being greatly reduced, haze is generated at high temperatures, and transparency is greatly reduced (temperature dependence of haze). 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 is likely to occur in the molded product, and accordingly, there remains a problem that impact strength, practically important weld appearance and surface impact are not sufficient, and transparency at a high temperature is remarkably lowered.

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.
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 flowability (moldability) of the aromatic polycarbonate resin composition and the chemical resistance of the molded article without impairing the high temperature transparency and heat resistance of the molded article. Flowability improver for resin, aromatic polycarbonate resin composition with improved melt fluidity and chemical resistance without impairing high-temperature transparency and heat resistance of the resulting molded product, and reduction in high-temperature transparency It is to provide a molded product excellent in heat resistance and chemical resistance (having less temperature dependence of haze).

  The fluidity improver (A) for aromatic polycarbonate-based resin of the present invention comprises 0.5 to 99.5% by mass of an aromatic vinyl monomer (a1), a monomer represented by the following formula (I) ( a2) A monomer mixture composed of 0.5 to 99.5% by mass and another monomer (a3) 0 to 40% by mass [wherein the total of the monomers (a1) to (a3) is 100% by mass %. ], A polymer having a glass transition temperature of 110 ° C. or higher and a mass average molecular weight of 5,000 to 200,000.

(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 contains the flow improver (A) for an aromatic polycarbonate resin of the present invention and the aromatic polycarbonate resin (B).
The molded article of the present invention is formed by injection molding the aromatic polycarbonate resin composition of the present invention.

The fluidity improver (A) for aromatic polycarbonate resin of the present invention is capable of melt flowability (moldability) and molding of an aromatic polycarbonate resin composition without impairing the high temperature transparency and heat resistance of the molded product. The chemical resistance of the product can be improved.
The aromatic polycarbonate resin composition of the present invention is excellent in melt fluidity and chemical resistance without impairing the high-temperature transparency, heat resistance, etc. of the obtained molded product, as compared with the conventional one.
The molded article of the present invention is excellent in heat resistance and chemical resistance because the decrease in high-temperature transparency is suppressed (the haze temperature dependency is small).

[Flowability improver (A)]
The flowability improver (A) for aromatic polycarbonate resin of the present invention (hereinafter referred to as flowability improver (A)) is 0.5 to 99.5% by mass of the aromatic vinyl monomer (a1). A monomer mixture composed of 0.5 to 99.5% by mass of the monomer (a2) represented by the following formula (I) and 0 to 40% by mass of the other monomer (a3) [however, The sum total of the monomers (a1) to (a3) is 100% by mass. Is a polymer having a glass transition temperature of 110 ° C. or higher and a mass average molecular weight of 5,000 to 200,000.

(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 (A) is a fragrance that exhibits phase separation behavior with the aromatic polycarbonate resin (B) at the time of melt molding and has a good level of peel resistance in the use temperature range of the molded product. In order to show the compatibility (affinity) with the aromatic polycarbonate resin (B), it does not impair the characteristics (transparency, heat resistance, etc.) of the aromatic polycarbonate resin (B), (Formability) and chemical resistance are improved.
In addition, since the temperature dependence of the refractive index of the fluidity improver (A) is close to the temperature dependence of the refractive index of the aromatic polycarbonate resin (B), the temperature dependence of haze is small and is not found in the past. Excellent high temperature transparency.

  In the fluidity improver (A), the mixing ratio (% by mass) of each monomer in the monomer mixture before polymerization, and each monomer constituent unit (% by mass) in the polymer after polymerization. Are preferably substantially the same. In order to obtain such a polymer, the polymerization rate of the monomer mixture is preferably 90% by mass or more, and more preferably 95% by mass or more. If the polymerization rate is 95% by mass or more, the mixing ratio (% by mass) of each monomer in the monomer mixture before polymerization and each monomer constituent unit (% by mass) in the polymer after polymerization There is no problem considering that they are substantially identical. When the polymerization rate is less than 90% by mass, the mixing ratio (% by mass) of each monomer in the monomer mixture before polymerization and the monomer constitutional unit (mass by mass) in the polymer after polymerization. %) May be different, and the optimum composition range may be shifted. Further, it is not preferable because it is necessary to purify the polymer and remove the unreacted monomer when recovering the obtained polymer.

When the fluidity improver (A) contains a predetermined amount of the aromatic vinyl monomer (a1) unit, it exhibits excellent fluidity and chemical resistance improvement effects.
Examples of the aromatic vinyl monomer (a1) 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, and it is particularly preferable to use styrene and α-methylstyrene in combination.

  When the aromatic vinyl monomer (a1) is a mixture of styrene and α-methylstyrene, the content of α-methylstyrene is 10 to 10% in the aromatic vinyl monomer (a1) (100% by mass). 70 mass% is preferable. When the content of α-methylstyrene is less than 10% by mass, the glass transition temperature of the obtained polymer is lowered, and there is a possibility that sufficient high-temperature transparency cannot be expressed. The content of α-methylstyrene is more preferably 20% by mass or more, and further preferably 30% by mass or more. When the content of α-methylstyrene exceeds 70% by mass, copolymerization with styrene and / or other monomers is deteriorated, so that the polymerization rate of the obtained polymer may be lowered. The content of α-methylstyrene is more preferably 60% by mass or less, and further preferably 50% by mass or less.

  Content of an aromatic vinyl monomer (a1) is 0.5-99.5 mass% in a monomer mixture (100 mass%). When the content of the aromatic vinyl monomer (a1) is within this range, the fluidity improver (A) exhibits an excellent effect of improving melt fluidity and chemical resistance. When the content of the aromatic vinyl monomer (a1) exceeds 99.5% by mass, the compatibility with the aromatic polycarbonate resin (B) 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 (a1) is less than 0.5% by mass, the compatibility with the aromatic polycarbonate resin (B) becomes too good, so that the phase separation behavior is fully exhibited during melting. It cannot be done, and the improvement effect of the melt fluidity tends to decrease, and the improvement effect of 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 (a1) 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 (a1), 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 (a2) 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 (a2) is 0.5-99.5 mass% in a monomer mixture (100 mass%). If content of a monomer (a2) exists in this range, a fluidity improver (A) will express the improvement effect of the outstanding compatibility (peeling resistance). When the content of the monomer (a2) is less than 0.5% by mass, the compatibility with the aromatic polycarbonate resin (B) 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 (a2) exceeds 99.5% by mass, the compatibility with the aromatic polycarbonate resin (B) 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 (a2) 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 (a2), 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 that constitutes the fluidity improver (A) can be copolymerized with the aromatic vinyl monomer (a1) and the monomer (a2) as required, as long as the above-described properties are not impaired. The monomer (a3) may be contained in an amount of 0 to 40% by mass.

  The other monomer (a3) 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 (a3) is 0-40 mass% in a monomer mixture (100 mass%). When the content of the monomer (a3) 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 (a3) 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 (A) is excellent in compatibility with the aromatic polycarbonate resin (B), the transparency of a molded product made of the aromatic polycarbonate resin composition containing the fluid polycarbonate resin is improved. The polymer constituting the fluidity improver (A) is a two-component system of an aromatic vinyl monomer (a1) and a monomer (a2) 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 that expresses extremely high transparency, a polymer comprising 0.5 to 40% by mass of an aromatic vinyl monomer (a1) and 60 to 99.5% by mass of a monomer (a2) ( A1) (total amount of both is 100% by mass), aromatic vinyl monomer (a1) 60-99.5% by mass and monomer (a2) 0.5-40% by mass There are two combinations (A2) (the total amount of both is 100% by mass).

  The glass transition temperature of the polymer constituting the fluidity improver (A) is 110 ° C. or higher. The “glass transition temperature” in the present invention means a peak temperature of tan δ obtained by conducting a dynamic viscoelasticity test of a polymer. If the glass transition temperature of the fluidity improver (A) is 110 ° C. or higher, the temperature dependence of the refractive index of the fluidity improver (A) is dependent on the temperature dependence of the refractive index of the aromatic polycarbonate resin (B). Thus, the obtained molded product can maintain good high-temperature transparency in the actual use temperature range (80 to 120 ° C.) at high temperatures. When the glass transition temperature of the fluidity improver (A) is less than 110 ° C., the fluidity improver (A) and the aromatic polycarbonate resin (at about 80 ° C. or higher) even when the transparency at room temperature is good Since the difference in refractive index from that of B) increases, the haze of the obtained molded product increases, which may impair good transparency. In order to maintain a high degree of transparency up to a higher temperature, the glass transition temperature of the fluidity improver (A) is preferably 120 ° C. or higher, more preferably 130 ° C. or higher.

  The polymer constituting the fluidity improver (A) has a mass average molecular weight of 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 (A), 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 (A) 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

[Aromatic polycarbonate resin (B)]
The aromatic polycarbonate resin (B) 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 (B) may be branched. In the case of the branched aromatic polycarbonate resin (B), 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 (B) 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 (B), 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-based resin (B) has a dicarboxylic acid or dicarboxylic acid chloride for the purpose of increasing the flame retardancy, copolymerizing a polymer or oligomer having a siloxane structure, or improving the melt fluidity during molding. Derivatives such as these may be copolymerized.
The molecular weight of the aromatic polycarbonate-based resin (B) is a viscosity average molecular weight converted from a 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 (B) may be mixed and used.

  As the resin material containing the aromatic polycarbonate resin (B), an aromatic polycarbonate polymer alloy obtained by combining the aromatic polycarbonate resin (B) 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 (B). Other resins and / or elastomers may be blended as necessary within a range that does not impair, specifically, within a range of 50 parts by mass or less with respect to 100 parts by mass of the aromatic polycarbonate resin (B).

  Examples of 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), polycaprolactone, and copolymers thereof; acrylic resins such as polymethyl methacrylate (PMMA) and copolymers having methyl methacrylate units; polypropylene Olefinic resins such as PP), polyethylene (PE), and ethylene- (meth) acrylic acid copolymer; polyurethane; silicone resin; syndiotactic PS; polyamide such as 6-nylon and 6,6-nylon; Various general-purpose resins or engineering plastics such as polyphenylene sulfide; polyether ketone; polysulfone; polyethersulfone polyamideimide;

  Examples of the elastomer include 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.

[Aromatic polycarbonate resin composition]
The aromatic polycarbonate resin composition of the present invention contains the fluidity improver (A) of the present invention and the aromatic polycarbonate resin (B).

  What is necessary is just to determine the compounding quantity of a fluid improvement agent (A) suitably according to a desired physical property. In order to obtain an effective effect of improving the melt fluidity without deteriorating the properties (transparency, heat resistance, impact resistance, etc.) of the aromatic polycarbonate resin (B), the blending of the fluidity improver (A) The amount is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the aromatic polycarbonate-based resin (B) (when other resins and / or elastomers are included, the total is 100 parts by mass including these). If the blending amount of the fluidity improver (A) 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 (A) exceeds 30 parts by mass, the excellent mechanical properties of the aromatic polycarbonate resin (B) may be impaired. The blending amount of the fluidity improver (A) is 1 part by mass with respect to 100 parts by mass of the aromatic polycarbonate-based resin (B) (when other resins and / or elastomers are included, the total is 100 parts by mass including these). Part or more, preferably 2 parts by weight or more, more preferably 3 parts by weight or more. Moreover, a fluidity improver (A) compounding quantity is 100 mass parts of aromatic polycarbonate-type resin (B) (when other resin and / or an elastomer are included, 100 mass parts in total including these), 25 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is particularly preferable.

  Furthermore, the aromatic polycarbonate-based resin composition of the present invention includes various stabilizers such as known ultraviolet absorbers, light stabilizers, antioxidants, thermal stabilizers, reinforcing agents, inorganic fillers, if necessary. You may mix | blend additives, such as an impact modifier, a mold release agent, an antistatic agent, a blueing agent, a flame retardant, and a fluoro olefin. For example, talc, mica, calcium carbonate, glass fiber, carbon fiber, potassium titanate fiber, or the like may be blended in order to improve the strength, rigidity, and flame retardancy of the molded product. Furthermore, in order to improve chemical resistance and the like, other engineering plastic compositions such as polyethylene terephthalate, and in order to improve impact resistance, a rubber-like elastic body having a core-shell two-layer structure may be blended.

  The aromatic polycarbonate resin composition of the present invention includes, for example, an aromatic polycarbonate resin (B), a fluidity improver (A), if necessary, other resins, elastomers, various stabilizers, inorganic fillers, difficulty Other additives such as a flame retardant and an antistatic agent can be prepared by mixing with a tumbler, a V-type blender, a super mixer, a nauter mixer, a Banbury mixer, a kneading roll, an extruder, or the like.

  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 (B) and the fluidity improver (A); A part of the resin-based resin (B), various additives and the fluidity improver (A) are blended, that is, the various additives are diluted with the aromatic polycarbonate-based resin (B) to obtain a master batch of various additives. Then, the method of blending this masterbatch and aromatic polycarbonate-type resin (B) 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 a molded product having a thickness of 2 mm is in the range of 0.1 to 5%. Moreover, when the above-mentioned polymer (A1) or polymer (A2) is used as the fluidity improver (A), 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 80-120 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 fluidity improver (A) of the present invention described above, the melt fluidity (moldability) and molding of the aromatic polycarbonate resin composition without impairing the high temperature transparency and heat resistance of the molded product. The chemical resistance of the product can be improved. Moreover, in the aromatic polycarbonate resin composition of the present invention, the melt flowability (moldability) and chemical resistance are compared with conventional ones without impairing the high temperature transparency and heat resistance of the molded product obtained. Excellent. In particular, the molded products obtained have excellent high-temperature transparency, chemical resistance, and melt flowability (moldability) of the resin composition. Therefore, demands for electrical / electronic / OA equipment and optical parts have been increasing in recent years. Suitable for precision machinery, automobiles, safety / medical use, building materials, miscellaneous large and thin injection molded products, 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 (A-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) and 290 parts of distilled water were charged. Heat to 60 ° C. in a water bath under a 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, and then 66 parts of styrene. A mixture of 17 parts of α-methylstyrene, 18 parts of phenyl methacrylate, 0.2 part of t-butyl hydroperoxide and 0.5 part of n-octyl mercaptan was added dropwise over 360 minutes. Then, it stirred at 60 degreeC for 60 minutes, and obtained the polymer emulsion.

  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 (flowability improver (A-1)) (polymerization rate was 97%). The polymer had a glass transition temperature of 124 ° C., a weight average molecular weight (Mw) of 48000, and a molecular weight distribution (Mw / Mn) of 2.1.

(Production Example 2)
Production of fluidity improver (A-2):
A polymer (fluidity improver (A-2)) was obtained in the same manner as in Production Example 1 except that 58 parts of styrene, 24 parts of α-methylstyrene, and 20 parts of phenyl methacrylate were changed ( The polymerization rate is 97%). The polymer had a glass transition temperature of 131 ° C., a weight average molecular weight (Mw) of 47000, and a molecular weight distribution (Mw / Mn) of 2.1.

(Production Example 3)
Production of fluidity improver (A-3):
A polymer (fluidity improver (A-3)) was obtained in the same manner as in Production Example 1 except that 48 parts of styrene, 32 parts of α-methylstyrene and 20 parts of phenyl methacrylate were changed ( The polymerization rate is 97%). The glass transition temperature of the polymer was 137 ° C., the weight average molecular weight (Mw) was 49000, and the molecular weight distribution (Mw / Mn) was 2.2.

(Production Example 4)
Production of fluidity improver (A'-4):
A polymer (flowability improver) was prepared in the same manner as in Production Example 1 except that 66 parts of styrene, 17 parts of α-methylstyrene and 18 parts of phenyl methacrylate were changed to 96 parts of styrene and 4 parts of n-butyl acrylate. (A'-4)) was obtained (the polymerization rate was 97%). The glass transition temperature of the polymer was 90 ° C., the mass average molecular weight (Mw) was 52000, and the molecular weight distribution (Mw / Mn) was 2.2.

  Table 1 shows the charged amount (parts) of each component, the polymerization rate, the glass transition temperature, the mass average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) of the obtained polymers in Production Examples 1 to 4. In the table, St is styrene, α-MSt is α-methylstyrene, PhMA is phenyl methacrylate, and BA is n-butyl acrylate. 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 L1225Z-100”, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 22,000.
PC2: Aromatic polycarbonate resin, “Panlite L1225ZL-100”, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 18,000.

A fluidity improver and an aromatic polycarbonate resin are mixed in the formulation shown in Table 2 (100 parts in total) and supplied to a twin screw extruder (model name “TEM-35”, manufactured by Toshiba Machine Co., Ltd.). The mixture was melt-kneaded at 270 ° 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., 100 ° C., and 120 ° C. in accordance with ASTM D1003.

As is apparent from the results in Table 2, the aromatic polycarbonate resin compositions obtained in Examples 1 to 3 have a small temperature dependency of the haze of the molded product (without impairing high-temperature transparency) and are heat resistant. The melt fluidity and the chemical resistance were remarkably improved without impairing the properties and the peel resistance, and the physical property balance was excellent.
On the other hand, the aromatic polycarbonate resin composition obtained in Comparative Example 1 has insufficient compatibility, and the glass transition temperature of the polymer constituting the fluidity improver is low. Transparency was not obtained.
Further, the aromatic polycarbonate resin compositions obtained in Comparative Examples 2 and 3 did not contain the fluidity improver (A), and sufficient fluidity and chemical resistance could not be obtained.

The aromatic polycarbonate resin composition of the present invention containing the fluidity improver (A) of the present invention has remarkable melt fluidity and chemical resistance without impairing the high temperature transparency, heat resistance, etc. of the obtained molded product. Due to its superiority, various types of injection-molded products for large and thin electrical / electronic / OA equipment, optical parts, precision machinery, automobiles, safety / medical use, building materials, and miscellaneous goods that have been increasingly demanded in recent years. And industrially extremely useful.

Claims (3)

Aromatic vinyl monomer (a1) 0.5-99.5 mass%, monomer (a2) represented by the following formula (I) 0.5-99.5 mass%, and other monomers (A3) Monomer mixture composed of 0 to 40% by mass [However, the total of the monomers (a1) to (a3) is 100% by mass. ], A fluidity improver for an aromatic polycarbonate resin, which is a polymer having a glass transition temperature of 110 ° C. or higher and a mass average molecular weight of 5,000 to 200,000.

(In formula (I), R ¹ is a hydrogen atom or a methyl group, and R ² is an optionally substituted phenyl group.) Fluidity improver (A) for aromatic polycarbonate resin according to claim 1,
An aromatic polycarbonate resin composition comprising: an aromatic polycarbonate resin (B). A molded product obtained by injection molding the aromatic polycarbonate resin composition according to claim 2.