JP2006336007A - Polycarbonate based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate based resin composition manifesting an excellent flow property, having an excellent impact resistance and elongation property. <P>SOLUTION: The polycarbonate based resin composition comprises (A) the polycarbonate based resin, (B) a high-impact polystyrene resin obtained by copolymerizing a diene based rubber, a styrene based monomer and a monomer copolymerizable with styrene monomer, and (C) a copolymer of a specific amount of unsaturated dicarboxylic anhydride obtained by copolymerizing an anhydrous unsaturated dicarboxylic acid monomer and a styrene based monomer and having ≤1.9 cps of solution viscosity, each in a specific ratio. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention comprises a polycarbonate resin composition comprising a polycarbonate resin, an impact polystyrene resin and an anhydrous unsaturated dicarboxylic acid copolymer, which has excellent fluidity during molding and has improved impact strength and elongation characteristics. provide.

  Polycarbonate resins have excellent heat resistance and impact resistance, and are widely applied to automotive parts, home appliances, OA equipment parts, etc. In recent years, the molding process requirements for polycarbonate resins have become increasingly severe due to the expansion of their application fields. For example, there is a growing demand for thin molding and a shortening of the molding cycle, and for polycarbonate resins, further improvement in molding processability has become a major issue.

  Factors important for molding processability of polycarbonate-based resin About improvement of fluidity, as a known technique, polycarbonate-based resin and acrylonitrile-diene-styrene resin (hereinafter referred to as ABS resin) or (meth) acrylate- A method of mixing a diene-styrene resin (hereinafter referred to as MBS resin) or an impact-resistant polystyrene resin (hereinafter referred to as HIPS resin) has been proposed. When the ABS resin or MBS resin is selected and mixed, the impact resistance of the polycarbonate resin can be improved, but the flowability during molding is insufficient. On the other hand, when HIPS resin is selected and mixed, fluidity during molding of polycarbonate resin can be improved, but the compatibility of both polycarbonate resin and HIPS resin is insufficient and the dispersibility of the mixture is not good. Further, delamination occurs in the molded product, and the tensile elongation decreases. In particular, in the case of a thin molded product, the surface easily peels off, and the practical impact strength is considerably reduced. Furthermore, in the case where a flame retardant is blended, the above-mentioned problem becomes more serious, and practically the industrial use range is limited.

  Further, in the assembly of a housing for general OA equipment or home appliances, a method of fixing with a simple screw nut type is usually employed. Therefore, if the resin composition having a low tensile elongation rate is used, a molded product and a metal screw are used. Cracks are likely to occur at the contact points (the boss, the resin composition and the molded product are integrally molded). How to improve the tensile elongation characteristics of the two resin compositions is an important problem to be solved when mixing the polycarbonate resin and the HIPS resin.

  In general, a method of adding a compatibilizer is used in order to improve defects generated when a HIPS resin is mixed with a polycarbonate resin. In that case, if the strength of the compatibilizer itself is insufficient, it is expected that the effect on the strength of the resin composition will be great. Generally, a high molecular weight polymer or copolymer is used as the compatibilizer.

In the existing technology, the compatibilizers used in mixing the polycarbonate resin and the HIPS resin are all high molecular weight compatibilizers, such as epoxy-modified styrene block copolymers, styrene- Examples thereof include maleic anhydride resins and terpene phenol resins. As an example of existing technology, for example, in Patent Document 1, a resin composition composed of a polycarbonate-based resin, a HIPS resin, and an epoxy-modified styrene-based block copolymer as a compatibilizing agent has an impact resistance of the resin composition as its effect. Improvement of surface property and surface impact property is described. In Patent Document 2, a resin composition composed of a polycarbonate resin, a HIPS resin, and a compatibilizer, the compatibilizer includes a styrene-acrylonitrile copolymer and a styrene-maleic anhydride copolymer. In the styrene-maleic anhydride copolymer, the maleic anhydride monomer content is about 8% by weight (low maleic anhydride content), and the solution viscosity is 2 to 10 cps. It is described as a polymer.
JP 2000-143912 A JP-A-8-034915

  However, even in the above-mentioned patent documents, the impact resistance strength and elongation characteristics of the resin composition are not improved to a satisfactory level, and particularly the improvement of the elongation characteristics of the resin is insufficient, so that the industrial needs are satisfied. It is the reality that is not made.

  An object of the present invention is to improve the above-mentioned deficiencies in the technology by using a polycarbonate-based resin (A), an impact-resistant polystyrene-based resin (B) and an anhydrous unsaturated dicarboxylic acid copolymer (C) (low molecular weight and anhydrous anhydride). An object of the present invention is to provide a resin composition having an excellent balance of physical properties obtained by melt-kneading a copolymer having a high saturated dicarboxylic acid content. Among them, the unsaturated dicarboxylic acid anhydride copolymer (C) was obtained by copolymerizing an unsaturated dicarboxylic acid monomer and a styrene monomer, and its solution viscosity was 1.9 cps or less, The content of the unsaturated dicarboxylic anhydride monomer is 10 to 60% by weight, thereby providing a polycarbonate resin composition having good process fluidity, impact strength and excellent elongation characteristics. In the present invention, there is also provided a polycarbonate resin composition that maintains a good balance of physical properties including good flame retardancy and processing fluidity, impact strength, and excellent elongation characteristics even when a flame retardant is added to the polycarbonate resin composition. .

  ADVANTAGE OF THE INVENTION According to this invention, the polycarbonate-type resin composition which has favorable process fluidity | liquidity, impact strength, and the outstanding elongation characteristic is provided. The present invention also provides a polycarbonate resin composition that maintains a good physical property balance of good flame retardancy and processing fluidity, impact strength, and excellent elongation characteristics even when a flame retardant is added.

The present invention provides a resin composition having good processing fluidity, impact strength and excellent elongation characteristics, specifically, polycarbonate resin (A) 25-98 wt% [resin (A) And ratio of resin (B) in total], impact-resistant polystyrene resin (B) 2 to 75% by weight [ratio in total of resin (A) and resin (B)], and the resin (A) and resin Containing 0.2 to 10 parts by weight of an unsaturated dicarboxylic anhydride copolymer (C) based on 100 parts by weight of the total of (B),
The resin (B) is obtained by copolymerizing a diene rubber and a monomer copolymerizable with a styrene monomer,
The copolymer (C) is obtained by copolymerization of an unsaturated unsaturated dicarboxylic acid monomer and a styrenic monomer, the solution viscosity is 1.9 cps or less, and the content of the unsaturated unsaturated dicarboxylic acid monomer Is 10 to 60% by weight [ratio in total of monomers constituting the copolymer (C)],
The present invention relates to a polycarbonate resin composition.

  Here, the unsaturated unsaturated dicarboxylic acid copolymer (C) was obtained by copolymerizing an unsaturated dicarboxylic acid monomer and a styrenic monomer, and its solution viscosity was 1.9 cps or less, and The content of the unsaturated dicarboxylic anhydride monomer is 10 to 60% by weight [ratio in the total of monomers constituting the copolymer (C)].

  The polycarbonate resin (A) of the present invention is a generally known polycarbonate or copolymer polycarbonate, and can be produced by existing techniques. For example, it is produced by a condensation polymerization reaction or a transesterification reaction in a homogeneous phase using an interfacial condensation polymerization method. All of the above production methods and their reactants, polymers, catalysts, solvents, and combinations of conditions are known in the art and are disclosed in U.S. Pat. It is described in the example. Bisphenol, which is a raw material for polycarbonate, is, for example, dihydroxybiphenyl, bishydroxyphenylalkyl, bishydroxyphenyldialkyl, bishydroxyphenyl sulfide, bishydroxyphenyl ether, bishydroxyphenyl ketone, bishydroxyphenyl sulfoxide, bishydroxyphenyl sulfone, cyclohexylene. It can be selected from bisphenols such as tenbisphenol, nuclear alkylated derivatives of these compounds, and mixtures thereof.

  Specific examples of the bisphenols include 4,4′-dihydroxybiphenyl, 2,2′-bis (4-hydroxyphenyl) propane, 2,4′-bis (4-hydroxyphenyl) -2-methylbutane, 1-bis (4-hydroxyphenyl) cyclohexane, α, α-bis (4-hydroxyphenyl) diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3- Chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl) -4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, α , α-bis (3,5-dimethyl-4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3,5-dichloro- 4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and the like. 2,2′-bis (4-hydroxyphenyl) propane, commonly referred to as bisphenol A, is preferred. The bisphenol reacts with phosgene to obtain an aromatic polycarbonate, or bisphenol and diphenyl carbonate are polymerized in advance by a production method disclosed in Japanese Patent Laid-Open No. 1-158033 and others, and low molecular weight There is a production method in which the polycarbonate resin (A) is produced by solid-phase polymerization after the coalescence.

  The polycarbonate resin (A) generally has a weight average molecular weight of 10,000 to 100,000, and the weight average molecular weight when used alone is preferably 20,000 to 100,000. On the other hand, when two types of polycarbonate resins having different weight average molecular weights are used in combination, preferably more than 20,000 to 100,000 and 30,000 to 20,000, more preferably 21,000 to 50,000 and 10,000 to 191,000 In either case, the difference in weight average molecular weight between the two types of polycarbonate (high molecular weight and low molecular weight) is preferably not less than 30,000, and more preferably not less than 6,000. In the present invention, when the polycarbonate resin (A) is used in combination with two polycarbonate resins having high and low weight average molecular weights, a good balance of physical properties can be obtained. In the present invention, the polycarbonate resin (a1) having a high weight average molecular weight (preferably more than 20,000 to 100,000, more preferably 21,000 to 50,000) and a low weight average molecular weight (preferably 30,000 to 20,000, more preferably (A1) / (a2) = 50 to 90/10 to 50 is preferable as the weight ratio of the polycarbonate resin (a2) of 10,000 to 11,000). The total amount of the resin comprising the polycarbonate resin (A) and the impact-resistant polystyrene resin (B) of the present invention is 100% by weight, and the amount of the polycarbonate resin (A) used is preferably 45 to 97% by weight, More preferably, it is 55 to 96% by weight. If the amount of the polycarbonate resin (A) used exceeds 98% by weight, the fluidity of the molding process of the resin composition becomes poor. On the other hand, if the amount of the polycarbonate resin (A) used is less than 25% by weight, the resin composition The impact strength and elongation properties of the object are deteriorated.

  The impact-resistant polystyrene resin (B) of the present invention is obtained by copolymerizing a diene rubber, a styrene monomer, and a copolymerizable monomer selected as necessary. Preferred is 97-80 parts by weight of styrenic monomer in the presence of 3-20 parts by weight of diene rubber, 0-17 parts by weight, preferably 0-5 parts by weight, more preferably 0-2 parts by weight. It is obtained by copolymerizing a part of the copolymerizable monomer, and a polymerization initiator, a chain transfer agent, and an appropriate amount of solvent selected as necessary. The polymerization may be a batch type or continuous type solution or bulk or bulk-suspension polymerization, and a solution or bulk polymerization method is particularly preferable. The reactor can be a fully mixed reactor (CSTR) or a plug flow reactor or a static mixed reactor, and several similar reactors can be used in series or in parallel, or a fully mixed and plugged reactor can be used. A flow reactor can be used in combination. The stirring speed of the reactor is preferably 5 to 55 rpm, the polymerization temperature is 80 to 250 ° C., and the weight average particle size of the rubber particles in the dispersed phase in the impact-resistant polystyrene resin (B) is preferably 0.1 to 10 μm.

  Examples of the diene resin include polybutadiene rubber (divided into high-cis polybutadiene rubber and low-cis polybutadiene rubber), polyisoprene rubber, styrene-butadiene copolymer, and styrene-isoprene copolymer. Examples thereof include polymers and ethylene-propylene-diene rubbers, and these can be used alone or in combination of two or more.

  Specific examples of the styrene monomer include styrene, α-methylstyrene, pt-butylstyrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, α -Methyl-p-methylstyrene, bromostyrene and the like are mentioned, among which styrene and α-methylstyrene are preferable.

  Specific examples of the copolymerizable monomer include acrylate monomers, methacrylate monomers, maleimide monomers, and acrylic acid monomers (for example, acrylic acid and methacrylic acid). Specific examples of the acrylate monomer include methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate, polyethylene glycol diacrylate, etc. Among them, butyl acrylate is preferable. On the other hand, specific examples of methacrylate monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, benzyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, 2-hydroxyethyl methacrylate, propylene oxide methacrylate, dimethylaminoethyl methacrylate. , Ethylene dimethacrylate, neopentyl dimethacrylate and the like. Among them, methyl methacrylate and butyl methacrylate are preferable. Specific examples of maleimide monomers include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-hexylmaleimide, N-octylmaleimide, N-dodecylmaleimide, N-cyclohexylmaleimide, N- Phenylmaleimide (referred to as PMI), N-2-methylmaleimide, N-2,3-dimethylphenylmaleimide, N-2,4-dimethylphenylmaleimide, N-2,3-diethylphenylmaleimide, N-2,4 -Diethylphenylmaleimide, N-2,3-dibutylphenylmaleimide, N-2,4-dibutylphenylmaleimide, N-2,6-dimethylphenylmaleimide, N-2,3-dichlorophenylmaleimide, N-2,4- Examples thereof include dichlorophenylmaleimide, N-2,3-dibromophenylmaleimide and N-2,4-dibromophenylmaleimide, and among them, N-phenylmaleimide is more preferable.

  The amount of copolymerizable monomer used in the high impact polystyrene resin (B) of the present invention is 0 to 40 parts by weight, preferably 2 to 40 parts by weight, more preferably 3 to 38 parts by weight. When a copolymerizable monomer is used, it is preferable to select a monomer that does not contain an acrylonitrile-based monomer component to obtain a material having good fluidity.

  An appropriate amount of solvent is used when polymerizing the high impact polystyrene resin (B). Specific examples thereof include benzene, toluene, ethylbenzene, p-xylene, o-xylene, m-xylene, pentane, octane, cyclohexane, methyl ethyl ketone, acetone, and methyl butyl ketone.

  After completion of the polymerization, the resulting polymerization solution is heated with a preheater, and then unreacted monomers and other volatile components are removed through a devolatilizer. A devolatization apparatus used for general devolatization includes a vacuum degassing tank apparatus or an extrusion degassing apparatus. The devolatilized polymer melt is extruded and pelletized to obtain the impact-resistant polystyrene resin (B) of the present invention.

  The amount of use of the impact-resistant polystyrene resin (B) of the present invention is 2 to 75% by weight, preferably 3 to 55% by weight, more preferably 100% by weight of the total of the resin (A) and the resin (B). Is 4 to 45% by weight. When the content of the impact-resistant polystyrene resin (B) exceeds 75% by weight of the resin composition, the softening point of the resin composition is lowered and the impact strength and elongation characteristics are deteriorated. On the other hand, if the content of the high-impact polystyrene resin (B) in the resin composition is less than 2% by weight, the fluidity during the molding process of the resin composition is deteriorated and the elongation characteristics are also deteriorated.

  The unsaturated dicarboxylic acid anhydride copolymer (C) of the present invention is obtained by copolymerizing an unsaturated dicarboxylic acid monomer and a styrene monomer. Specific examples of the unsaturated dicarboxylic anhydride monomer include maleic anhydride, citraconic anhydride, itaconic anhydride, and aconitic anhydride, and maleic anhydride is more preferable.

  Specific examples of the styrenic monomer of the unsaturated unsaturated dicarboxylic acid copolymer (C) include the same styrenic monomers listed in the above-mentioned impact-resistant polystyrene resin (B).

Examples of the polymerization of the unsaturated dicarboxylic acid anhydride copolymer (C) of the present invention include batch polymerization or continuous polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization. Here, as an example of continuous solution polymerization, 15 to 60% by weight of an unsaturated dicarboxylic anhydride monomer [a ratio in the total of monomers constituting the copolymer (C)] and a styrene monomer 40 A raw material solution consisting of ˜85% by weight [ratio in total of monomers constituting the copolymer (C)] and an appropriate amount of a solvent, a polymerization initiator and a chain transfer agent is continuously fed into a reactor to carry out polymerization. The polymerization temperature is 110-240 ° C, the polymerization time is 0.5-10 hours, the reactor pressure is 1.0-11 kg / cm ² , and the reactor is a strip screw type stirring leaf, propeller type stirring leaf, or other stirring with high shear stress It is equipped with a leaf, and the reactor is achieved by one or a combination of different types of reactors consisting of a continuous stirred reactor (CSTR), a plug flow reactor, or a static mixed reactor, but more preferable The first reactor employs a continuous stirred reactor (CSTR) and further connects the second and / or subsequent reactors, the subsequent reactors being continuous stirred reactors, plug flow reactors. Alternatively, a static mixing reactor or the like is used. Each of the above monomers or additives is continuously fed to the first reactor and / or the second reactor and / or subsequent reactors, and if necessary, simply to the second and / or subsequent reactors. A polymerization reaction is carried out by adding a monomer, a chain transfer agent, a polymerization initiator and the like, and the final monomer conversion is 30 to 95%. After passing through a devolatilizer to remove low-volatile components such as unreacted monomers and solvents, the components are returned to the raw material tank and used again as a raw material solution.

  The devolatilization apparatus is a single or twin screw extruder with a devolatilization port, and a devolatilization aid (for example, water, cyclohexane, carbon dioxide, etc.) is added to the extruder as necessary. Moreover, a kneading zone and a push feed zone can be installed in the extruder as required.

The unsaturated dicarboxylic acid anhydride copolymer (C) of the present invention is an example of a batch type solution polymerization method. 15-60 wt% of unsaturated dicarboxylic acid monomer [monomer constituting the copolymer (C) Of the total amount of styrene monomer and 40 to 85% by weight (ratio of the total amount of monomers constituting the copolymer (C)) and an appropriate amount of solvent, polymerization initiator, chain transfer agent, etc. The raw material solution is continuously fed to the reactor, polymerization is carried out under the conditions of a polymerization temperature of 70 to 230 ° C., a polymerization time of 0.5 to 12 hours, and a reactor pressure of 0.5 to 10 kg / cm ^2. The unsaturated dicarboxylic acid copolymer (C) is obtained through volatilization, extrusion, and drying.

  In the unsaturated dicarboxylic acid anhydride copolymer (C) of the present invention, the content of the unsaturated dicarboxylic acid monomer is 10 to 60% by weight in the total of the monomers constituting the copolymer (C). And preferably 14 to 58% by weight, more preferably 18 to 55% by weight. When the content of the unsaturated dicarboxylic anhydride monomer is less than 10% by weight, the impact strength and elongation characteristics of the resin composition are not sufficiently improved. On the other hand, when the content of the unsaturated dicarboxylic acid monomer exceeds 60% by weight, the hue of the resin composition is deteriorated.

  The solution viscosity of the unsaturated dicarboxylic acid anhydride copolymer (C) of the present invention is 1.9 cps or less (1.9 mPa · s or less), preferably 0.1 to 1.8 cps (0.1 to 1.8 mPa · s), more preferably 0.3 to 1.6 cps (0.3 to 1.6 mPa · s). The solution viscosity is an index of molecular weight, but the measurement method is to dissolve the copolymer in methyl ethyl ketone to make a 10% by weight copolymer solution, put 10 ml of the copolymer solution in a viscometer, and set the temperature at 25 ° C. Measure with.

  When the solution viscosity of the unsaturated unsaturated dicarboxylic acid copolymer (C) of the present invention exceeds 1.9 cps, the impact strength and elongation characteristics of the resin composition are lowered. Control of the solution viscosity of the copolymer (C) is achieved through adjustment of the polymerization temperature, the type of polymerization initiator, the type of chain transfer agent and the amount used. The polymerization temperature is about 70 ° C to 250 ° C.

  Specific examples of the polymerization initiator used in the polymerization of the unsaturated dicarboxylic anhydride copolymer (C) of the present invention include benzoyl peroxide, dicumyl peroxide, t-butyl peroxide, and t-butyl hydroperoxide. , Cumene hydroperoxide, t-butylperoxybenzoate, bis-2-ethylhexyl peroxydicarbonate, t-butylperoxyisopropyl carbonate (referred to as BPIC), cyclohexanone peroxide, 2,2'-azobisisobutyro Nitriles, 1,1′-azobiscyclohexane-1-carbonitrile, 2,2′-azobis-2-methylbutyronitrile and the like can be mentioned. The amount of the polymerization initiator used is usually 0.1 to 10 parts by weight with respect to 100 parts by weight of the raw material monomer.

  Specific examples of the chain transfer agent used for polymerization of the unsaturated dicarboxylic anhydride (C) include methyl mercaptan, n-butyl mercaptan, cyclohexyl mercaptan, n-dodecyl mercaptan, stearyl mercaptan, and t-dodecyl mercaptan (referred to as TDM). ), N-propyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, t-nonyl mercaptan, and the like. The amount of the chain transfer agent used is 0 to 5 parts by weight with respect to 100 parts by weight of the raw material monomer.

  Specific examples of the solvent used for the polymerization of the unsaturated dicarboxylic anhydride copolymer (C) include benzene, toluene, ethylbenzene, p-xylene, o-xylene, m-xylene, and pentane, octane, cyclohexane, and Examples thereof include methyl ethyl ketone, acetone, and methyl isobutyl ketone. The amount of the solvent used is 0 to 200 parts by weight based on 100 parts by weight of the raw material monomer.

  The unsaturated dicarboxylic anhydride copolymer (C) of the present invention is 0.2 to 10 parts by weight, preferably 0.3 to 100 parts by weight with respect to 100 parts by weight in total of the polycarbonate resin (A) and the impact-resistant polystyrene resin (B). 8.0 parts by weight, more preferably 0.4 to 7.0 parts by weight. When the amount of the unsaturated unsaturated dicarboxylic acid copolymer (C) used is less than 0.2 parts by weight, the impact strength of the resin composition is lowered and the elongation property is also deteriorated. On the other hand, when the amount of the unsaturated unsaturated dicarboxylic acid copolymer (C) used exceeds 10 parts by weight, both the impact strength and elongation properties of the resin composition are deteriorated.

  In order to achieve better physical properties of the resin composition of the present invention, an impact modifier can be used. Other impact modifiers include (meth) acrylate-diene-styrene copolymers, acrylonitrile-diene-styrene copolymers, and silicon-containing rubber graft copolymers. The amount used is preferably 1 to 14 parts by weight with respect to 100 parts by weight of the total of the resin (A) and the resin (B).

  The method for producing the impact modifier acrylonitrile-diene-styrene copolymer is preferably an emulsion graft polymerization method. For example, a styrene monomer, acrylonitrile in the presence of a diene rubber emulsion. An acrylonitrile-diene system having a weight average particle size of 0.05 to 0.8 μm when graft polymerization is carried out using a monomer mixture comprising a system monomer and a copolymerizable monomer selected as necessary -A styrene copolymer is obtained. Alternatively, a graft polymer composed of rubber particles having different weight average particle diameters is manufactured and mixed to obtain a bimodal distribution of graft copolymer emulsion, and pelletized acrylonitrile system through steps such as coagulation, dehydration and drying A diene-styrene copolymer is obtained.

  Specific examples of the diene rubber emulsion include polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, butadiene- (meth) acrylate copolymer, isoprene-butylacrylate copolymer. A polymer is mentioned.

  Examples of the copolymerizable monomer in the acrylonitrile-diene-styrene copolymer include acrylate monomers, methacrylate monomers, and maleimide monomers. Specific examples of the acrylate monomer, methacrylate monomer and maleimide monomer are the same as those described in the section of impact resistant polystyrene resin (B).

  The production method of the impact modifier (meth) acrylate-diene-styrene copolymer is preferably an emulsion graft polymerization method. Examples of the polymerization method include graft polymerization of a monomer mixture comprising a styrene monomer and a (meth) acrylate monomer in the presence of a diene rubber emulsion, and a (meth) acrylate-diene system. -A styrene copolymer is obtained.

  The (meth) acrylate-diene-styrene copolymer has a core-shell structure, and the core phase is a diene-based rubber component, while the shell phase is a (meth) acrylate monomer. In addition, it is mainly formed of a styrene monomer. Here, the diene-based rubber component is, for example, polymerization of butadiene, isoprene, 1,3-pentadiene, or copolymerization of these diene monomers with styrene, acrylonitrile, (meth) acrylate monomers, etc. The glass transition temperature is 0 ° C. or lower.

The (meth) acrylate monomer includes an acrylate monomer and a methacrylate monomer. Specific examples of the acrylate monomer and methacrylate monomer are the same as those described in the section of the impact resistant polystyrene resin (B).

  As a method for producing the (meth) acrylate-diene-styrene copolymer, for example, JP 58-59258, JP 61-81455, JP 63-286463, JP, JP-A-1-141944, JP-A-6-200137, US invention patent No. 4180494, and the like.

  The production of a silicon-containing rubber graft copolymer that is an impact modifier of the present invention involves the graft polymerization of a silicon-containing rubber with a styrene monomer, an acrylonitrile monomer, and a (meth) acrylate monomer. The emulsion graft polymerization method is preferred. Taking the emulsion graft polymerization method as an example, a rubber graft is obtained by graft polymerizing a monomer comprising a styrene monomer, an acrylonitrile monomer, a (meth) acrylate monomer, etc. in the presence of a silicon-containing rubber. A copolymer is produced. Specific examples of the silicon-containing rubber include a composite rubber formed from a polyorganosiloxane and a monomer such as a (meth) acrylate monomer, or a polyorganosiloxane and a poly (meth) acrylate rubber. Composite rubber. The form of the silicon-containing rubber graft copolymer is a core-shell structure, the core phase is formed from a rubber component mainly composed of silicon-containing rubber, and one shell phase is a styrene monomer, an acrylonitrile monomer, It is formed from a (meth) acrylate monomer.

  Another object of the present invention is to have a physical property balance comprising good flame retardancy, processing fluidity, impact strength, and excellent elongation characteristics even when a flame retardant is added to the polycarbonate resin composition. That is. The polycarbonate resin composition of the present invention, a flame retardant and a flame retardant aid can be kneaded together to obtain a flame retardant resin composition having good flame retardancy and physical property balance. Examples of the flame retardant include phosphorus flame retardants and halogen flame retardants. Specific examples of halogen flame retardants include decabromodiphenyl ether, ethylenebistetrabromophthalimide, 1,2-bispentabromophenylethane, tetrabromobisphenol A, brominated epoxy resin oligomer, tris (tribromophenyl) phosphate, etc. Is mentioned.

  On the other hand, specific examples of the phosphorus-based flame retardant compound include tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tris-isopropyl biphenyl phosphate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate. , Tributoxyethyl phosphate, octyl diphenyl phosphate, orthophenylphenol phosphate, pentaerythritol phosphate, neopetyl glycol phosphate, substituted neopetyl glycol phosphonate, nitrogen-containing phosphate, and the following chemical formula ( Aromatic phosphate esters shown in 1) are listed. Of these, aromatic phosphates represented by the chemical formula (1) are preferred.

[In the chemical formula (1), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ represent the same or different aromatic group containing no halogen. X is the following chemical formula (2) to (4)

In formulas (2) to (4), R ^{1 to} R ⁸ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, Y is a direct bond, O, S , SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, and Ph represents a phenyl group. In the chemical formula (1), n is an integer of 0 or more. In the chemical formula (1), k and m are each an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less. ]

  The aromatic phosphate ester may be a mixture of aromatic phosphates having different n or different structures.

  In the formula of the chemical formula (1), n is an integer of 0 or more, and the upper limit is preferably 40 or less from the viewpoint of flame retardancy. Preferably it is 0-10, Most preferably, it is 0-5.

  K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably k or m is an integer of 0 or more and 1 or less, particularly preferably k or m is 1.

In the chemical formulas (2) to (4), R ^{1 to} R ⁸ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Here, specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, neopentyl, and tert-pentyl group. Among them, hydrogen, methyl group, and ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups not containing halogen. Examples of the aromatic group include aromatic groups having a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton, and those having a benzene skeleton or a naphthalene skeleton are preferable. These may be substituted with a halogen-free organic residue (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include phenyl groups, tolyl groups, xylyl groups, cumyl groups, mesityl groups, naphthyl groups, indenyl groups, anthryl groups and the like, but phenyl groups, tolyl groups, xylyl groups, cumyl groups, naphthyl groups. Group is preferable, and phenyl group, tolyl group and xylyl group are particularly preferable.

  As commercially available phosphoric acid esters, one or more selected from Daihachi Chemical Co., Ltd. PX-200, PX-201, PX-130, CR-733S, TPP, CR-741, CR747, TCP, TXP, CDP Can be used.

  The amount of the flame retardant used is preferably 1 to 40 parts by weight with respect to 100 parts by weight as the total of the resin (A) and the resin (B).

  Specific examples of the flame retardant aid include antimony trioxide, antimony pentoxide, chlorinated polyethylene, polytetrafluoroethylene, polyhexafluoropropylene, tetrafluoroethylene / hexapropylene copolymer, tetrafluoroethylene / perfluoro. Examples thereof include alkyl vinyl ether copolymers, tetrafluoroethylene / ethylene copolymers, hexafluoropropylene / propylene copolymers, polyvinylidene fluoride, vinylidene fluoride / ethylene copolymers, and among them, polytetrafluoroethylene is preferred. The amount of the flame retardant aid used is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total of the resin (A) and the resin (B).

  In the present invention, other additives can be blended within a range that does not significantly impair the effect of the resin composition. Examples include colorants, fillers, light stabilizers, heat stabilizers, plasticizers, lubricants, mold release agents, viscosity increasing agents, antistatic agents, antioxidants, and conductive agents.

  Examples of the other additives include butyl stearate ester plasticizers, polyester plasticizers, polydimethylsiloxane organosiloxanes, higher fatty acids and metal salts thereof, hindered amine antioxidants, and the like. Single use or mixed use is possible. The amount of the other additive used is 0 to 5 parts by weight with respect to 100 parts by weight of the resin composition.

  For example, glass fiber, diatomaceous earth, calcium carbonate, carbon black or the like can be added to the resin composition of the present invention as necessary. The amount of these used is 0 to 200 parts by weight with respect to 100 parts by weight of the resin composition.

  In addition, other copolymers can be further blended in the resin composition of the present invention. For example, styrene- (meth) acrylate-acrylonitrile copolymer, styrene- (meth) acrylate copolymer, styrene- (meth) acrylate-acrylonitrile-maleimide copolymer, styrene- ( Examples thereof include (meth) acrylate-maleimide copolymers, (meth) acrylate-maleimide copolymers, polyphenol resins, novolac resins, polyphenylene oxide resins, polybutylene terephthalates, and polyethylene terephthalates. The amount of these other copolymers used is 0 to 200 parts by weight with respect to 100 parts by weight of the resin composition.

  The resin composition of the present invention is obtained by melt-kneading the above-mentioned resins, copolymers and additives using a Brabender plastograph, Banbury mixer, kneader, roller press, uniaxial or biaxial general kneader. It is done. The kneading is generally performed at 160 to 280 ° C, more preferably 180 to 250 ° C. There is no particular limitation on the kneading order of each preparation component.

The use of the resin composition of the present invention is not particularly limited, and can be applied to methods such as injection molding, compression molding, extrusion molding, blow molding, vacuum molding and other thermoforming and hollow molding, and various molded products such as sheets and films. Manufactures molded products.

According to the present invention, the polycarbonate-based resin (A) is 25 to 98% by weight [ratio in the total of the resin (A) and the resin (B)], the impact-resistant polystyrene resin (B) is 2 to 75% by weight [resin (A) And 0.2 to 10 parts by weight of the unsaturated unsaturated dicarboxylic acid copolymer (C) with respect to a total of 100 parts by weight of the resin (A) and the resin (B). A process for producing a polycarbonate-based resin composition comprising the steps of:
The resin (B) is obtained by copolymerizing a diene rubber and a monomer copolymerizable with a styrene monomer,
The copolymer (C) is obtained by copolymerization of an unsaturated unsaturated dicarboxylic acid monomer and a styrenic monomer, the solution viscosity is 1.9 cps or less, and the content of the unsaturated unsaturated dicarboxylic acid monomer Is 10 to 60% by weight [ratio in total of monomers constituting the copolymer (C)],
A manufacturing method is provided.

Measurements of physical properties in Examples and Comparative Examples are as follows.
[1] Fluid melt index (MI)
In accordance with the ASTM-D1238 standard, the flow rate for 10 minutes is measured under a load of 10 kg and a melting temperature of 220 ° C. The unit is g / 10 minutes.

[2] Softening temperature (SP)
Measured according to ASTM-D1525 standard. The unit is ° C.

[3] Izod impact strength (IZ)
Measured according to ASTM D-256 (notched, 1/8 inch thick). The unit is kg-cm / cm.

[4] Elongation characteristics (EL)
Measure according to ASTM D-638 (1/8 inch thick dumbbell sheet). Units%.

[5] Combustion test
Test according to UL94 V-0 or UL94 V-2 standard. A sheet of resin composition (125 mm × 13 mm × 2.5 mm) is burned with a flame and then tested to obtain a level of UL94 V-0 or UL94 V-2.

[6] Measurement of solution viscosity (cps) of unsaturated dicarboxylic acid anhydride copolymer (C) An unsaturated dicarboxylic acid copolymer (C) is dissolved in methyl ethyl ketone to prepare a 10 wt% copolymer solution. Take 10 ml of the copolymer solution, put it in a viscometer, and measure the falling time t1 in a thermostatic bath at a temperature of 25 ° C. Also, using a standard solution for viscometer verification of the existing viscosity (preparing a solution according to JIS Z-8809-1978), measure the falling seconds t0 by the same measurement method, and calculate the viscosity tube coefficient K by the following formula: calculate.
K = (η0 × d) / (t0 × d0)
η0: viscosity of standard solution at 25 ° C (cps)
t0: Standard solution drop time at 25 ° C (sec)
d: Density of 10% by weight copolymer solution (g / cm ³ )
d0: density of standard solution at 25 ° C (g / cm ³ )
Subsequently, the solution viscosity (cps) is obtained by multiplying the falling seconds (t1) of the copolymer solution by the viscosity tube coefficient (K). (Solution viscosity = K x t1)

The code | symbol used for an Example and a comparative example represents the following meaning.
-PC-1: Polycarbonate resin (A). Asahi Kasei Co., Ltd., product name PC-110, molecular weight about 26,000.
-PC-2: Polycarbonate resin (A). Asahi Kasei Co., Ltd., trade name PC-175, molecular weight about 15,000.
-HIPS: impact-resistant polystyrene resin (B). Product name PH-888G, molecular weight approx. Rubber content 9% by weight, styrene content 91% by weight.
ABS: Acrylonitrile-diene-styrene copolymer. Product name PA-709S, rubber content 25% by weight, manufactured by Kitami Jitsugyo Co., Ltd.
MBS: (meth) acrylate-diene-styrene copolymer. Product name FPC MBS M-51, rubber content 70% by weight, manufactured by Tai Plastics.
・ Silicone modifier: silicon-containing rubber graft copolymer. Product name Metablen SX-005, manufactured by Mitsubishi Rayon Co., Ltd.
LSMA-1: An unsaturated dicarboxylic acid copolymer (C). Maleic anhydride content 25% by weight, styrene content 75% by weight. The solution viscosity is 0.8 cps (manufactured by Atofina, trade name SMA-3000, molecular weight about 3000).
LSMA-2: An unsaturated dicarboxylic acid copolymer (C). Maleic anhydride content 40 wt%, styrene content 60 wt%. The solution viscosity is 1.6 cps (molecular weight about 15,000).
LSMA-3: An unsaturated dicarboxylic acid copolymer (C). Maleic anhydride content 50 wt%, styrene content 50 wt%. The solution viscosity is 0.72 cps (manufactured by Atofina, trade name SMA-1000, molecular weight about 1000).
LSMA-4: An unsaturated dicarboxylic anhydride copolymer. Maleic anhydride content 25% by weight, styrene content 75% by weight. The solution viscosity is 5 cps.
LSMA-5: An anhydrous unsaturated dicarboxylic acid copolymer. Maleic anhydride content 8 wt%, styrene content 92 wt%. The solution viscosity is 0.8 cps.
LSMA-6: an unsaturated dicarboxylic anhydride copolymer. Maleic anhydride content 8 wt%, styrene content 92 wt%. The solution viscosity is 5 cps.
LSMA-7: An unsaturated dicarboxylic anhydride copolymer. Maleic anhydride content 65% by weight, styrene content 35% by weight. The solution viscosity is 0.8 cps.
・ BDP: Phosphorus flame retardant. Product name: CR-741 flame retardant, manufactured by Daihachi Chemical Co., Ltd.
・ PX-200: Phosphorus flame retardant. Product name: PX-200 flame retardant, manufactured by Daihachi Chemical Co., Ltd.
-TPP: phosphoric acid triphenyl ester, phosphorus flame retardant. Product name: TPP flame retardant, manufactured by Daihachi Chemical Co., Ltd.
PTFE: polytetrafluoroethylene. Product name is 6CJ.

Example 1
A resin comprising 71% by weight of a polycarbonate resin (PC-1), 19% by weight of a polycarbonate resin (PC-2) and 10% by weight of an impact polystyrene resin (HIPS), and a total of 100 parts by weight of the above resins Add 2.1 parts by weight of unsaturated dicarboxylic acid anhydride copolymer (LSMA-1) and 8.0 parts by weight of (meth) acrylate-diene-styrene copolymer (MBS). After kneading at a set temperature of 260 ° C., a pellet-shaped resin composition of the present invention was obtained. Table 1 shows the blending composition and physical property measurement results of the obtained resin composition.

Examples 2-10
Each resin composition of the present invention was obtained as pellets under the same operating conditions as in Example 1 with the blending contents shown in Table 1. Table 1 shows the blending composition and physical property measurement results of each resin composition.

Comparative Example 1
A resin comprising 71% by weight of a polycarbonate resin (PC-1), 19% by weight of a polycarbonate resin (PC-2) and 10% by weight of an impact polystyrene resin (HIPS), and a total of 100 parts by weight of the above resins After adding 8.0 parts by weight of a (meth) acrylate-diene-styrene copolymer (MBS), kneading at a set temperature of 260 ° C. using a twin screw extruder with an exhaust port, A resin composition was obtained. Table 2 shows the blending composition and physical property measurement results of the obtained resin composition.

Comparative Examples 2-8
With the blending contents shown in Table 2, pellet-shaped resin compositions were obtained in the same manner as in Comparative Example 1 (LSMA addition was the same as in Example 1). Table 2 shows the composition of each resin composition and the physical property measurement results.

Comparative Example 9
A resin comprising 71% by weight of a polycarbonate resin (PC-1), 19% by weight of a polycarbonate resin (PC-2) and 10% by weight of an impact polystyrene resin (HIPS), and a total of 100 parts by weight of the above resins Add 2.1 parts by weight of unsaturated dicarboxylic acid anhydride copolymer (LSMA-7) and 8.0 parts by weight of (meth) acrylate-diene-styrene copolymer (MBS), and add a twin screw extruder with an exhaust port. After kneading at a set temperature of 260 ° C., a pellet-shaped resin composition was obtained. The resulting resin composition had a poor hue and turned brown.

Examples 11-12 and Comparative Examples 10-11
Each pellet-shaped resin composition was obtained under the same operating conditions as in Example 1 with the blending contents shown in Table 3. Table 3 shows the blending composition and physical property measurement results of each resin composition.

Example 13
A resin comprising 71% by weight of a polycarbonate resin (PC-1), 19% by weight of a polycarbonate resin (PC-2) and 10% by weight of an impact polystyrene resin (HIPS), and a total of 100 parts by weight of the above resins Unsaturated unsaturated dicarboxylic acid copolymer (LSMA-1) 2.1 parts by weight, (meth) acrylate-diene-styrene copolymer (MBS) 8.0 parts by weight, and further phosphorus flame retardant (BDP) 16 Part by weight, 1.6 parts by weight of polytetrafluoroethylene (PTFE) were added, and after kneading the mixture at a set temperature of 245 ° C. using a twin screw extruder with an exhaust port, a pellet-shaped resin composition was prepared. Obtained. Table 4 shows the blending composition and physical property measurement results of the obtained resin composition.

Examples 14-16 and Comparative Examples 12-15
With the contents shown in Table 4, pellet-shaped resin compositions were obtained under the same operating conditions as in Example 13. Table 4 shows the respective resin composition blend compositions and physical property measurement results obtained.

  In the table, the weight% of PC-1, PC-2, and HIPS is a ratio in the total of 100 weight%. Moreover, the weight part is a ratio with respect to a total of 100 parts by weight of PC-1, PC-2, and HIPS (the same applies hereinafter).

  As can be seen from the results of Examples and Comparative Examples, when the amount of the unsaturated unsaturated dicarboxylic acid copolymer (C) added in Comparative Example 1 and Comparative Example 2 is less than 0.2 parts by weight, the impact strength of the resin composition And the elongation performance is significantly reduced. As can be seen from Comparative Example 3, when the amount of the unsaturated unsaturated carboxylic acid copolymer (C) added exceeds 10 parts by weight, the impact strength of the resin composition is significantly lowered and the softening temperature is also lowered. As can be seen from Comparative Example 4, when the solution viscosity of the unsaturated unsaturated dicarboxylic acid copolymer exceeds 1.9 cps, the impact strength and elongation performance of the resin composition deteriorate. As can be seen from Comparative Example 5, when the maleic anhydride content of the unsaturated dicarboxylic anhydride copolymer is less than 10% by weight, the softening temperature of the resin composition is lowered, and the impact strength and elongation performance are deteriorated. As can be seen from Comparative Example 6, when the maleic anhydride content of the unsaturated dicarboxylic anhydride copolymer is less than 10% by weight and the solution viscosity exceeds 1.9 cps, the impact strength and elongation performance of the resin composition are deteriorated. As can be seen from Comparative Example 7, when the amount of the impact-resistant polystyrene resin (B) used is less than 2 parts by weight, the flow melt index (MI) of the resin composition is low, the processability is poor, and the elongation performance is sufficient. Not improved. As can be seen from Comparative Example 8, when the amount of the impact-resistant polystyrene resin (B) used exceeds 75 parts by weight, the softening temperature of the resin composition is low, the impact strength is greatly reduced, and the elongation performance is poor. As can be seen from Comparative Example 9, when the maleic anhydride content of the unsaturated dicarboxylic anhydride copolymer exceeds 60% by weight, the hue of the resin composition becomes extremely poor. As can be seen from the comparison between Example 11 and Comparative Example 10, the impact strength of the resin composition is lowered and the elongation performance is greatly lowered unless the unsaturated dicarboxylic acid copolymer (C) is added. As can be seen from a comparison between Example 12 and Comparative Example 11, unless the unsaturated dicarboxylic acid copolymer (C) is added, the impact strength of the resin composition is lowered and the elongation performance is greatly lowered. Comparative Examples 12 to 15 are comparative examples in which a flame retardant was added to the resin composition. First, as can be seen from a comparison between Example 13 and Comparative Example 12, the anhydrous saturated dicarboxylic acid copolymer (C) was 0.2. When the amount is less than parts by weight, the impact strength of the resin composition is lowered and the elongation performance is significantly lowered. In Comparative Example 13, since the solution viscosity of the unsaturated dicarboxylic anhydride copolymer (C) exceeds 1.9 cps, the impact strength and elongation performance of the resin composition are deteriorated. In Comparative Example 14, since the maleic anhydride content in the unsaturated dicarboxylic anhydride copolymer (C) was less than 10% by weight, the impact strength and elongation performance of the resin composition deteriorated. In Comparative Example 15, since the maleic anhydride content in the unsaturated dicarboxylic anhydride copolymer (C) is less than 10% by weight and the solution viscosity exceeds 1.9 cps, the elongation performance of the resin composition is deteriorated.

  On the other hand, as can be seen from Examples 1 to 16 in Tables 1 to 4, polycarbonate resin (A) 25 to 98% by weight in the resin composition of the present invention [in total of resin (A) and resin (B) Ratio], impact-resistant polystyrene-based resin (B) 2 to 75% by weight (ratio in the total of resin (A) and resin (B)), and the solution viscosity is 1.9 cps or less, and anhydrous unsaturated dicarboxylic acid The unsaturated dicarboxylic acid copolymer (C) having a monomer unit content of 10 to 60% by weight (ratio in the total of monomers constituting the copolymer (C)) is the resin (A) and the resin. When the amount is 0.2 to 10 parts by weight relative to the total of 100 parts by weight of (B), a resin composition having good fluidity, impact strength and elongation characteristics can be obtained. Moreover, when a flame retardant is added to the polycarbonate resin composition of the present invention, a resin having good flame retardant properties and physical property balance can be obtained.

Claims (4)

Polycarbonate resin (A) 25 to 98% by weight [ratio of the total of resin (A) and resin (B)], impact polystyrene resin (B) 2 to 75% by weight [resin (A) and resin (B ), And 0.2 to 10 parts by weight of the unsaturated dicarboxylic acid anhydride copolymer (C) with respect to a total of 100 parts by weight of the resin (A) and the resin (B),
The resin (B) is obtained by copolymerizing a diene rubber and a monomer copolymerizable with a styrene monomer,
The copolymer (C) is obtained by copolymerization of an unsaturated unsaturated dicarboxylic acid monomer and a styrenic monomer, the solution viscosity is 1.9 cps or less, and the content of the unsaturated unsaturated dicarboxylic acid monomer Is 10 to 60% by weight [ratio in total of monomers constituting the copolymer (C)],
Polycarbonate resin composition. The polycarbonate resin composition according to claim 1, further comprising an impact modifier. The impact modifier is selected from a (meth) acrylate-diene-styrene copolymer, an acrylonitrile-diene-styrene copolymer, and a silicon-containing rubber graft copolymer, and a resin (A ) And the resin (B), the polycarbonate resin composition according to claim 2, containing 1 to 14 parts by weight with respect to 100 parts by weight in total. The polycarbonate-based resin composition according to claim 1, further comprising 1 to 40 parts by weight of a phosphorus-based flame retardant based on a total of 100 parts by weight of the resin (A) and the resin (B).