JP2010077379A - Polycarbonate resin composition and method of producing molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in balance between impact resistance and rigidity and excellent in hydrolysis resistance. <P>SOLUTION: The polycarbonate resin composition includes: 100 pts.mass of a matrix resin component comprising 50-99 mass% of a polycarbonate resin (A) and 1-50 mass% of an inorganic filler (B); and 0.5-30 pts.mass of a graft copolymer (C). The graft copolymer (C) is obtained by polymerizing a monomer component (g) including at least any one of an aromatic vinyl monomer (a), a vinyl cyanide monomer (b), and an alkyl (meth)acrylate (c) in the presence of a composite rubber (r) containing polyorganosiloxane and polyalkyl (meth)acrylate and having a mass average particle size of 120 nm or less. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polycarbonate resin composition excellent in impact resistance, rigidity, and hydrolysis resistance. Moreover, it is related with the manufacturing method of the molded object which shape | molds the resin composition and obtains a molded object.

In recent years, in housing applications such as OA equipment, IT equipment, and home appliances, the weight of each equipment has been reduced and the size has been reduced, and thus the housing member has been required to be thinner. Therefore, high rigidity is required for the resin material for the housing member. Moreover, since the integration density of electrical and electronic equipment is high, the temperature inside the equipment tends to be high, and heat resistance is required for the resin material for the housing member.
For this reason, polycarbonate resin is widely used as the resin material for the housing member, but higher rigidity and heat resistance are required.
As a method of increasing the rigidity and heat resistance of a polycarbonate resin, a method of adding an inorganic filler is known. However, when an inorganic filler is added, the impact resistance tends to decrease, so an impact strength modifier is often used in combination.

For example, Patent Document 1 proposes a resin composition comprising a polycarbonate resin and its oligomer, glass fiber, and an impact strength modifier. Patent Document 2 proposes a resin composition comprising a polycarbonate resin, an impact strength modifier, a PTFE-containing powder, and a filler. However, the resin compositions proposed in Patent Documents 1 and 2 have a problem that the impact resistance is improved, but the rigidity is insufficient, so that the thinned product cannot be sufficiently thinned.
Further, the polycarbonate resin has a defect that it easily undergoes hydrolysis, and countermeasures are required. However, none of these patent documents mentions this.

Japanese Patent Laid-Open No. 9-12858 JP 2004-10823 A

  An object of this invention is to provide the manufacturing method of the polycarbonate resin composition and the molded object which are excellent in the balance of impact resistance and rigidity, and are excellent in hydrolysis resistance.

The present invention has the following configuration.
[1] 0.5-100 mass of graft copolymer (C) with respect to 100 mass parts of the matrix resin component consisting of 50-99 mass% of polycarbonate resin (A) and 1-50 mass% of inorganic filler (B). Part
The graft copolymer (C) is an aromatic vinyl monomer (a) in the presence of a composite rubber (r) containing a polyorganosiloxane and a polyalkyl (meth) acrylate and having a mass average particle diameter of 120 nm or less. A polycarbonate resin composition obtained by polymerizing a monomer component (g) containing at least one of a vinyl cyanide monomer (b) and an alkyl (meth) acrylate (c).
[2] The mass ratio (r / g) of the composite rubber (r) to the monomer component (g) is 10 to 60/40 to 90 (provided that the total of (r) and (g) is 100. The polycarbonate resin composition according to [1].
[3] A method for producing a molded article by molding the polycarbonate resin composition according to [1] or [2].

  According to the polycarbonate resin composition and the method for producing a molded article of the present invention, a molded article having an excellent balance between impact resistance and rigidity and excellent in hydrolysis resistance can be obtained.

Hereinafter, the present invention will be described in detail.
The polycarbonate resin composition of the present invention contains a matrix resin component composed of a polycarbonate resin (A) and an inorganic filler (B), and a graft copolymer (C).

The polycarbonate resin (A) is preferably an aromatic polycarbonate resin because of its high impact resistance and rigidity.
The aromatic polycarbonate resin is usually obtained by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method.
Examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, and 2,2-bis (4-hydroxy-3,5-dimethylphenyl). ) Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) sulfone. Among these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferable. A dihydric phenol may be used individually by 1 type, and may use 2 or more types together.
Examples of the carbonate precursor include carbonyl hydride, carbonic acid diester, haloformate, and the like. Specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and a mixture thereof can be used.

When phosgene is used as the carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a solvent.
As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
As the solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used.
In order to accelerate the reaction, for example, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. In this case, the reaction temperature is preferably 0 to 40 ° C., and the reaction time is preferably several minutes to 5 hours.

When carbonic acid diester is used as a carbonate precursor and an aromatic polycarbonate resin is produced by transesterification, it is produced by stirring a predetermined proportion of aromatic dihydroxy component and carbonic acid diester under an inert gas atmosphere. A method of distilling alcohol or phenols is employed.
The reaction temperature in this case varies depending on the boiling point of the alcohol or phenol produced, but is usually in the range of 120 to 300 ° C. In order to distill off the alcohol and phenol produced during the reaction, the reactor is preferably decompressed from the initial stage of the reaction.
In order to accelerate the reaction, a catalyst usually used for transesterification may be used.
Examples of the carbonic acid diester include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate. Diphenyl carbonate is preferred because of its high reactivity.
Moreover, when manufacturing an aromatic polycarbonate resin, you may use a molecular weight modifier etc. suitably.
The aromatic polycarbonate resin thus obtained may be used alone or in combination of two or more.

  The viscosity average molecular weight of the polycarbonate resin (A) is preferably 10,000 to 60,000, and more preferably 15,000 to 30,000. If the viscosity average molecular weight of the polycarbonate resin (A) is 10,000 or more, impact resistance and rigidity can be further increased, and if it is 60,000 or less, the fluidity is not significantly impaired.

As the inorganic filler (B), those having various shapes such as a fibrous shape, a particulate shape, a powder shape, a plate shape, and a needle shape can be used. Examples of the inorganic filler (B) include glass fibers (including those coated with metals), carbon fibers (including those coated with metals), potassium titanate, asbestos, silicon carbide, silicon nitride, ceramic fibers, Metal fiber, aramid fiber, barium sulfate, calcium sulfate, calcium silicate, calcium carbonate, magnesium carbonate, antimony trioxide, zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, mica, talc, kaolin, pyrophyllite , Bentonite, sericite, zeolite, wollastonite, alumina, clay, ferrite, graphite, gypsum, glass beads, glass balloon and quartz. These inorganic fillers may be used alone or in combination of two or more.
Among the inorganic fillers (B), plate-like inorganic fillers are preferred because the effects of improving impact resistance and rigidity due to the incorporation of the graft copolymer (C) are remarkably exhibited. Examples of the plate-like inorganic filler include talc, mica, and plate-like alumina.

  The content rate of an inorganic filler (B) is 1-50 mass% when a matrix resin component is 100 mass%, and it is preferable that it is 3-30 mass%. When the content of the inorganic filler (B) is 1% by mass or more, a molded article having high rigidity and excellent heat resistance, fatigue characteristics, and the like can be obtained. Moreover, if the content rate of an inorganic filler (B) is 50 mass% or less, the molded object excellent in impact resistance will be obtained.

  In the presence of the composite rubber (r) containing a polyorganosiloxane and a polyalkyl (meth) acrylate and having a mass average particle diameter of 120 nm or less, the graft copolymer (C) contains an aromatic vinyl monomer (a), It is obtained by polymerizing a monomer component (g) containing at least one of vinyl cyanide monomer (b) and alkyl (meth) acrylate (c).

  In the polyorganosiloxane, the organosiloxane is a grafting agent for polyorganosiloxane (hereinafter referred to as “siloxane crosslinking agent”) and, if necessary, a crosslinking agent for polyorganosiloxane (hereinafter referred to as “siloxane crosslinking agent”). It is polymerized via.

The organosiloxane is preferably a cyclic organosiloxane having 3 or more members, more preferably a 3 to 6 members.
Examples of the cyclic organosiloxane include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclohexane. Tetrasiloxane is mentioned. These cyclic organosiloxanes may be used alone or in combination of two or more.

  The content of the organosiloxane is preferably 60 to 99.9% by mass when the mixture of the organosiloxane, the siloxane crossing agent and the siloxane crosslinking agent (hereinafter referred to as “organosiloxane mixture”) is 100% by mass. 70-99.9 mass% is more preferable. When the organosiloxane content is 60% by mass or more, a molded article having excellent impact resistance at low temperatures can be obtained. If the organosiloxane content is 99.9% by mass or less, a molded article having stable impact resistance can be obtained.

Examples of the siloxane crossing agent include those capable of bonding to an organosiloxane via a siloxane bond and forming a bond with a polyalkyl (meth) acrylate in the composite rubber. An alkoxysilane compound having a functional group capable of reacting with is preferred.
Examples of the siloxane crossing agent include β- (meth) acryloyloxyethyldimethoxymethylsilane, γ- (meth) acryloyloxypropyldimethoxymethylsilane, γ- (meth) acryloyloxypropylmethoxydimethylsilane, γ- (meth) acryloyl. (Meth) acryloyloxy such as oxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylethoxydiethylsilane, γ- (meth) acryloyloxypropyldiethoxymethylsilane, δ- (meth) acryloyloxybutyldiethoxymethylsilane Silanes; vinyl siloxanes such as tetramethyltetravinylcyclotetrasiloxane; vinylphenyl silanes such as p-vinylphenyldimethoxymethylsilane; and γ-mercaptopropyldimethoxymethyl Mercaptosilanes such as silane and γ-mercaptopropyltrimethoxysilane are exemplified. These may be used alone or in combination of two or more.

  The content of the siloxane crossing agent is preferably 0.1 to 10% by mass when the organosiloxane mixture is 100% by mass. When the content of the siloxane crossing agent is 0.1% by mass or more, the graft polymerization of the monomer component (g) with respect to the composite rubber (r) becomes possible. Moreover, if the content rate of a siloxane crossing agent is 10 mass% or less, the balance of the molecular weight and number of the polymer of a graft part will become favorable.

Examples of the siloxane cross-linking agent include those having three or four functional groups capable of bonding to an organosiloxane.
Examples of the siloxane crosslinking agent include trialkoxyalkylsilanes such as trimethoxymethylsilane; trialkoxyarylsilanes such as triethoxyphenylsilane; and tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, and tetrabutoxysilane. Examples include tetraalkoxysilane. These may be used alone or in combination of two or more.
Among these, tetraalkoxysilane is preferable, and tetraethoxysilane is more preferable.

  The content of the siloxane crosslinking agent is preferably 30% by mass or less based on 100% by mass of the organosiloxane mixture. When the content of the siloxane crosslinking agent is 30% by mass or less, a molded article having excellent impact resistance can be obtained.

Examples of the method for producing the polyorganosiloxane include a method by emulsion polymerization of an organosiloxane mixture. An example of a method for emulsion polymerization of an organosiloxane mixture is shown below.
First, an emulsifier and water are added to the organosiloxane mixture to obtain a latex of the organosiloxane mixture. Subsequently, after the latex of the organosiloxane mixture is microparticulated by the method described later, an acid catalyst is mixed with the microparticulated latex and emulsion polymerization is performed.
Another method includes adding an emulsifier, water, and an acid catalyst to the organosiloxane mixture to form a latex, and then finely pulverizing the latex, followed by emulsion polymerization.

Examples of the emulsifier used in the emulsion polymerization include anionic emulsifiers such as sodium alkylbenzene sulfonate, sodium alkyl sulfonate, and sodium polyoxyethylene alkyl sulfate. These may be used alone or in combination of two or more.
Among these, sulfonic acid-based emulsifiers such as sodium alkylbenzene sulfonate and sodium alkyl sulfonate are preferable because they can be easily emulsion polymerized.

  The amount of the emulsifier used is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the organosiloxane mixture because a stable dispersion state of the latex can be obtained. Moreover, the usage-amount of an emulsifier has the preferable point of 15 mass parts or less with respect to 100 mass parts of organosiloxane mixtures from the point which suppresses coloring of the polycarbonate resin composition by the color of an emulsifier.

  Examples of the method for forming the fine particles of the latex include a method using a homomixer that makes the hydrophobic substance in the latex fine particles by a shearing force by high-speed rotation, and a homogenizer that makes fine particles by a jet output from a high-pressure generator. Among these, the method of using a high-pressure emulsifier such as a homogenizer is preferable in that a latex having a small particle size distribution can be obtained.

When the acid catalyst is mixed before the latex is finely divided, the acid catalyst can be added to and mixed with the organosiloxane mixture, the emulsifier and water as an aqueous solution or as a solid.
In addition, when the acid catalyst is mixed after the latex is finely divided, the acid catalyst is used as an aqueous solution in order to easily control the particle diameter of the resulting polyorganosiloxane, and the finely divided latex is added to the hot acid catalyst aqueous solution. A method of dropping and polymerizing at a constant rate is preferable.
Examples of the acid catalyst include sulfonic acids such as aliphatic sulfonic acid, aliphatic substituted benzene sulfonic acid, and aliphatic substituted naphthalene sulfonic acid, and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These may be used alone or in combination of two or more.
Among these, aliphatic-substituted benzenesulfonic acid is preferable and n-dodecylbenzenesulfonic acid is more preferable because it is excellent in stabilizing the polyorganosiloxane latex.

The amount of the acid catalyst used is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the organosiloxane mixture.
In the method of dropping the latex of the organosiloxane mixture after atomization into a high-temperature acid catalyst aqueous solution at a constant rate, the polymerization time is preferably about 1 hour after completion of dropping of the latex. In the method in which the latex is made fine after the acid catalyst is added, the polymerization time is preferably 2 hours or more, more preferably 5 hours or more. The polymerization temperature is preferably 50 ° C. or higher, more preferably 80 ° C. or higher.
The polymerization can be stopped by cooling the reaction solution and further neutralizing with an alkaline substance such as sodium hydroxide, potassium hydroxide or sodium carbonate.

  Polyalkyl (meth) acrylates include alkyl (meth) acrylates, graft crossover agents for polyalkyl (meth) acrylates (hereinafter referred to as “acrylic crossover agents”), and if necessary, crosslinkers for polyalkyl (meth) acrylates. (Hereinafter referred to as “acrylic crosslinking agent”).

Examples of the alkyl (meth) acrylate include alkyl acrylate such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, and the like. And alkyl methacrylate having 6 or more carbon atoms in the alkyl group. These may be used alone or in combination of two or more.
Among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferable because impact resistance can be further improved.

  The content of the alkyl (meth) acrylate was 100% by mass of a mixture of the alkyl (meth) acrylate, the acrylic cross-linking agent, and if necessary, an acrylic crosslinking agent (hereinafter referred to as “alkyl (meth) acrylate mixture”). 80 to 99.99% by mass is preferable, and 90 to 99.99% by mass is more preferable. When the alkyl (meth) acrylate content is 80% by mass or more, a molded article having excellent impact resistance can be obtained. Moreover, if the content rate of an alkyl (meth) acrylate is 99.99 mass% or less, a molded object with stable impact resistance will be obtained.

The acrylic crossover agent has two or more polymerizable unsaturated groups that react with alkyl (meth) acrylate, and has a polymerizable unsaturated group such as an allyl group that is different in reactivity from the (meth) acryloyl group. Monomer. By having a polymerizable unsaturated group having different reactivity, a vinyl monomer is grafted to the polymerizable unsaturated group present in the acrylic cross-linking agent unit in the obtained polyalkyl (meth) acrylate, A graft portion is formed.
Specific examples of the acrylic crossing agent include allyl methacrylate, triallyl cyanurate, and triallyl isocyanate. These may be used alone or in combination of two or more.

  The content of the acrylic crossover agent is preferably 0.01 to 10% by mass when the alkyl (meth) acrylate mixture is 100% by mass. When the content of the acrylic crossing agent is 0.01% by mass or more, a sufficient number of graft polymerization starting points can be formed in the polyalkyl (meth) acrylate. Moreover, if the content rate of an acrylic crossing agent is 10 mass% or less, the elasticity of polyalkyl (meth) acrylate can be maintained.

The acrylic crosslinking agent has two or more functional groups that react with the alkyl (meth) acrylate and forms a crosslinked structure in the polyalkyl (meth) acrylate.
Specific examples of the acrylic crosslinking agent include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethyloltetra (meth) acrylate and divinylbenzene. These may be used alone or in combination of two or more.

  As for the content rate of an acrylic crosslinking agent, 10 mass% or less when an alkyl (meth) acrylate mixture is 100 mass% is preferable. If the content rate of an acrylic crosslinking agent is 10 mass% or less, the elasticity of a polyalkyl (meth) acrylate can be maintained.

As a manufacturing method of polyalkyl (meth) acrylate, the method of carrying out emulsion polymerization of the alkyl (meth) acrylate mixture in presence of polyorganosiloxane is mentioned, for example.
Examples of the method for adding the alkyl (meth) acrylate mixture to the polyorganosiloxane include a method in which the entire amount of the alkyl (meth) acrylate mixture is added all at once, and a method in which the addition is divided. When adding in divided portions, it may be added continuously or intermittently.
In this production method, as the polymerization of the alkyl (meth) acrylate mixture proceeds, a graft copolymer in which polyalkyl (meth) acrylate is graft-polymerized to polyorganosiloxane due to the presence of a siloxane crosslinker or an acrylic crosslinker, A cross-linked network structure entangled with each other at the interface of siloxane and polyalkyl (meth) acrylate is formed, and a composite rubber that cannot be separated from each other is obtained. A homopolymer of polyalkyl (meth) acrylate is also obtained.

When polymerizing the alkyl (meth) acrylate mixture, water, a radical polymerization initiator, a chain transfer agent for controlling the molecular weight of the polyalkyl (meth) acrylate, an emulsifier, and the like can be added as necessary.
At the time of addition of the alkyl (meth) acrylate mixture, the alkyl (meth) acrylate mixture is made into a latex, and this latex is made into a fine particle by the same method as the fine particle formation of the latex of the organosiloxane mixture described above, and then a polyorganosiloxane latex. Can be added.

Examples of the radical polymerization initiator include a peroxide, an azo polymerization initiator, and a redox polymerization initiator in which an oxidizing agent and a reducing agent are combined. Among these, a redox polymerization initiator is preferable, and a combination of ferrous sulfate, sodium pyrophosphate, glucose, and hydroperoxide, a redox polymerization initiator and ferrous sulfate, ethylenediaminetetraacetic acid disodium salt, Rongalite, A redox polymerization initiator in combination with hydroperoxide is particularly preferred.
Examples of the chain transfer agent include mercaptan compounds, terpene compounds, and α-methylstyrene dimers.

Examples of the emulsifier include various carboxylates such as sodium sarcosine, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, and rosin acid soap, alkyl sulfate, alkyl benzene sulfonate, sodium alkyl sulfonate, polyoxyethylene alkyl sulfate. Anionic emulsifiers such as sodium are listed. These can stably hold the latex at the time of emulsion polymerization and increase the polymerization rate, and can be used alone or in combination of two or more.
In the emulsion polymerization of the alkyl (meth) acrylate mixture, the emulsifier present in the polyorganosiloxane latex may be diverted to emulsion polymerization without adding a new emulsifier.

  The content of polyalkyl (meth) acrylate in the composite rubber (100% by mass) of polyorganosiloxane and polyalkyl (meth) acrylate is 5 to 99% by mass (the content of polyorganosiloxane is 1 to 95% by mass). The content is preferably 10 to 95% by mass (polyorganosiloxane content is 5 to 90% by mass). When the polyalkyl (meth) acrylate content is 5% by mass or more, a molded article having stable impact resistance in a wide molding region can be obtained. Moreover, if the content rate of polyalkyl (meth) acrylate is 99 mass% or less, the molded object excellent in the impact resistance at the time of low temperature, a flame retardance, mold release property, and insulation will be obtained.

The mass average particle size (d _w ) of the composite rubber (r) is 120 nm or less, preferably 100 nm or less. When the mass average particle diameter (d _w ) is 120 nm or less, impact resistance can be improved without reducing the rigidity of the molded body.
The mass average particle diameter (d _w ) of the composite rubber (r) is preferably 20 nm or more, and more preferably 50 nm or more. If the mass average particle diameter (d _w ) is 20 nm or more, impact resistance can be improved without impairing dispersibility in the molded product.

The graft copolymer (C) includes at least one of an aromatic vinyl monomer (a), a vinyl cyanide monomer (b), and an alkyl (meth) acrylate (c) on the composite rubber (r). It can be obtained by adding a monomer component (g) containing water and, if necessary, water, an emulsifier, a radical polymerization initiator, a chain transfer agent and the like, and graft polymerization.
As the emulsifier, the radical polymerization initiator, the chain transfer agent and the like used for the graft polymerization of the graft copolymer, the same ones used in the production of the polyalkyl (meth) acrylate can be used.

  In the step of obtaining the graft copolymer (C), the mass ratio (r / g) between the composite rubber (r) and the monomer component (g) is in the range of 10 to 60/40 to 90 (provided that (The sum of (r) and (g) is 100). When the ratio of the composite rubber (r) is 10% by mass or more (the ratio of the monomer component (g) is 90% by mass or less), a molded article having excellent impact resistance can be obtained. Moreover, if the ratio of the composite rubber (r) is 60% by mass or less (the ratio of the monomer component (g) is 40% by mass or more), a molded article having an excellent balance between impact resistance and rigidity can be obtained.

  In this graft polymerization, a free polymer of the monomer component (g) alone that is not grafted to the composite rubber (r) is by-produced. Therefore, the graft copolymer (C) is polymerized without grafting the monomer component (g) onto the composite rubber (r) and the monomer component (g) without grafting onto the composite rubber (r). It is a mixture with the non-grafting component.

Examples of the aromatic vinyl monomer (a) include styrene, α-methylstyrene, and vinyl toluene. Of these, styrene is particularly preferable. Moreover, these aromatic vinyl monomers may be used individually by 1 type, and may use 2 or more types together.
Examples of the vinyl cyanide monomer (b) include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-ethylacrylonitrile. Of these, acrylonitrile is particularly preferred. Moreover, these vinyl cyanide monomers may be used individually by 1 type, and may use 2 or more types together.

Examples of the alkyl (meth) acrylate (c) include methyl acrylate, ethyl acrylate, n-butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, propyl methacrylate, 2 -Ethylhexyl methacrylate, glycidyl methacrylate are mentioned. Of these, methyl methacrylate is preferred.
Alkyl (meth) acrylate may be used individually by 1 type, and may use 2 or more types together.

The ratio of the aromatic vinyl monomer (a), the vinyl cyanide monomer (b) and the alkyl (meth) acrylate (c) used for the graft polymerization in the monomer component (g) is not particularly limited. However, when the monomer component (g) includes the aromatic vinyl monomer (a) and the vinyl cyanide monomer (b), from the viewpoint of heat resistance and chemical resistance, the aromatic vinyl monomer In the total amount of 100% by mass of the monomer (a) and the vinyl cyanide monomer (b), the content of the vinyl cyanide monomer (b) is preferably 10 to 50% by mass.
When the monomer component (g) contains an alkyl methacrylate (c) and an alkyl acrylate (c), from the viewpoint of compatibility and dispersibility of the graft copolymer (C), the alkyl methacrylate ( In 100 mass% of the total amount of c) and alkyl acrylate (c), the content of alkyl acrylate (c) is preferably 0.1 to 20 mass%.

As the monomer component (g), examples of the monomer (d) copolymerizable with the monomers (a) to (c) include, for example, an ethylenically unsaturated carboxylic acid monomer and a vinyl halide monomer. A monomer and a maleimide monomer may be contained.
Examples of the ethylenically unsaturated carboxylic acid monomer include monocarboxylic acids and dicarboxylic acids such as acrylic acid, methacrylic acid, maleic acid, and itaconic acid. These ethylenically unsaturated carboxylic acid monomers may be used individually by 1 type, and may use 2 or more types together.
Examples of the vinyl halide monomer include vinyl chloride and vinylidene chloride. These vinyl halide monomers may be used alone or in combination of two or more.

Examples of the maleimide monomer include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and N-methylmaleimide. These maleimide monomers may be used alone or in combination of two or more.
In addition to the above monomers, monomers capable of emulsion polymerization such as ethylene, propylene, vinyl acetate, and vinylpyridine can also be used.
Furthermore, a cross-linking agent such as divinylbenzene, 1,3-butylene dimethacrylate, allyl methacrylate, or a chain transfer agent such as mercaptans may be used in combination.

According to the graft polymerization, a latex of the graft copolymer (C) is obtained. From the latex of the graft copolymer (C), the graft copolymer (C) can be recovered as a powder by a coagulation and drying method or a spray drying method.
As a method by coagulation and drying, for example, a salt such as calcium chloride, calcium acetate, magnesium sulfate or an acid such as sulfuric acid is appropriately coagulated as a coagulant, and then coagulated by heat treatment and then filtered. And a method of recovering as powder after washing and dehydration.
Examples of the spray drying method include a method of spraying latex in a heated and decompressed container. The spray-drying method is preferable because it can be easily handled as a powder.

  The mass average particle diameter of the graft copolymer (C) is preferably 80 to 1000 nm. If the mass average particle diameter of the graft copolymer (C) is 80 nm or more, a molded article having excellent impact resistance can be obtained. Moreover, if the mass average particle diameter of the graft copolymer (C) is 1000 nm or less, the productivity of the graft copolymer (C) will be good.

  The blending amount of the graft copolymer (C) in the polycarbonate resin composition of the present invention is 0.5 to 30 parts by mass with respect to 100 parts by mass of the matrix resin component because the resulting molded article has excellent impact strength. 3 to 20 parts by mass is preferable. If the compounding quantity of a graft copolymer (C) is 0.5 mass part or more, the impact resistance of the obtained molded object will improve. Moreover, if the compounding quantity of a graft copolymer (C) is 30 mass parts or less, the improvement effect of the rigidity and heat resistance which an inorganic filler (B) has will fully be exhibited.

Various additives can be blended in the polycarbonate resin composition of the present invention as necessary.
Examples of the additive include triphenyl phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, diphenyl hydrogen phosphite, irganox 1076 [stearyl-β- (3,5-di- t-butyl-4-hydroxyphenyl) propionate manufactured by Ciba Japan Co., Ltd.]; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-) Weather resistance improvers such as 3 ′, 5′-di-t-amylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2-hydroxy-4-octoxybenzophenone; Tetrabromobisphenol A (TBA), TBA polycarbonate oligo -, Halogen flame retardants such as TBA tribromophenol, TBA epoxy oligomer, brominated polystyrene, chlorinated paraffin, dechlorane plus; triphenyl phosphate, tricresyl phosphate, halogen-containing phosphate, condensed phosphoric acid Phosphoric esters such as esters, phosphoric amides, red phosphorus, ammonium polyphosphate, phosphorous flame retardants such as ammonium phosphazene compounds; nitrogen flame retardants such as triazine compounds; metal salts such as zinc borate, aluminum hydroxide, water Inorganic flame retardants such as metal hydroxides such as magnesium oxide and metal oxides such as antimony trioxide; silicone flame retardants; plasticizers; antistatic agents; mold release agents; dyes and pigments; heat resistance improvers; Agents; fluidity improvers; conductivity-imparting agents; surfactants; compatibilizers; antifogging agents; foaming agents and antibacterial agents.

The polycarbonate resin composition of the present invention includes, for example, a step of obtaining a graft copolymer (C) and a graft copolymer (C) in a matrix resin component comprising a polycarbonate resin (A) and an inorganic filler (B). And the process of manufacturing.
The process of obtaining a graft copolymer is as the manufacturing method of the said graft copolymer (C). As described above, the blending amount of the graft copolymer (C) in the matrix resin component is 0.5 to 30 parts by mass with respect to 100 parts by mass of the matrix resin component.

  As a specific example of the method for producing the polycarbonate composition, the graft copolymer (C) obtained by the above production method, the polycarbonate resin (A), the inorganic filler (B), and, if necessary, an additive are added to Henschel. After blending with a mixer, tumbler mixer, etc., the resulting mixture is melt-mixed with an extruder, kneader, mixer, etc., and other components are sequentially mixed with the previously melted component (A) or (C) Is mentioned. Further, the polycarbonate resin (A), the inorganic filler (B), the graft copolymer (C) and, if necessary, a mixture of various additives may be directly put into an injection molding machine for molding.

Conventionally, when an inorganic filler (B) is blended with a polycarbonate resin (A), hydrolysis of the polycarbonate resin (A) occurs at the interface, and physical properties tend to be lowered. However, in the polycarbonate resin composition of the present invention, since the graft copolymer (C) added to the polycarbonate resin (A) and the inorganic filler (B) is present around the inorganic filler (B), the polycarbonate resin It becomes difficult for the inorganic filler (B) to come into direct contact with (A). Therefore, hydrolysis resistance is improved.
Moreover, according to the graft copolymer (C), impact resistance can be improved without reducing rigidity.

The method for producing a molded body of the present invention is a method for obtaining a molded body by molding the polycarbonate resin composition by various molding methods.
Examples of the molding method include injection molding, extrusion molding, vacuum molding, compression molding, and blow molding.

  The molded product obtained by the present invention has an excellent balance between impact resistance and rigidity and is excellent in hydrolysis resistance. For example, a copier, a facsimile transceiver, a printer, a desktop type / notebook type / tower type / Server-type computers, personal digital assistants (PDAs), mobile phones / PHS, televisions, video decks, housings and chassis parts for various OA / information / home appliances such as audio equipment, housings for PHS switches, telephone switches, etc., air conditioners / coolers It is particularly suitably used for applications such as housings for indoor and outdoor units, housings for home appliances, tableware applications, display components, and various building material members.

Hereinafter, the present invention will be described specifically by way of examples. In the following description, “part” means “part by mass”, and “%” means “% by mass”.
In the following examples, the latex mass average particle diameter was measured by the method shown in (1) below. Moreover, about the polycarbonate resin composition, Izod impact strength, a bending characteristic, and hydrolysis resistance were evaluated by the method shown to (2)-(4).

(1) Mass average particle diameter (d _w )
A sample obtained by diluting latex with distilled water was used as a sample, and a mass average particle size was measured under the following conditions using a CHDF2000 type particle size distribution meter manufactured by Matec, USA.
Using a capillary cartridge for particle separation dedicated to CHDF2000 type particle size distribution meter manufactured by Matec, Inc. in the United States and a carrier liquid, with the liquidity being neutral, the flow rate being 1.4 mL / min, the pressure being 28 MPa, and the temperature being kept at 35 ° C. Then, 0.1 mL of a diluted latex sample having a concentration of 3% was used for the measurement. In addition, as the standard particle size substance, monodispersed polystyrene with a known particle size manufactured by Duke of USA was used, and a total of 12 samples were used within a range of 30 to 800 nm.

(2) Izod impact strength A test piece for measuring Izod impact strength (1/8 inch, notched) having a width of 63.5 mm, a height of 12.7 mm, and a thickness of 3.2 mm was prepared, and ASTM D256 was used using the test piece. By the method, Izod impact strength was measured at 23 ° C.

(3) Bending characteristics A 3.2 mm-thickness test piece was prepared, and bending characteristics (bending strength, bending elastic modulus) were measured by a method based on ASTM D790 using the test piece.

(4) Hydrolysis resistance Using a pressure cooker test apparatus, the pellets molded with the polycarbonate resin composition are allowed to stand for 60 hours in an atmosphere at a temperature of 120 ° C. and a relative humidity of 100%. The melt index (MI) was measured under the following conditions in accordance with JIS K7210.
Temperature 300 ° C, load 21.2N: (talc 1, mica)
Temperature 250 ° C., load 50.0 N: (plate-like alumina, GF, talc 2)

  The above evaluations (2) to (4) were performed under absolutely dry conditions.

Reference Example 1 Production of Latex of Composite Rubber (r-1) 97.5 parts of octamethylcyclotetrasiloxane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 2 parts of tetraethoxysilane were mixed to prepare an organosiloxane. 100 parts of a mixture were obtained. To 100 parts of this organosiloxane mixture, 200 parts of deionized water in which 1.0 part of sodium dodecylbenzenesulfonate was dissolved was added and stirred for 5 minutes at 10,000 rpm with a homomixer and mixed. Further, it was passed twice through a homogenizer at a pressure of 20 MPa to obtain a latex of an organosiloxane mixture after micronization.
Next, 10 parts of dodecylbenzenesulfonic acid and 190 parts of deionized water were put into a separable flask equipped with a thermometer, a condenser, and a stirring device to prepare a 10% aqueous solution of dodecylbenzenesulfonic acid. In a state where this aqueous solution of dodecylbenzenesulfonic acid was heated to 85 ° C., 300 parts of latex of the organosiloxane mixture after the micronization was dropped over 2 hours. After maintaining the temperature for 3 hours after the completion of the dropping, the reaction product was obtained by cooling.
Further, this reaction product was kept at room temperature for 6 hours and then neutralized with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane latex. 15 g of this latex was sampled and dried at 180 ° C. for 30 minutes to obtain a solid content of 18.1%. Moreover, the mass average particle diameter (d _w ) of this latex was 62 nm.

Into a separable flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, and a stirrer, 54.2 parts (9.8 parts as a solid content) of the polyorganosiloxane latex were charged. Next, 150 parts of deionized water was added, and then a mixture of 90.2 parts of n-butyl acrylate, 0.05 parts of allyl methacrylate and 0.4 parts of t-butyl hydroperoxide was added. Next, the atmosphere in the flask was replaced with nitrogen by passing nitrogen, and the temperature was raised to 50 ° C.
When the liquid temperature reached 50 ° C., an aqueous solution in which 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt and 0.3 part of Rongalite were dissolved in 10 parts of deionized water was added, Radical polymerization was performed for 5 hours. Then, the temperature in a separable flask was hold | maintained at 65 degreeC for 1 hour, and the latex of the composite rubber (r-1) containing polyorganosiloxane and polyalkyl (meth) acrylate was obtained.
The solid content concentration of the latex of the composite rubber (r-1) was 29.1%, and the mass average particle diameter (d _w ) was 97 nm.

Reference Example 2 Production of Latex of Composite Rubber (r-2) 97.5 parts of octamethylcyclotetrasiloxane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 2 parts of tetraethoxysilane were mixed to prepare organo 100 parts of a siloxane mixture were obtained. To 100 parts of this organosiloxane mixture was added 0.67 part of sodium dodecylbenzenesulfonate and 200 parts of deionized water in which 0.67 part of dodecylbenzenesulfonate was dissolved, and the mixture was stirred for 5 minutes at 10,000 rpm with a homomixer. did. Further, it was passed twice through a homogenizer at a pressure of 20 MPa to obtain a latex of an organosiloxane mixture after micronization.
Next, the latex of the organosiloxane mixture after micronization is put into a separable flask equipped with a thermometer, a cooling tube, and a stirring device, and after maintaining the temperature for 7 hours while being heated to 80 ° C., it is cooled. The reaction product was obtained.
Further, this reaction product was kept at room temperature for 6 hours and then neutralized with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane latex. The latex had a solid content concentration of 29.3% and a mass average particle diameter (d _w ) of 214 nm.

Into a separable flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring device, 33.4 parts (9.8 parts as solid content) of the polyorganosiloxane latex was charged. Next, after adding 171 parts of deionized water, a mixture of 90.2 parts of n-butyl acrylate, 0.05 parts of allyl methacrylate and 0.4 parts of t-butyl hydroperoxide was added. Next, the atmosphere in the flask was replaced with nitrogen by passing nitrogen, and the temperature was raised to 50 ° C.
When the liquid temperature reached 50 ° C., an aqueous solution in which 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt and 0.3 part of Rongalite were dissolved in 10 parts of deionized water was added, Radical polymerization was performed for 5 hours. Then, the temperature in a separable flask was hold | maintained at 65 degreeC for 1 hour, and the latex of the composite rubber (r-2) containing polyorganosiloxane and polyalkyl (meth) acrylate was obtained.
The solid content concentration of the latex of the composite rubber (r-2) was 30.6%, and the mass average particle diameter (d _w ) was 210 nm.

Reference Example 3 Production of Latex of Composite Rubber (r-3) 97.5 parts of octamethylcyclotetrasiloxane, 0.5 part of γ-methacryloyloxypropyldimethoxymethylsilane and 2 parts of tetraethoxysilane were mixed to prepare organo 100 parts of a siloxane mixture were obtained. To 100 parts of this organosiloxane mixture, 150 parts of deionized water in which 1.0 part of sodium dodecylbenzenesulfonate was dissolved was added and mixed with a homomixer by stirring at 10,000 rpm for 5 minutes. Further, it was passed twice through a homogenizer at a pressure of 20 MPa to obtain a latex of an organosiloxane mixture after micronization.
Next, a latex of the organosiloxane mixture after micronization is put into a separable flask equipped with a thermometer, a condenser, and a stirrer, and further a mixture of 0.2 part of sulfuric acid and 49.8 parts of deionized water. Was added over 3 minutes. While maintaining the temperature of the resulting mixture at 80 ° C. for 7 hours, the mixture was cooled to obtain a reaction product.
Further, this reaction product was kept at room temperature for 6 hours and then neutralized with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane latex. The latex had a solid content concentration of 29.8% and a mass average particle diameter (d _w ) of 338 nm.

Into a separable flask equipped with a thermometer, a cooling tube, a nitrogen introducing tube, and a stirring device, 32.8 parts (9.8 parts as a solid content) of the polyorganosiloxane latex was charged. Then, after adding 196 parts deionized water, a mixture of 90.2 parts n-butyl acrylate, 0.05 parts allyl methacrylate and 0.4 parts t-butyl hydroperoxide was added. Next, the atmosphere in the flask was replaced with nitrogen by passing nitrogen, and the temperature was raised to 50 ° C.
When the liquid temperature reached 50 ° C., an aqueous solution in which 0.001 part of ferrous sulfate, 0.003 part of ethylenediaminetetraacetic acid disodium salt and 0.3 part of Rongalite were dissolved in 10 parts of deionized water was added, Radical polymerization was performed for 5 hours. Thereafter, the temperature in the separable flask was kept at 65 ° C. for 1 hour to obtain a latex of a composite rubber (r-3) containing polyorganosiloxane and polyalkyl (meth) acrylate.
The solid content concentration of the latex of the composite rubber (r-3) was 28.8%, and the mass average particle diameter (d _w ) was 275 nm.

(Production Example 1) Production of graft copolymer (C-1) Composite rubber (r-1) obtained in Reference Example 1 in a separable flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, and a stirring device 90 parts of latex (in terms of solid content) was added. Next, 9.5 parts of methyl methacrylate and 0.5 of n-butyl acrylate, which are monomer components (g), and t-butyl hydroperoxide (0.024 parts with respect to 100 parts of monomer component (g)) ) Was added dropwise over 15 minutes, the temperature in the separable flask was kept at 60 ° C. for 2 hours, and graft polymerization onto the composite rubber (r-1) was carried out to obtain a graft copolymer (C-1 ) Latex was obtained.
The obtained latex was added to 5 parts (in terms of solid content) of 18% calcium acetate aqueous solution with respect to 100 parts of the graft copolymer (C-1), salted out, dehydrated and dried, and powdered. The graft copolymer (C-1) was obtained.

(Production Examples 2 to 11) Production of Graft Copolymers (C-2) to (C-11) Except that the type and amount of the composite rubber and the composition and amount of the monomer component were changed as shown in Table 1. Were the same as in Production Example 1 to obtain graft copolymers (C-2) to (C-11).

The abbreviations in Table 1 indicate the following compounds.
MMA: Methyl methacrylate BA: n-butyl acrylate AN: Acrylonitrile St: Styrene

Example 1
Polycarbonate resin (A) (Mitsubishi Engineering Plastics Co., Ltd., trade name: Iupilon S2000F) 90% and talc 1 (Hayashi Kasei Co., Ltd., trade name: Micron White # 5000S) as inorganic filler (B) 10% and 5 parts of the graft copolymer (C-1) obtained in Production Example 1 (based on a total amount of 100 parts of (A) and (B)) were blended.
The blend was melt kneaded using a twin-screw extruder (PCM-30 manufactured by Ikekai Iron Works Co., Ltd.) to obtain a pellet of a polycarbonate resin composition.
After the pellets were dried, test pieces were molded using an injection molding machine (SE100DU manufactured by Sumitomo Heavy Industries, Ltd.), and the evaluations (2) to (4) were performed. The evaluation results are shown in Table 2.
The cylinder temperature of the extruder and the injection molding machine was 280 ° C., and the mold temperature was 80 ° C.

(Examples 2-19 and Comparative Examples 1-16)
Instead of the graft copolymer (C-1), the graft copolymers shown in Tables 2 to 5 were used, and the other specimens were molded in the same manner as in Example 1, and the above (2) to (4). Evaluation was performed. The evaluation results are shown in Tables 2-5.
In addition, mica in the inorganic filler (B) in the table is “A-41S” manufactured by Yamaguchi Mica Co., Ltd., plate-like alumina is “Seraph 610” manufactured by Kinsei Matec Co., Ltd., and GF (glass fiber) is Nippon Electric Glass. “ECS03 T-187” (fiber diameter: 13 μm, sizing agent: aminosilane, fiber length: 3 mm product) manufactured by Co., Ltd., and talc 2 used “Microace P-6” manufactured by Nippon Talc Co., Ltd.
Of the inorganic fillers used in the examples, talc 1, talc 2, mica, and plate-like alumina are all plate-like inorganic fillers.

The polycarbonate resin compositions of Examples 1 to 19 in which the graft copolymers (C-1) to (C-7) containing the composite rubber (r) having a mass average particle diameter of 120 nm or less were blended were obtained moldings. It was excellent in the balance between impact resistance and rigidity, and also excellent in hydrolysis resistance.
Comparative Examples 1 to 3, 5, 6, 8, 9, 11, 12 in which the graft copolymers (C-8) to (C-11) containing the composite rubber (r) having a mass average particle diameter exceeding 120 nm were blended. , 14, 15 were inferior in the balance of impact resistance and rigidity of the resulting molded article.
The polycarbonate resin compositions of Comparative Examples 4, 7, 10, 13, and 16 in which the graft copolymer (C) was not blended had low impact resistance and poor hydrolysis resistance.

Claims (3)

Containing 0.5-30 parts by mass of the graft copolymer (C) with respect to 100 parts by mass of the matrix resin component consisting of 50-99% by mass of the polycarbonate resin (A) and 1-50% by mass of the inorganic filler (B). And
The graft copolymer (C) is an aromatic vinyl monomer (a) in the presence of a composite rubber (r) containing a polyorganosiloxane and a polyalkyl (meth) acrylate and having a mass average particle diameter of 120 nm or less. A polycarbonate resin composition obtained by polymerizing a monomer component (g) containing at least one of a vinyl cyanide monomer (b) and an alkyl (meth) acrylate (c).   The mass ratio (r / g) between the composite rubber (r) and the monomer component (g) is 10 to 60/40 to 90 (provided that the total of (r) and (g) is 100). The polycarbonate resin composition according to claim 1.   A method for producing a molded body by molding the polycarbonate resin composition according to claim 1.