JP2010241943A - Aromatic polycarbonate resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition that is excellent in mechanical characteristics and flame retardancy, can reduce environmental burden, and suppresses the generation of mold and has improvement in odor even if a naturally-derived organic filler is blended to reduce environmental burden. <P>SOLUTION: The aromatic polycarbonate resin composition includes a composition composed of (A) an aromatic polycarbonate resin, (B) an aromatic polycarbonate/polyorganosiloxane copolymer, (C) an aliphatic polyester and (D) a naturally-derived organic filler and further (E) nanoporous carbon incorporated into the composition. A molded article produced by molding the polycarbonate resin composition is provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention comprises an aromatic polycarbonate resin, an aromatic polycarbonate-polyorganosiloxane copolymer, an aliphatic polyester resin and a stabilizer, and a resin composition having excellent mechanical properties and flame retardancy, and the same. The present invention relates to a molded body. This resin composition can be used in the fields of OA equipment, information communication equipment, home appliances and the like.

Polycarbonate resins have excellent mechanical properties such as impact resistance, heat resistance, and transparency, so they are used in various fields such as electrical, electronic, OA equipment, machinery, and automobiles. In addition, there is a problem of reducing the load on the environment, which has been a problem in recent years in terms of degradability after use.
On the other hand, many aliphatic polyester resins are biodegradable, and have attracted a great deal of attention in that the burden on the environment after use is small. In particular, polylactic acid resins made from plant-derived raw materials such as corn and sugarcane are ultimately developed as environmentally friendly resins because they can be degraded to water and carbon dioxide (carbon neutral). Progressing. Furthermore, since it has a high melting point as a vegetable plastic and can be melt-molded, it is expected to be used as a practically excellent vegetable / biodegradable resin (for example, Patent Document 1). Also, some petroleum-derived aliphatic polyester resins (for example, Patent Document 2 and the like) have been attracting attention since some of the raw materials are supposed to be switched to plant-derived materials in the future.
However, since aliphatic polyester resins such as polylactic acid have low mechanical properties such as heat resistance, it is difficult to use a single unit as a molded product for a member that requires mechanical strength.
Therefore, attempts have been made to solve this problem by alloying an aliphatic polyester resin with an aromatic polycarbonate (for example, Patent Documents 3 and 4).
On the other hand, as one of the methods for improving the mechanical properties and heat resistance of the aliphatic polyester resin, a method using an inorganic filler such as glass fiber has been studied. There are problems such as an increase in the specific gravity of the product and an increase in the environmental impact due to an increase in residues that become garbage during incineration or disposal. In order to solve these methods, a method of blending a naturally-derived organic filler having a light specific gravity and a small environmental burden is being compared with an inorganic filler.

Regarding the method of increasing the rigidity using an inorganic filler such as glass fiber or carbon fiber, there is a problem that accompanied by a decrease in fluidity and an increase in specific gravity. For this reason, the use of organic fillers has been studied as an alternative. For example, Patent Document 5 describes the content of blending a naturally-derived organic filler with a polyester resin such as polylactic acid, but there is no description regarding improvement of fluidity and rigidity.
Further, Patent Documents 6 and 7 propose attempts to improve the physical properties by blending carbon nanotubes or carbon black with the above-described alloyed aromatic polycarbonate / aliphatic polyester.
However, improvement in flame retardancy of the composition in which a naturally-derived organic filler is added to an aromatic polycarbonate / aliphatic polyester that has been alloyed and improvement in mold generation caused by blending a naturally-derived organic filler, There is no patent document that mentions that the odor caused by the high temperature of naturally-derived organic fillers during melt mixing and molding can be improved.

JP-A-8-245866 Japanese Patent Laid-Open No. 7-330954 JP 7-324159 A JP 2006-28299 A JP 2006-117768 A JP 2006-104335 A JP 2007-2111110 A

  The present invention has been made under such circumstances, and is excellent in mechanical properties and flame retardancy, and can reduce the environmental load. Even if a natural organic filler is added to reduce the environmental load, It is an object of the present invention to provide an aromatic polycarbonate resin composition in which generation of odor is suppressed and odor is improved, and a molded body using the same.

As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that aromatic polycarbonate resins and / or aromatic polycarbonate-polyorganosiloxane copolymers, aliphatic polyester resins, naturally occurring organic fillers and nanoporous materials It has been found that the object can be achieved by an aromatic polycarbonate resin composition containing a predetermined amount of carbon. The present invention is quiet based on such knowledge.
That is, the present invention includes the following (1) (A) aromatic polycarbonate resin 98 to 0% by mass, (B) aromatic polycarbonate-polyorganosiloxane copolymer 0 to 98% by mass [(A) and (B) are Neither of them is 0], (C) a composition comprising 1% by weight or more and less than 99% by weight of an aliphatic polyester and (D) 1-80% by weight of an organic filler derived from nature [(A) to (D )) Is 100% by mass] with respect to 100 parts by mass, further comprising (E) 0.01-30 parts by mass of nanoporous carbon,
(2) The aromatic polycarbonate resin composition according to the above (1), wherein the (E) nanoporous carbon is a hollow particle having an average particle diameter of 20 to 50 nm and has a pore having an average pore diameter of 5 nm or less on the particle surface.
(3) The aromatic polycarbonate resin composition according to (1) or (2), wherein the (C) aliphatic polyester is at least one selected from polylactic acid, polybutylene succinate, polybutylene adipate, and polycaprolactone. object,
(4) The said (D) natural origin organic filler is what was made into the long fiber pellet, and average fiber length is a thing of 3-12 mm in any one of said (1)-(3) Aromatic polycarbonate resin composition,
(5) The fragrance according to (4), wherein (D) the naturally-derived organic filler is obtained by pelletizing at least one selected from jute fiber, rayon fiber, bamboo fiber, kenaf fiber and hemp fiber. Group polycarbonate resin composition,
(6) The aromatic polycarbonate resin composition according to any one of (1) to (5), further containing a halogen-free phosphorus-based flame retardant as the component (F),
(7) The aromatic polycarbonate resin composition according to any one of (1) to (6), further containing an inorganic filler as a component (G),
(8) The aromatic polycarbonate resin composition according to any one of the above (1) to (7), which further contains polyfluoroethylene as the component (H),
(9) The aromatic polycarbonate resin composition according to any one of (1) to (8), further comprising at least one selected from a carbodiimide compound, an epoxy compound, an isocyanate compound, and an oxazoline compound as the component (I). And (10) a molded article obtained by molding the aromatic polycarbonate resin composition according to any one of (1) to (9) above.

  According to the present invention, it is excellent in mechanical properties and flame retardancy, and can reduce the environmental load, and even when a natural organic filler is blended for reducing the environmental load, the occurrence of mold is suppressed and the odor is reduced. An improved aromatic polycarbonate resin composition and a molded body using the same can be provided.

First, the component (A) will be described in detail.
The aromatic polycarbonate which is the component (A) in the aromatic polycarbonate resin composition [hereinafter referred to as aromatic PC resin composition] of the present invention [hereinafter referred to as aromatic PC] is not particularly limited and may be various. . Usually, aromatic PC produced by a reaction between a dihydric phenol and a carbonate precursor (see, for example, JP 2000-169692 A) can be used.
Specifically, a dihydric phenol and a carbonate precursor are prepared by a solution method or a melting method using an inert organic solvent, that is, a reaction of a dihydric phenol and phosgene, a transesterification reaction of a dihydric phenol and diphenyl carbonate, or the like. The manufactured one can be used.
Various divalent phenols can be mentioned, and in particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy). Phenyl) ethane, bis (hydroxyphenyl) alkali series such as 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, Examples thereof include bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, and bis (4-hydroxyphenyl) ketone.
Particularly preferred dihydric phenols are bis (hydroxyphenyl) alkanes, particularly bisphenol A. The carbonate precursor is carbonyl halide, carbonyl ester, haloformate or the like, and specifically, phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate or the like. In addition, examples of the dihydric phenol include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in combination of two or more.
The aromatic PC in the present invention may have a branched structure. Examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris ( 4-hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglysin, trimellitic acid, isatin bis (o-cresol) and the like.

  In order to adjust the molecular weight, various materials can be used as long as they are usually used for polymerization of PC. Specifically, as monohydric phenol, for example, phenol, on-butylphenol, mn-butylphenol, pn-butylphenol, o-isobutylphenol, m-isobutylphenol, p-isobutylphenol, ot -Butylphenol, mt-butylphenol, pt-butylphenol, on-pentylphenol, mn-pentylphenol, pn-pentylphenol, on-hexylphenol, mn-hexylphenol, pn-hexylphenol, pt-octylphenol, o-cyclohexylphenol, m-cyclohexylphenol, p-cyclohexylphenol, o-phenylphenol, m-phenylphenol, p-phenylphenol, on-nonylphenol M-nonylphenol, pn-nonylphenol, o-cumylphenol, m-cumylphenol, p-cumylphenol, o-naphthylphenol, m-naphthylphenol, p-naphthylphenol; 2,5-di 2,4-di-t-butylphenol; 3,5-di-t-butylphenol; 2,5-dicumylphenol; 3,5-dicumylphenol; p-cresol, bromophenol, tribromo Phenol, monoalkylphenol having a linear or branched alkyl group having an average carbon number of 12 to 35 in the ortho position, meta position or para position; 9- (4-hydroxyphenyl) -9- (4-methoxyphenyl) fluorene 9- (4-hydroxy-3-methylphenyl) -9- (4-methoxy-3-methylphenyl); Le) fluorene; 4- (1-adamantyl) phenol and the like. Among these monohydric phenols, pt-butylphenol, p-cumylphenol, p-phenylphenol and the like are preferably used.

There are various inert organic solvents used in the solution method. For example, dichloromethane (methylene chloride); trichloromethane; carbon tetrachloride; 1,1-dichloroethane; 1,2-dichloroethane; 1,1,1-trichloroethane; 1,1,2-trichloroethane; -Tetrachloroethane; 1,1,2,2-tetrachloroethane; pentachloroethane; chlorinated hydrocarbons such as chlorobenzene, toluene, acetophenone, and the like. These organic solvents may be used alone or in combination of two or more. Of these, methylene chloride is particularly preferred.
The aromatic PC as the component (A) of the present invention has a viscosity average molecular weight of 10,000 to 100,000, preferably 11,000 to 40,000, from the viewpoint of mechanical strength and moldability. Particularly preferred is 12,000 to 25,000. (A) Content in aromatic PC resin composition of aromatic PC which is a component is 98 mass%-0 mass%, Preferably it is 80-0 mass%.

Next, the component (B) will be described in detail.
The aromatic polycarbonate-polyorganosiloxane copolymer which is the component (B) in the aromatic PC resin composition of the present invention is a copolymer having an aromatic polycarbonate part and a polyorganosiloxane part in the molecule. Disclosure in JP-A-50-29695, JP-A-3-292359, JP-A-4-202465, JP-A-8-81620, JP-A-8-302178, and JP-A-10-7897 The copolymer currently made can be mentioned.
The aromatic polycarbonate-polyorganosiloxane copolymer which is the component (B) in the aromatic PC resin composition of the present invention can be obtained by the following method.
For example, an aromatic polycarbonate oligomer constituting an aromatic polycarbonate part produced in advance and a polyorganosiloxane having a reactive group at the terminal constituting a polyorganosiloxane part (segment) are mixed with methylene chloride, chlorobenzene, chloroform, etc. Dissolve in a solvent, add an aqueous alkali hydroxide solution of dihydric phenol, and use a tertiary amine (such as triethylamine) or a quaternary ammonium salt (such as trimethylbenzylammonium chloride) as a catalyst. It can be produced by interfacial polycondensation reaction in the presence of a terminator.
What is necessary is just to select suitably content of the polyorganosiloxane part in aromatic polycarbonate polyorganosiloxane according to the flame retardance level requested | required as a final aromatic PC resin composition.
(B) The ratio of the polyorganosiloxane part in a component becomes like this. Preferably it is 0.3-10 mass% with respect to the total amount of (A)-(D) component, More preferably, it is 0.5-5 mass%. is there. When the ratio of the polyorganosiloxane portion exceeds 10% by mass, the heat resistance of the aromatic PC resin composition and the molded article may be significantly lowered, and the cost of the resin is increased. In the preferred range, a more excellent flame retardant material can be obtained.
The compounding quantity in the aromatic PC resin composition of the (B) component obtained by the above methods is 0-98 mass%, Preferably it is 0-80 mass%.
In the aromatic PC resin composition of the present invention, both the component (A) and the component (B) are not 0.

Next, the component (C) will be described in detail.
As the (C) component aliphatic polyester, a polylactic acid or a copolymer of lactic acid and hydroxycarboxylic acid, a polyglycolic acid resin, or a polyester obtained by dehydration polycondensation of a polybasic acid and a polyhydric alcohol is used. be able to.
Polylactic acid is synthesized by ring-opening polymerization from a cyclic dimer of lactic acid, usually called lactide, and its production method is described in US Pat. No. 1,995,970 and US Pat. No. 2,362,511. U.S. Pat. No. 2,683,136 and the like.
A copolymer of lactic acid and other hydroxycarboxylic acid is usually synthesized by ring-opening polymerization from a cyclic ester intermediate of lactide and hydroxycarboxylic acid, and the production method thereof is described in US Pat. No. 3,635,956. U.S. Pat. No. 3,797,499 and the like.
In the case of producing a lactic acid resin by direct dehydration polycondensation without using ring-opening polymerization, lactic acids and, if necessary, other hydroxycarboxylic acid, preferably an organic solvent, particularly a phenyl ether solvent is present. It is suitable for the present invention by polymerizing by a method in which azeotropic dehydration condensation is carried out and water is removed from the solvent distilled off by azeotropic distillation, and the solvent which has been made substantially anhydrous is returned to the reaction system. A lactic acid resin having a polymerization degree is obtained.
As raw lactic acids, any of L- and D-lactic acid, a mixture thereof, or lactide which is a dimer of lactic acid can be used.
Examples of other hydroxycarboxylic acids that can be used in combination with lactic acids include glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, and 6-hydroxycaproic acid. Cyclic ester intermediates of hydroxycarboxylic acid, for example, glycolide, which is a dimer of glycolic acid, and ε-caprolactone, which is a cyclic ester of 6-hydroxycaproic acid, can also be used. In the production of the lactic acid-based resin, an appropriate molecular weight regulator, a branching agent, other modifiers, and the like can be blended. In addition, lactic acids and hydroxycarboxylic acids as copolymer components can be used alone or in combination of two or more, and two or more of the obtained lactic acid resins can be mixed and used.
As the aliphatic polyester of component (C), polylactic acid is excellent in terms of fluidity and thermal / mechanical properties, preferably has a large molecular weight, and more preferably has a weight average molecular weight of 30,000 or more.
Polyesters obtained by dehydration polycondensation of polybasic acids and polyhydric alcohols include polyethylene adipate resin, polyethylene succinate resin, polybutylene adipate resin, polybutylene succinate resin, polyethylene succinate-adipate resin, polybutylene succinate. Nate-adipate resin. Among these, polybutylene succinate resin is preferable from the viewpoint of availability and excellent biodegradability.
Regarding aliphatic polyesters, polyesters made from aliphatic dicarboxylic acids, aliphatic diols, and lactic acid can also be used. Further, it may be a copolymer of different aliphatic polyesters. Two or more types may be used (polylactic acid is preferable for obtaining a material having high rigidity).
The molecular weight and molecular weight distribution of the polyester resin are not particularly limited, but from the viewpoint of molding processability, the weight average molecular weight is preferably 20,000 or more, more preferably 40,000 or more, and further preferably 80,000 or more. The upper limit is not particularly limited, but is preferably 500,000 or less, more preferably 300,000 or less, and further preferably 250,000 or less in terms of moldability.
The content of the aliphatic polyester as the component (C) in the aromatic PC resin composition is 1 or more and less than 99% by mass, but if the amount of the component (C) is too large, the heat distortion temperature Is significantly reduced, the component (C) is preferably 20 to 50% by mass with respect to the total amount of the components (A) and (B) of 80 to 50% by mass.
By setting the blending amount of the component (C) to 20% by mass or more, the characteristics of the aliphatic polyester can be expressed.

Next, the component (D) will be described in detail.
Specific examples of the naturally-occurring organic filler of component (D) include rice husk, wood chips, okara, waste paper pulverized materials, clothing pulverized materials and other chip-shaped materials, cotton fibers, hemp fibers, bamboo fibers, and wood fibers. Plant fibers such as kenaf fiber, hemp fiber, jute fiber, banana fiber, coconut fiber, or pulp and cellulose fibers processed from these plant fibers and fiber forms such as animal fibers such as silk, wool, angora, cashmere, camel , Paper powder, wood powder, bamboo powder, cellulose powder, rice husk powder, fruit husk powder, chitin powder, chitosan powder, protein, starch, etc., from the viewpoint of heat resistance, Wood powder, bamboo powder, cellulose powder, rice husk powder, fruit shell powder, chitin powder, chitosan powder, protein powder, starch powder, cotton fiber, hemp fiber, bamboo fiber, wood fiber , Kenaf fiber, hemp fibers, jute fibers, banana fibers, vegetable fibers such as coconut fiber preferably, paper powder, wood powder, bamboo powder, bamboo fiber, kenaf fiber, hemp fiber, jute fiber more preferable. In addition, these naturally-derived organic fillers may be collected directly from natural products, but from the viewpoint of protecting the global environment and conserving resources, waste materials such as waste paper, waste wood and old clothes are recycled. May be used. Waste paper is OA paper such as newspaper, magazine, and copy paper, other recycled pulp, or paperboard such as corrugated cardboard, cardboard, paper tube, etc. Although it may be used, from the viewpoint of heat resistance, crushed products of paperboard such as newspaper and corrugated cardboard, cardboard and paper tube are preferable. Specific examples of the wood include coniferous wood such as pine, cedar, oak, and fir, and broad-leaved wood such as beech, shii, and eucalyptus, and the type is not limited.
Naturally-derived organic fillers that have been surface-treated may be used, such as alkali treatment, heat treatment, acetylation treatment, cyanoethylation treatment, silane coupling treatment, and glyogisal treatment. It is preferable to use this organic filler because it tends to improve not only heat resistance but also mechanical properties.
The component (D) is preferably blended with the component (C) in advance and pelletized into long fibers. Examples of the blending method include a method using a long fiber pellet production apparatus. The average fiber length is preferably 3 to 12 mm. The natural organic filler (D) preferably contains at least one or more selected from jute fiber, rayon fiber, bamboo fiber, kenaf fiber, hemp fiber, etc. from the viewpoint of high tensile strength. From the balance of rigidity and various physical properties, the total amount of components (A) to (D) is 100% by mass, and the amount of component (D) is 1 to 80% by mass, preferably 3 to 40% by mass. More preferably, it is 5-25 mass%.
By making the blending amount of component (D) 1% by mass or more, it contributes to improvement of rigidity, reduction of specific gravity and environmental load reduction, and by making it 40% by mass or less, mechanical properties are lowered. To prevent.

Next, the component (E) will be described in detail.
The component (E) in the present invention is nanoporous carbon, and the shape thereof is particularly spherical and hollow with an average particle diameter of 20 to 50 nm, and the surface has innumerable pores of 5 nm or less, particularly about 2 nm. .
Nanoporous carbon (B) in the aromatic polycarbonate resin composition of the present invention is a new nanomaterial after conventional carbon nanotubes, nanodiamonds, ceramics nanofibers, and nanocerametals. 529403 and the like.
Nanoporous carbon is a carbon particle having pores on the particle surface, and is used in filters, membranes, absorbents, catalyst carriers, electrode materials, etc. because of its expanded surface area and microporous structure. . Depending on the pore dimensions (diameter or width), those below 2 nm are considered micropores, those with 2-50 nm as mesopores and those above 50 nm as macropores.
In the present invention, nanoporous carbon which is hollow particles having an average particle diameter of 20 to 50 nm and has pores having an average pore diameter of 5 nm or less on the particle surface is preferably used.
(E) The compounding quantity of a component is 0.01-30 mass parts with respect to 100 mass parts of total amounts of (A)-(D) component, Preferably it is 0.1-20 mass parts.
By blending 0.01 parts by mass or more, flame retardancy is improved, and it is possible to impart an antistatic effect, an antibacterial property and a deodorizing effect due to the development of electrical conductivity. By controlling the blending amount to 30 parts by mass or less, it is possible to prevent the cost from increasing and to prevent the properties of the molded product formed from the resin composition from deteriorating.

Next, the halogen-free phosphorus-based flame retardant, which is the component (F) blended as necessary, will be described.
As the halogen-free phosphorus-based flame retardant, any organic compound having a phosphorus atom and not containing a halogen can be used without particular limitation. Of these, phosphate ester compounds having one or more ester oxygen atoms directly bonded to phosphorus atoms and red phosphorus (various surface-treated red phosphorus with organic compounds, inorganic compounds, etc.) are preferably used.
The phosphate ester compound may be a monomer, dimer, oligomer, polymer or a mixture thereof. Specifically, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (2-ethylhexyl) phosphate, diisopropyl Phenyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, trinaphthyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, resorcinol-diphenyl phosphate, trioxybenzene triphosphate, cresyl diphenyl phosphate, or these Substitution products, condensates, etc. It is.
When a halogen-free phosphorus-based flame retardant is blended, it is preferably 0.05 to 20 parts by mass, more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the total amount of the components (A) to (D). is there.
By setting the blending amount to 0.05 parts by mass or more, the target flame retardancy (V-0) can be obtained, and by setting the blending amount to 20 parts by mass or less, physical properties such as impact strength are lowered. To prevent it.
Examples of commercially available halogen-free phosphate ester compounds include TPP [triphenyl phosphate], TXP [trixylenyl phosphate], CR-733S [resorcinol bis (diphenyl phosphate)] manufactured by Daihachi Chemical Industry Co., Ltd. CR-741 [bisphenol A bisdiphenyl phosphate], PX200 [1,3-phenylene-teslakis (2,6-dimethylphenyl) phosphate], PX201 [1,4-phenylene-tetrakis (2,6-dimethylphenyl) Phosphate ester], PX202 [4,4′-biphenylene-teslakis) 2,6-dimethylphenyl) phosphate ester] and the like.

Next, the inorganic filler which is the component (G) blended as necessary will be described.
The inorganic filler can further improve the rigidity and flame retardancy of the molded product. Examples of the inorganic filler include talc, mica, kaolin, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, glass fiber, carbon fiber, and potassium titanate fiber. Of these, plate-like talc and mica, and fibrous fillers are preferable, and talc is particularly preferable.
Talc is a hydrated silicate of magnesium, and commercially available products can be used. Talc may contain trace amounts of aluminum oxide, calcium oxide and iron oxide in addition to the main components of silicic acid and magnesium oxide. To produce the aromatic PC resin composition of the present invention, May be included. Moreover, the average particle diameter of inorganic fillers, such as a talc, is 0.1-50 micrometers normally, Preferably, it is 0.2-20 micrometers. By containing these inorganic fillers, particularly talc, the blending amount of the halogen-free phosphate ester as a flame retardant can be reduced while improving the rigidity.
Here, the amount of the inorganic filler that is the component (G) is preferably 1 to 50 parts by mass, more preferably 100 parts by mass relative to the total amount of the components (A) to (D). 2 to 30 parts by mass. Here, if it is less than 1 part by mass, the intended effect of improving the rigidity and flame retardancy may not be sufficient, and if it exceeds 50 parts by mass, the impact resistance and melt fluidity may be reduced. The thickness of the product, the resin flow length, etc. can be appropriately determined in consideration of the required performance and moldability of the molded product.

Next, the polyfluoroolefin which is the component (H) blended as necessary will be described.
Polyfluoroolefin is used for the purpose of preventing melt dripping during combustion in a flame retardancy test or the like. Here, the polyfluoroolefin is usually a polymer or copolymer containing a fluoroethylene structure, and examples thereof include a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, and a tetrafluoroethylene. It is a copolymer of ethylene and an ethylene monomer that does not contain fluorine. Polytetrafluoroethylene (PTFE) is preferable, and the average molecular weight is preferably 500,000 or more, and particularly preferably 500,000 to 10,000,000. As polytetrafluoroethylene that can be used in the present invention, all of the currently known types can be used.
In addition, when polytetrafluoroethylene having a fibril forming ability is used, it is possible to impart higher melt dripping prevention property. Although there is no restriction | limiting in particular in the polytetrafluoroethylene (PTFE) which has a fibril formation ability, For example, what is classified into the type 3 in ASTM standard is mentioned. Specific examples thereof include, for example, Teflon 6-J (Mitsui / DuPont Fluoro Chemical), Polyflon D-1, Polyflon F-103, Polyflon F201 (Daikin Industries), CD076 (Asahi Glass Fluoropolymers), etc. Can be mentioned.
Other than those classified as type 3 above, for example, Algoflon F5 (manufactured by Montefluos), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries) and the like can be mentioned. These polytetrafluoroethylene (PTFE) may be used independently and may combine 2 or more types. The polytetrafluoroethylene (PTFE) having the fibril-forming ability as described above is a pressure of 6.9 to 689.5 kPa in the presence of sodium, potassium, ammonium peroxydisulfide, for example, in an aqueous solvent. The polymerization is carried out at a temperature of 0 to 200 ° C., preferably 20 to 100 ° C.
The compounding amount of the polyfluoroolefin is preferably 0 to 2 parts by mass, more preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the total amount of the components (A) to (D). By setting the blending amount to 0.05 part by mass or more, the melt dripping preventing property in the intended flame retardance is sufficient. Moreover, the effect corresponding to a compounding quantity is acquired by making a compounding quantity into 2 mass parts or less, and it has a favorable influence on impact resistance and a molded article external appearance. Therefore, it can be appropriately determined in consideration of the amount of use and the like according to the degree of flame retardancy and thickness required for each molded product.

Next, the carbodiimide compound, the epoxy compound, the isocyanate compound, and the oxazoline compound, which are components (I) to be blended as necessary, will be described.
(I) It is preferable that the compounding quantity in the case of mix | blending a component is 1-10 mass parts with respect to 100 mass parts of total amounts of said component (A)-(D).
This component (I) has an effect of promoting the compatibilization of the above-mentioned components, and particularly stabilizing the component (C) (hydrolysis preventing effect). Epoxy compounds and carbodiimide compounds are particularly preferable. Two or more of these compounds may be added in combination.
The addition time of component (I) is not particularly limited, but it is not limited to stabilizing component (C), but can improve mechanical properties and durability. It is preferable to knead with other components after melt-kneading in advance.

  In the aromatic PC resin composition of the present invention, various additives may be blended as necessary in addition to the above-mentioned components as long as the effects of the present invention are not impaired. For example, UV absorbers such as benzotriazoles and benzophenones, light stabilizers such as hindered amines, internal lubricants such as aliphatic carboxylic acid esters, paraffins, silicone oils, polyethylene waxes, conventional flame retardants, Examples include flame retardant aids, mold release agents, antistatic agents, and colorants.

Next, the manufacturing method of the aromatic PC resin composition of this invention is demonstrated. In the aromatic PC resin composition of the present invention, the above-mentioned components (A) to (E) are mixed in the above proportions as necessary, and various optional components (F) to (I) are blended as necessary. These general ingredients are blended at an appropriate ratio and kneaded.
For compounding and kneading, premixing is performed using a commonly used equipment such as a ribbon blender or a drum tumbler, and then a Henschel mixer, a Banbury mixer, a single screw extruder, a twin screw extruder, a multi screw extruder, a kneader. Or the like. The heating temperature at the time of kneading is usually appropriately selected in the range of 220 to 280 ° C. The aromatic PC resin composition of the present invention is an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a press molding method, a vacuum, using the above melt kneading molding machine or the obtained pellet as a raw material. Various molded products can be manufactured by a molding method, a foam molding method, or the like. However, by the melt kneading method, a pellet-shaped molding raw material is manufactured, and then, using this pellet, it is particularly suitable for manufacturing an injection molded product by injection molding or injection compression molding where releasability is most problematic. Can be used. In addition, as the injection molding method, a gas injection molding method for preventing the appearance of sink marks or for reducing the weight can be employed.
The aliphatic polyester as the component (C) and the naturally-derived organic filler as the component (D) are preferably manufactured separately as a master batch.
It is preferable to produce a masterbatch using a melt-moldable aliphatic polyester [component (C)] and a naturally-derived organic filler [component (D)] as the main raw materials.
In the production of the masterbatch, the production process is not particularly limited, for example, a melt-kneading method using a normal biaxial kneader or the like [a method of kneading a naturally-derived organic filler and a molten aliphatic polyester], After impregnating the melted aliphatic polyester with the natural organic filler, cooling and cutting, the aliphatic polyester powder is attached to the natural organic filler by the dry method or wet method, and after melting this, Any method of cooling and cutting may be used.
For the production of the master batch, a method using a long fiber pellet production apparatus may be applied.
In the production of the long fiber pellets, it is necessary that the aliphatic polyester can be melted by any production method. Further, when the aromatic PC resin composition of the present invention is obtained from an intermediate material such as long fiber pellets, the intermediate material needs to be capable of molding such as injection molding. In the present invention, the condition that the aliphatic polyester can be melt-molded is to satisfy this need.
In addition, the aliphatic polyester used for manufacture of a masterbatch and the aliphatic polyester used as a component (C) in the aromatic PC resin composition of this invention may be the same or different.
When the natural-derived organic filler which is the component (D) is formed into a long fiber pellet, the longer the fiber length of the natural-derived organic filler, the greater the content in the aromatic PC resin composition obtained after the molding process. The fiber length of the fiber is long and the mechanical properties are improved. Therefore, the fiber length of the naturally derived organic filler as component (D) is preferably as long as possible. For example, in the case of long fiber pellets, it is desirable that the fiber length of the naturally derived organic filler is approximately equal to the pellet length.

The present invention also provides a molded article obtained by molding the above-described aromatic PC resin composition of the present invention.
A molded product formed by molding the aromatic PC resin composition of the present invention, preferably an injection molded product (including injection compression) is a copier, fax machine, television, radio, tape recorder, video deck, personal computer, printer, telephone. It is used for OA equipment such as information terminals, refrigerators, microwave ovens, home appliances, housings and various parts of electrical / electronic equipment.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these examples.

<Production Example 1: Production of aromatic polycarbonate (PC) -polyorganosiloxane (PDMS) copolymer>
(1) Production of PC oligomer 60 kg of bisphenol A was dissolved in 400 liters of a 5% by mass sodium hydroxide aqueous solution to prepare a sodium hydroxide aqueous solution of bisphenol A.
Next, this aqueous solution of bisphenol A in sodium hydroxide maintained at room temperature at a flow rate of 138 liter / hour and methylene chloride at a flow rate of 69 liter / hour was passed through an orifice plate through a tubular reactor having an inner diameter of 10 mm and a tube length of 10 m. Introduced, phosgene was co-flowed therethrough and blown at a flow rate of 10.7 kg / hour, and the reaction was continued for 3 hours.
Here, the tubular reactor used was a double tube, and the cooling temperature of the reaction liquid was maintained at 25 ° C. through the jacket portion through cooling water.
The pH of the effluent was adjusted to 10-11.
The reaction solution thus obtained was allowed to stand to separate and remove the aqueous phase, and the methylene chloride phase (220 liters) was collected to obtain a PC oligomer (concentration 317 g / liter). The degree of polymerization of the PC oligomer obtained here was 2 to 4, and the concentration of the chloroformate group was 0.7 mol / liter.

(2) Production of terminal-modified polycarbonate 10 liters of the PC oligomer obtained in (1) above was placed in a 50 liter stirred container, and p-dodecylphenol (containing branched dodecyl group) [manufactured by Yuka Schenectady Co., Ltd.] 162 g were dissolved.
Next, an aqueous sodium hydroxide solution (53 g of sodium hydroxide, 1 liter of water) and 5.8 ml of triethylamine were added and reacted for 1 hour with stirring at 300 rpm.
Then, bisphenol A sodium hydroxide solution (bisphenol A: 720 g, sodium hydroxide 412 g, water 5.5 liters) was mixed into the above system, 8 liters of methylene chloride was added, and the mixture was reacted for 1 hour with stirring at 500 rpm. It was.
After completion of the reaction, 7 liters of methylene chloride and 5 liters of water were added, stirred for 10 minutes at 500 rpm, allowed to stand after stopping the stirring, and the organic phase and the aqueous phase were separated.
The organic phase obtained was washed with 5 liters of alkali (0.03 mol / liter-NaOH), 5 liters of acid (0.2 mol / liter-hydrochloric acid) and 5 liters of water (twice) in this order.
Thereafter, methylene chloride was evaporated to obtain a flaky polymer. The viscosity average molecular weight was 17,500.

(3) Production of reactive PDMS 1,483 g of octamethylcyclotetrasiloxane, 96 g of 1,1,3,3-tetramethyldisiloxane and 35 g of sulfuric acid (86% by mass) were mixed and stirred at room temperature for 17 hours. did. Thereafter, the oil phase was separated, 25 g of sodium bicarbonate was added, and the mixture was stirred for 1 hour.
After filtration, vacuum distillation was performed at 150 ° C. and 4 × 10 ² Pa (3 torr) to obtain low-boiling substances and an oily substance was obtained.
To a mixture of 60 g of 2-allylphenol and 0.0014 g of platinum as a platinum chloride-alcolate complex, 294 g of the oil obtained in (2) above was added at a temperature of 90 ° C. The mixture was stirred for 3 hours while maintaining the temperature at 90 to 115 ° C.
The product was extracted with methylene chloride and washed 3 times with 80 wt% aqueous methanol to remove excess 2-allylphenol. The product was dried over anhydrous sodium sulfate and heated to 115 ° C. in vacuo to remove the solvent.
The terminal phenol PDMS obtained had 30 repeats of dimethylsilanooxy units as measured by NMR.

(4) Production of PC-PDMS copolymer 182 g of the reactive PDMS obtained in the above (3) was dissolved in 2 liters of methylene chloride, and 10 liters of the PC oligomer obtained in the above (1) were mixed.
Thereto were added 26 g of sodium hydroxide dissolved in 1 liter of water and 5.7 ml of triethylamine, and the mixture was stirred and reacted at 500 rpm at room temperature for 1 hour.
After completion of the reaction, the above reaction system was added with 600 g of bisphenol A dissolved in 5 liters of a 5.2 mass% aqueous sodium hydroxide solution, 8 liters of methylene chloride and 96 g of p-tert-butylphenol, and brought to room temperature at 500 rpm. The mixture was reacted for 2 hours with stirring.

After the reaction, 5 liters of methylene chloride was added, and further washed with 5 liters of water, washed with 5 liters of 0.03 mol / liter aqueous sodium hydroxide, washed with 5 liters of 0.2 mol / liter hydrochloric acid, and washed with 5 liters of water. Two liters of water washing were sequentially performed, and finally methylene chloride was removed to obtain a flaky PC-PDMS copolymer.
The obtained PC-PDMS copolymer was vacuum-dried at 120 ° C. for 24 hours. The viscosity average molecular weight was 17,000, and the PDMS content was 3.0% by mass.

The viscosity average molecular weight and the PDPS content were determined as follows.
(1) Viscosity average molecular weight (Mv)
The viscosity of the methylene chloride solution at 20 ° C. was measured with an Ubbelohde viscometer, and the intrinsic viscosity [η] was determined from the viscosity.
[Η] = 1.23 × 10 ⁻⁵ Mv ^0.83
(2) PDMS content
^It was determined based on the intensity ratio between the isopropyl methyl group peak of bisphenol A found at 1.7 ppm by ¹ H-NMR and the methyl group peak of dimethylsiloxane found at 0.2 ppm.

<Measurement method of evaluation characteristics>
(1) Flame retardancy Using a test piece having a thickness of 1.5 mm, the flame retardancy was evaluated according to the UL94 combustion test.
(2) Tensile modulus Measured according to JIS K 7161 (units in Tables 1 and 2: MPa).
(3) Flexural modulus Measured according to ASTM D790 (unit: MPa).
(4) Antifungal property Measured according to JIS Z2911, and evaluated according to the following criteria.
○: Growth of mold inoculated on the test piece is not recognized, or the growth area does not exceed 1/3.
X: The growth area of mold inoculated on the test piece exceeds 1/3.
(5) Deodorizing effect Judgment was made based on the presence or absence of odors produced by natural fibers at the time of molding, and evaluated according to the following criteria.
○: There is no smell.
X: There is a peculiar odor.
(6) Electrical conductivity (antistatic effect)
Using a flat test piece having a thickness of 1/8 inch, the measurement was performed in an atmosphere of 23 ° C. and a humidity of 50%, and the evaluation was made according to the following criteria (unit: Ω / □).
○: Resistance value is 10 ⁻¹³ Ω / □ or more.
×: Resistance value is less than 10 ⁻¹³ Ω / □.

[Examples 1-9 and Comparative Examples 1-7]
The masterbatch containing the component (C) and the component (D) was produced at a temperature of 280 ° C. using a long fiber pellet production apparatus “KOSLFP-112” manufactured by Kobe Steel.
Extrusion pelletization of each component was performed at a temperature of 260 ° C. using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd., model name: TEM35).
The test piece was molded at a temperature of 240 ° C. using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., model name: IS100EN).
Each component used is as follows.
(A) Aromatic polycarbonate resin: Toughlon A1900
[Viscosity average molecular weight: 19,500, manufactured by Idemitsu Kosan Co., Ltd.]
(B) Aromatic polycarbonate-polyorganosiloxane copolymer (aromatic polycarbonate-polydimethylsiloxane copolymer): The PC-PDMS copolymer obtained in Production Example 1 was used.
(C) Aliphatic polyester resin 1: polylactic acid LACEA H-100 (manufactured by Mitsui Chemicals)
(C) Aliphatic polyester resin 2: Polybutylene succinate “GSPla AZ81T (Mitsubishi Chemical Corporation)”
(D) Natural product-derived organic filler 1: long fiber in which jute (average fiber length 3-12 mm) is impregnated with polylactic acid (D) natural product-derived organic filler 2: rayon (average fiber length 3-12 mm) Long fibers impregnated with polylactic acid (E) porous carbon (nanoporous carbon): average particle size 20-50 nm, spherical (hollow) surface with pores of about 2 nm (EAZY-N, INC)
(E) Carbon black (trade name: Mitsubishi Carbon Black M-100, manufactured by Mitsubishi Chemical Corporation)
(F) Halogen-free phosphorus flame retardant 1: aromatic phosphate ester flame retardant (trade name: PX-200, manufactured by Daihachi Chemical Co., Ltd.)
(F) Halogen-free phosphorus-based flame retardant 2: phenol-based resin stabilization treatment red phosphorus (trade name: Nova Red Excel 140, manufactured by Phosphor Chemical Industries)
(G) Inorganic filler: Talc “TP-A25 (manufactured by Fuji Talc)”
(H) Polyfluoroolefin: Polytetrafluoroethylene “CD076 (Asahi Glass Fluoropolymers)”
(I) Epoxy compound: Bisphenol A epoxy resin “Epiclon AM-040-P (Dainippon Ink Co., Ltd.)”
(I) Carbodiimide compound: Dicyclohexylcarbodiimide “Carbodilite LA-1 (Nisshinbo Industries, Inc.)”
(I) Isocyanate compound: 1,3-bis (isocyanate methyl) cyclohexane “Takenate 600 (Mitsui Chemical Polyurethanes)”
(I) Oxazoline compound: Oxazoline group-containing reactive polystyrene “Epocross RPS-1005 (manufactured by Nippon Shokubai Co., Ltd.)”
Tables 1 and 2 show the composition of each component and the results obtained in Examples and Comparative Examples.

From the results shown in Tables 1 and 2, the following is clear.
In Examples 1 to 4 and 6 to 9, by adding nanoporous carbon, the flame retardancy is improved as compared with Comparative Examples 1, 2, 4 to 6, 8, and 9 in which the nanoporous carbon is not added. It is seen and has antifungal and deodorant properties.
In Comparative Examples 3 and 7 in which carbon black was blended, the antifungal and deodorant properties exhibited when nanoporous carbon was blended as in Examples 2 and 6 were not observed.
In Example 5, by increasing the amount of nanoporous carbon added, the surface resistivity is low, that is, the electrical conductivity is improved and the antistatic effect is imparted. In Comparative Example 5 in which it is not blended, the surface specific resistance value is high, that is, the electrical conductivity is low, and the antistatic property is poor.

  The aromatic PC resin composition of the present invention has excellent characteristics and can be used in the fields of OA equipment, information communication equipment, home appliances, and the like.

Claims (10)

  (A) Aromatic polycarbonate resin 98 to 0% by mass, (B) Aromatic polycarbonate-polyorganosiloxane copolymer 0 to 98% by mass (both (A) and (B) are not 0), ( C) Composition comprising 1% by mass or more of aliphatic polyester and less than 99% by mass and (D) 1 to 80% by mass of organic filler derived from nature [the total amount of (A) to (D) is 100% by mass] 100 An aromatic polycarbonate resin composition comprising 0.01 to 30 parts by mass of (E) nanoporous carbon with respect to parts by mass.   The aromatic polycarbonate resin composition according to claim 1, wherein the (E) nanoporous carbon is a hollow particle having an average particle diameter of 20 to 50 nm and has pores having an average pore diameter of 5 nm or less on the particle surface.   The aromatic polycarbonate resin composition according to claim 1 or 2, wherein the (C) aliphatic polyester is at least one selected from polylactic acid, polybutylene succinate, polybutylene adipate, and polycaprolactone.   The aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the (D) naturally-derived organic filler is pelletized into long fibers and has an average fiber length of 3 to 12 mm. object.   The aromatic polycarbonate resin composition according to claim 4, wherein the (D) naturally-derived organic filler is obtained by pelletizing at least one selected from jute fiber, rayon fiber, bamboo fiber, kenaf fiber and hemp fiber. object.   Furthermore, the aromatic polycarbonate resin composition in any one of Claims 1-5 which contains a halogen-free phosphorus flame retardant as (F) component.   Furthermore, the aromatic polycarbonate resin composition in any one of Claims 1-6 containing an inorganic filler as (G) component.   Furthermore, the aromatic polycarbonate resin composition in any one of Claims 1-7 which contains polyfluoroethylene as (H) component.   Furthermore, the aromatic polycarbonate resin composition in any one of Claims 1-8 which contains at least 1 chosen from a carbodiimide compound, an epoxy compound, an isocyanate compound, and an oxazoline compound as (I) component.   The molded object formed by shape | molding the aromatic polycarbonate resin composition in any one of Claims 1-9.