JP2006257182A - Polycarbonate resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition satisfying the severe requirement of flame retardancy, impact resistance and dimensional stability, further having good flexural characteristics, heat resistance, thermal stability and appearance properties, and comprehensively having excellent properties good in balance. <P>SOLUTION: The polycarbonate resin composition is obtained by compounding (A) 100 pts.wt. aromatic polycarbonate resin, (B) 1-150 pts.wt. glass-based inorganic filler obtained by combining (a) a glass chopped fiber (CS) with (b) at least one kind selected from (b-1) a glass milled fiber (NF) and (b-2) glass flakes (GFL), (C) 0.001-5 pts.wt. at east one kind of flame retardants selected from an alkali metal salt and an alkaline earth metal salt of a perfluoroalkanedisulfonimide represented by a specific formula. The molded article is obtained by melt-molding the resin composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a flame retardant reinforced polycarbonate resin composition. More specifically, it meets the requirements of severe flame retardancy, impact resistance and dimensional stability, and has excellent bending properties, heat resistance, thermal stability, appearance performance, and excellent overall balance And a molded product obtained by molding the polycarbonate resin composition.

  Polycarbonate resin has excellent impact resistance, heat resistance (DTUL), thermal stability, dimensional stability, and electrical characteristics, so it is widely used industrially in the automotive field, OA equipment field, electrical / electronic field, etc. Yes. Further, in fields where higher mechanical strength and heat resistance (DTUL) are required, reinforced polycarbonate resins having improved physical properties by blending inorganic fillers such as glass fibers are used. About this reinforcement | strengthening polycarbonate resin, there is a strong demand of flame retardance focusing on uses, such as an OA apparatus and household appliances, like a normal polycarbonate resin.

  Conventionally, brominated flame retardants have been used exclusively in order to meet such demands for flame retardancy, but all of these problems have the potential to cause environmental pollution. Various reinforced polycarbonate resins that have been flame-retarded by other methods without using a flame retardant have been proposed.

  For example, Patent Document 1 discloses a resin composition in which a perfluoroalkanesulfonic acid metal salt and a monohydric alcohol or a sulfated metal salt of a polyhydric alcohol are blended with a polycarbonate resin reinforced with an inorganic filler. . Patent Document 2 discloses an organopolysiloxane containing a perfluoroalkanesulfonic acid metal salt and an organoxysilyl group bonded to a silicon atom via a divalent hydrocarbon group in a polycarbonate resin reinforced with an inorganic filler. The resin composition which mix | blended is disclosed.

  Patent Document 3 discloses a resin composition in which a polycarbonate resin reinforced with an inorganic filler is blended with an alkoxysilane compound and / or a silicone compound having a Si—H bond, and a fluorinated polyolefin. Further, Patent Document 4 discloses a resin composition in which a perfluoroalkanesulfonic acid metal salt is blended with a polycarbonate resin reinforced with an inorganic filler.

  In Patent Documents 1 to 4 described above, only a metal salt of perfluoroalkanesulfonic acid is disclosed as a flame retardant. In addition, these documents disclose various types of inorganic fillers such as glass-based fillers, but the specific forms thereof are the physical properties of the resin composition (flame resistance, impact resistance and There is no suggestion about the effects on dimensional stability.

  On the other hand, Patent Document 5 discloses a resin composition comprising a polycarbonate resin and an alkali (earth) metal salt of a perfluorodisulfonic acid compound containing perfluoroalkanedisulfonimide as a flame retardant. . In Patent Document 5, there is no example in which an inorganic filler is blended, and the specific form of the glass-based filler used as the inorganic filler is the physical properties of the resin composition (flame resistance, impact resistance and dimensional stability). There is no suggestion about the effects on sex.

  In general, when an inorganic filler such as a glass-based filler is added to the resin composition, the rigidity is improved, but the impact resistance and dimensional stability tend to decrease. Therefore, even a resin composition containing an inorganic filler satisfies the severe flame resistance, impact resistance, and dimensional stability requirements demanded in the recent electrical and electronic fields, and further has good bending properties. There has been a demand for the appearance of a polycarbonate resin composition having characteristics, heat resistance, thermal stability, appearance performance, and excellent performance with a good overall balance.

JP-A-6-287427 JP-A-6-329894 JP 2003-82217 A JP 2003-105184 A JP 2003-246986 A

  The object of the present invention is to meet the requirements of severe flame retardancy, impact resistance and dimensional stability, and also has excellent bending characteristics, heat resistance, thermal stability, appearance performance, and excellent balance with a comprehensive balance Another object of the present invention is to provide a polycarbonate resin composition having excellent performance and a molded product obtained by molding the polycarbonate resin composition.

  As a result of intensive studies in order to solve the above problems, the present inventors have obtained a resin composition comprising (A) an aromatic polycarbonate resin and (B) an inorganic filler and (C) a metal salt flame retardant. In a product, (B) a glass-based inorganic filler having a specific form is used in combination as an inorganic filler, and (C) a perfluoroalkanedisulfonimide represented by a specific formula as a metal salt-based flame retardant By using the alkali (earth) metal salt of, it meets the requirements of severe flame retardancy, impact resistance and dimensional stability, and also has good bending properties, heat resistance, thermal stability and appearance performance The present inventors have found that a polycarbonate resin composition having excellent performance with a good overall balance can be obtained, and the present invention has been completed.

That is, the gist of the present invention is as follows.
(A) For 100 parts by weight of the aromatic polycarbonate resin,
(B) (a) Glass fiber chopped strand (CS) was combined with at least one (b) selected from (b-1) glass fiber milled fiber (MF) and (b-2) glass flake (GFL). 1 to 150 parts by weight of a glass-based inorganic filler,
(C) Perfluoroalkanedisulfonimide alkali metal salt represented by the following general formulas (C-1) and (C-2), and at least one flame retardant selected from alkaline earth metal salts 0.001 to 0.001 5 parts by weight,
The present invention resides in a polycarbonate resin composition characterized by blending and a molded article characterized by molding the polycarbonate resin composition.

（一般式（Ｃ−１）中、Ｒ_１及びＲ_２は、各々独立に、炭素数１〜８のパーフルオロアルキル基を示し、Ｍはアルカリ金属又はアルカリ土類金属を示す。ｎはＭの価数である。）

(In General Formula (C-1), R ₁ and R ₂ each independently represent a perfluoroalkyl group having 1 to 8 carbon atoms, M represents an alkali metal or an alkaline earth metal, and n represents M. It is a valence.)

（一般式（Ｃ−２）中、Ｒｆは炭素数４〜７個のパーフルオロシクロアルキル基で置換されていても良い、総炭素数２〜１２の直鎖状又は分岐状パーフルオロアルキレン基を示し、Ｍ'はアルカリ金属又はアルカリ土類金属を示す。ｎはＭ'の価数である。）

(In General Formula (C-2), Rf represents a linear or branched perfluoroalkylene group having 2 to 12 carbon atoms, which may be substituted with a 4 to 7 carbon perfluorocycloalkyl group. M ′ represents an alkali metal or an alkaline earth metal, and n is the valence of M ′.)

The polycarbonate resin composition of the present invention satisfies the requirements of severe flame retardancy, impact resistance and dimensional stability, and also has good bending characteristics, heat resistance, thermal stability, and appearance performance, and is comprehensively balanced. Therefore, it is suitable for OA equipment and home appliance parts (internal parts or external parts). Specifically, it is suitable for parts such as a personal computer, a notebook personal computer, a printer, a mobile terminal, a mobile phone, and a liquid crystal TV, a lens barrel of a liquid crystal projector, and the like.
In addition, the resin composition of the present invention has greatly improved thermal stability during molding processing compared to a composition containing a conventional bromine-based or phosphate ester-based flame retardant. Even under the severe molding conditions required by the production, appearance defects such as silver streaks and pearly luster, or deterioration of physical properties can be suppressed.
Therefore, the polycarbonate resin composition of the present invention is particularly suitably used for applications such as electronic information equipment parts that are required to be light and small.

Hereinafter, the present invention will be described in detail.
(A) Aromatic polycarbonate resin The (A) aromatic polycarbonate resin used in the present invention is obtained by reacting an aromatic dihydroxy compound or a mixture of this and a small amount of a polyhydroxy compound with phosgene or a carbonic acid diester. The thermoplastic aromatic polycarbonate polymer or copolymer which may be obtained and may be branched is said. As a method for producing the aromatic polycarbonate resin, a method such as an interfacial polycondensation method (phosgene method) or a melt polymerization method (transesterification method) can be employed.

  As raw material aromatic dihydroxy compounds, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol and 4 , 4'-dihydroxydiphenyl and the like, or two or more selected from bisphenol A are preferable.

  In order to obtain a branched aromatic polycarbonate resin, a part of these aromatic dihydroxy compounds is mixed with phloroglucin, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -2-heptene, 4, 6-dimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -3-heptene, 1,3,5-tris Polyhydroxy compounds such as (4-hydroxyphenyl) benzene and 1,1,1-tris (4-hydroxyphenyl) ethane, or 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5 -Chlorisatin bisphenol, 5,7-dichloroisatin bisphenol or 5-bromoisatin bisphenol It may be used in place of. The amount of these substitute compounds used is 0.01 to 10 mol%, preferably 0.1 to 2 mol%, based on the total amount of the aromatic dihydroxy compound and the polyhydroxy compound.

  The aromatic polycarbonate resin (A) of the present invention is preferably a polycarbonate copolymer derived from 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) or other aromatic dihydroxy compounds. Examples thereof include a polymer, and further, a polymer having a siloxane structure or a copolymer of oligomers can be used.

(A) In order to adjust the molecular weight of the aromatic polycarbonate resin, a monovalent aromatic hydroxy compound may be used. Examples of the monovalent aromatic hydroxy compound include m- or p-methylphenol, m- or p-propylphenol, pt-butylphenol, or a long-chain alkyl-substituted phenol.
The molecular weight of the aromatic polycarbonate resin is a viscosity average molecular weight converted from the solution viscosity measured at a temperature of 25 ° C. using methylene chloride as a solvent, preferably 15,000 to 30,000, more preferably 18,000 to 25,000. preferable.

(B) Glass-based inorganic filler The glass-based inorganic filler as the component (B) used in the resin composition of the present invention includes (a) glass fiber chopped strand (CS) and (b-1) glass. An inorganic filler formed by combining and blending at least one (b) selected from fiber milled fiber (MF) and (b-2) glass flakes (GFL).

Examples of the glass-based inorganic filler include glass compositions such as A glass, C glass, and E glass. Among the inorganic fillers used in the present invention, E glass (non-alkali glass) is used. (A) It is preferable in that it does not adversely affect the aromatic polycarbonate resin.

Glass fiber chopped strands (CS) are glass fibers (strands) obtained by bundling dozens to thousands of single glass fibers (filaments) into a predetermined length. The cross-sectional shape when cut at a right angle is usually a perfect circle or a polygon.
The (a) glass fiber chopped strand (CS) used in the present invention has a substantially columnar shape such as a columnar shape or a prismatic shape, and has an average fiber diameter of 1 to 25 μm, preferably 8 to 15 μm. The average length in the major axis direction is 1 mm to 10 mm, preferably 2 mm to 5 mm.

Here, the average fiber length and the average length are 1000 inorganic inorganic materials arbitrarily selected after spreading the inorganic filler on the glass as much as possible, observing it with an optical microscope at 40 to 100 times, and taking a picture. Each of the fillers can be obtained by measuring the maximum diameter and length with a caliper and taking the addition average (hereinafter, the same applies to the shapes of the milled fiber (MF) and the glass flake (GFL)). .
In the chopped strand (CS) having an average fiber diameter of less than 1 μm, the bulk density is small, the uniform dispersibility of the glass fiber is lowered, and the moldability tends to be impaired. On the other hand, if the average fiber diameter is larger than 25 μm, the appearance of the molded product is impaired and the reinforcing effect tends to be insufficient.

  The (a) glass fiber chopped strand (CS) in the present invention is preferably surface-treated with a sizing agent or a coupling agent. These surface treatments converge single fibers and give lubricity to the fiber surface, prevent damage to the fiber surface, improve the adhesion between glass fiber and aromatic polycarbonate resin, and have high mechanical properties. Strength is achieved.

  Examples of the sizing agent that can be used in the present invention include urethane-based, acrylic-based, acrylonitrile-styrene copolymer systems, epoxy-based systems, and the like. Particularly, urethane-based or epoxy-based sizing agents have the hue and heat resistance of the polycarbonate resin composition. This is preferable in that it is not impaired. Examples of the urethane sizing agent include resins having a urethane bond obtained by a reaction between a polyhydric alcohol and diisocyanate or triisocyanate, and examples of the epoxy sizing agent include bisphenol A type and alicyclic type epoxy resins. It is done.

  Examples of the coupling agent that can be used in the present invention include silane-based, titanate-based, aluminum-based, chromium-based, zirconium-based, and borane-based. Among these, silane-based coupling agents are preferable.

  As the silane coupling agent, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris (2-methoxyethoxy) silane, γ- Methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ -Mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc., among which γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β- (Aminoethyl) -γ-aminopropyl Use or combination of one or more coupling agents selected from trimethoxysilane are particularly preferred.

  There are no particular restrictions on the method of treating glass fibers using these sizing agents and / or coupling agents, and conventional methods such as dip coating, roller coating, spray coating, flow coating, spray coating, etc. This method can be used.

The glass fiber milled fiber (MF) is obtained by pulverizing the glass fiber (strand) described above. The (b-1) glass fiber milled fiber (MF) used in the present invention is a columnar or prismatic shape. The average fiber diameter is 1 to 25 μm, preferably 5 to 17 μm, the average length is 1 to 500 μm, preferably 10 to 300 μm, and more preferably 20 to 200 μm. Say things.
In a short fiber milled fiber (MF) having an average fiber diameter of less than 1 μm, moldability is impaired, and when the average fiber diameter is greater than 25 μm, the appearance is impaired and the reinforcing effect tends to be insufficient. .

Glass flakes (GFL) are usually glass flakes having an average particle diameter (average maximum diameter) of 10 to 4000 μm (4 mm) and an average thickness of several μm, and are used in the present invention (b-2). Glass flake (GFL) refers to those having an average particle diameter of 2000 μm or less, preferably in the range of 500 to 1500 μm, and an average thickness of 1 to 10 μm, preferably 2 to 6 μm.
Glass flakes (GFL) having an average particle size exceeding 2000 μm cause classification when blending each component of the resin composition, making it difficult to uniformly disperse with the aromatic polycarbonate resin, and causing spots on the molded product. Tend to occur.
As (b-2) glass flakes (GFL) of the present invention, as in the case of glass fibers, various couplings such as silanes and titanates are used in order to improve the adhesion to the aromatic polycarbonate resin. It is desirable to use a surface-treated product.

In the present invention, as described above, the glass-based inorganic filler as the component (B) includes (b-1) glass fiber milled fiber (MF) and (b) together with (a) glass fiber chopped strand (CS). -2) Although it mixes and combines at least 1 sort (b) chosen from glass flakes (GFL), it was mix | blended as these (B) components contained in the polycarbonate resin composition of this invention. When paying attention to all glass-based inorganic fillers, the L / D ratio (aspect ratio) is preferably 5 ≦ L / D ≦ 40, more preferably 7 ≦ L / D ≦ 35, It is preferable that 9 ≦ L / D ≦ 30. When L / D is less than 5, it becomes difficult to improve the heat distortion temperature of the molded product, the Izod impact strength tends to decrease, and the reinforcing effect tends to decrease. On the other hand, when L / D exceeds 40, combustibility tends to decrease.

  Note that L in the case of glass fibers (CS, MF) is the length in the major axis direction, D is the diameter of the surface perpendicular to the major axis direction, and L in the case of glass flakes (GFL) is It is the length of the major axis (the maximum diameter on the scale surface), and D is the length of the minor axis diameter (the shortest diameter on the scale surface).

In the present invention, the aspect ratio (L / D) of the (B) glass-based inorganic filler contained in the polycarbonate resin composition can be measured by the following procedure.
(1) The resin composition is burned at 600 to 700 ° C. or dissolved in methylene chloride to remove the polycarbonate resin component, and the inorganic filler is isolated.
(2) The isolated inorganic filler is spread on the glass so as not to overlap as much as possible, and is observed with an optical microscope at 40 to 100 times and photographed.
(3) From the obtained photograph, in the case of glass fiber (CS or MF), the length (L) and the maximum diameter (D), and in the case of glass flake (GFL), the long axis diameter (L) The minor axis diameter (D) is measured with a caliper, and the L / D of each inorganic filler is determined. In the present invention, L and D of 1000 inorganic fillers were arbitrarily measured from the photographed images, and the addition average of L / D values was obtained.

  In the present invention, (a) glass fiber chopped strand (CS) and (b-1) glass fiber milled fiber (MF) having the above-mentioned shapes are 5/95 to 95/5 in CS / MF (weight ratio). Further, it is preferably blended in the range of 80/20 to 20/80, particularly 70/30 to 30/70. In addition, (a) glass fiber chopped strands (CS) and (b-2) glass flakes (GFL) having the above-mentioned shapes have a CS / GFL (weight ratio) of 5/95 to 95/5, more preferably 80 / It is preferable to blend in the range of 20-20 / 80, particularly 60 / 20-20 / 80.

In the present invention, (b-1) glass fiber milled fiber (MF) and (b-2) glass flake (GFL) can be blended together with (a) glass fiber chopped strand (CS). In this case, the blending ratio of CS / MF / GFL (weight ratio) is 5/95/95 to 95/5/5, more preferably 80/20/20 to 20/80/80, particularly 70/30/30. It is preferable to mix in the range of -30/70/70.
The aspect ratio (L / D) mentioned above can be made into a preferable range by mix | blending each inorganic filler so that it may become such a ratio.

The total amount of the glass-based inorganic filler as the component (B) of the present invention is 1 to 150 parts by weight, more preferably 3 to 120 parts by weight, particularly 5 to 100 parts per 100 parts by weight of the aromatic polycarbonate resin. Part by weight is preferred. (B) If the compounding amount of the glass-based inorganic filler is less than 1 part by weight, the reinforcing effect is insufficient, and if it exceeds 150 parts by weight, the moldability and flame retardancy tend to be reduced.
In general, as the inorganic filler, in addition to those corresponding to the component (B) (CS, MF, GFL) of the present invention, there are various known inorganic fillers. As long as the above requirements are satisfied, these other inorganic fillers may be blended for the purpose of further improving mechanical strength and dimensional stability.

  Other inorganic fillers that may be blended in the resin composition of the present invention include, for example, glass beads, talc, mica, calcium silicate, potassium titanate and aluminum borate whiskers, carbon fibers, silicon carbide Examples thereof include fibers, aromatic polyamide fibers, stainless steel fibers, silica, and titanium oxide. Among these inorganic fillers, it is preferable to mix glass beads. Glass beads are fine spherical glass balls having an average particle diameter of 10 to 70 μm. Similarly to glass fibers, glass beads that are surface-treated with a silane coupling agent are preferable from the viewpoint of affinity with an aromatic polycarbonate resin.

(C) Flame retardant (C) Flame retardant used in the present invention is an alkali metal salt of perfluoroalkanedisulfonimide represented by the following general formulas (C-1) and (C-2), and alkaline earth It contains at least one selected from metal salts.

（一般式（Ｃ−１）中、Ｒ_１及びＲ_２は、各々独立に炭素数１〜８のパーフルオロアルキル基を示し、Ｍは、アルカリ金属又はアルカリ土類金属を示す。ｎはＭの価数である。）

(In General Formula (C-1), R ₁ and R ₂ each independently represents a C 1-8 perfluoroalkyl group, M represents an alkali metal or an alkaline earth metal, and n represents M. It is a valence.)

(In General Formula (C-2), Rf represents a linear or branched perfluoroalkylene group having 2 to 12 carbon atoms which may be substituted with a C4 to C7 perfluorocycloalkyl group. M ′ represents an alkali metal or an alkaline earth metal, and n is the valence of M ′.)

  The alkali metal salt or alkaline earth metal salt of the perfluoroalkane disulfonimide compound represented by the general formula (C-1) or (C-2) is used together with the specific (B) glass-based inorganic filler of the present invention. By blending, it can exhibit high flame retardancy compared to alkali metal salt of perfluoroalkane monosulfonic acid or its alkaline earth metal salt that has been generally used as a flame retardant, and polycarbonate. The resin composition exhibits excellent thermal stability.

  In the general formulas (C-1) and (C-2), the alkali metal or alkaline earth metal represented by M and M ′ is an alkali metal selected from Li, Na, K, Rb, and Cs, or Mg, An alkaline earth metal selected from Ca, Sr, and Ba can be given. Among these, (C) Li, Na, K are preferable as the alkali metal, and Mg, Ca are preferable as the alkaline earth metal from the viewpoint of compatibility between the flame retardant and the aromatic polycarbonate resin and imparting flame retardancy. Further, an alkali metal is preferable, and K is particularly preferable.

R ₁ and R ₂ in the general formula (C-1) each independently represent a perfluoroalkyl group having 1 to 8 carbon atoms, preferably 2 to 7 carbon atoms, more preferably 3 to 6 carbon atoms, It may be branched. When the carbon number of the perfluoroalkyl group exceeds 8, the compatibility with the aromatic polycarbonate resin is deteriorated and the appearance of the molded product tends to be deteriorated.
Rf in the general formula (C-2) is a linear or branched perfluoroalkylene group having 2 to 12, preferably 2 to 6, more preferably 2 to 3 carbon atoms, and 4 to 7 carbon atoms. The perfluorocycloalkyl group may be substituted. Among them, Rf is preferably a perfluoroalkylene group that is not substituted with a perfluorocycloalkyl group. If the total number of carbon atoms exceeds 12, the compatibility with the aromatic polycarbonate resin deteriorates, so that the appearance of the surface of the molded product tends to deteriorate.

  Specific examples of the perfluoroalkanedisulfonimide metal salt represented by the general formula (C-1) include bis (perfluoromethane) disulfonimide, bis (perfluoroethane) disulfonimide, bis (perfluoropropane) disulfonimide, Alkali metal salts such as bis (perfluorobutane) disulfonimide, bis (perfluoropentane) disulfonimide, bis (perfluorohexane) disulfonimide, bis (perfluoroheptane) disulfonimide, bis (perfluorooctane) disulfonimide Or alkaline-earth metal salt is mentioned. Among these, salts of bis (perfluoropropane) disulfonimide and bis (perfluorobutane) disulfonimide are preferable from the viewpoint of compatibility with an aromatic polycarbonate resin and imparting flame retardancy.

  Specific examples of the perfluoroalkanedisulfonimide metal salt represented by the general formula (C-2) include cyclic perfluoroethanedisulfonimide, cyclic 1,3-perfluoropropane disulfonimide, and cyclic 1,4-perfluorobutanedisulfone. Examples thereof include salts of imide, cyclic 1,5-perfluoropentane disulfonimide, cyclic 1,6-perfluorohexane disulfonimide and the like. Among these, a salt of cyclic 1,3-perfluoropropane disulfonimide or cyclic 1,4-perfluorobutane disulfonimide is preferable from the viewpoint of compatibility with an aromatic polycarbonate resin and imparting flame retardancy.

  The amount of the flame retardant (C) to be blended in the resin composition of the present invention is 0.001 to 5 parts by weight, preferably 0.001 to 2 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin (A). Part, more preferably 0.001 to 1 part by weight. (C) If the amount of the flame retardant is less than 0.001 part by weight, the flame retarding effect is difficult to obtain, whereas if it exceeds 5 parts by weight, decomposition of the polycarbonate tends to occur. Further, the blending ratio (weight ratio) of (B) glass-based inorganic filler and (C) flame retardant blended in the resin composition of the present invention is (B) :( C), usually 5000: 1 to 1. : 1, more preferably 3000: 1 to 50: 1, particularly 1000: 1 to 100: 1.

(D) Fluoropolyolefin The resin composition of the present invention preferably contains (D) a fluorinated polyolefin in order to impart anti-drip properties. (D) The fluorinated polyolefin refers to a polymer having a structure in which all or most of the hydrogen atoms of the polyolefin are substituted by fluorine atoms. For example, polytetrafluoroethylene, tetrafluoroethylene, hexafluoropropylene, Of these, polytetrafluoroethylene is preferable. As polytetrafluoroethylene, polytetrafluoroethylene having the ability to form fibrils, that is, polytetrafluoroethylene showing a tendency to bind polymers to form a fibrous structure, prevents dripping during combustion. preferable.

  (D) Although the compounding quantity of fluorinated polyolefin is the quantity which does not exceed 5 weight part with respect to 100 weight part of aromatic polycarbonate resin, in order to acquire sufficient dripping prevention effect, 0.01-5 weight part And preferably 0.02 to 3 parts by weight, more preferably 0.05 to 2 parts by weight. When the blending amount of the fluorinated polyolefin is less than 0.01 parts by weight, the dripping prevention effect is low and the flame retardancy tends to be insufficient, and when it exceeds 5 parts by weight, the extrudability and moldability tend to be impaired. is there.

  The blending ratio (weight ratio) of (B) glass-based inorganic filler and (D) fluorinated polyolefin blended in the resin composition of the present invention is (B) :( D), usually 5000: 1 to 1. 1: 1, more preferably 3000: 1 to 50: 1, and particularly preferably 1000: 1 to 100: 1. Furthermore, the blending ratio (weight ratio) of (C) flame retardant and (D) fluorinated polyolefin blended in the resin composition of the present invention is (C) :( D), usually 200: 1 to 1: 200. Further, 100: 1 to 1: 100, particularly 10: 1 to 1:10 are preferable.

(E) Polycarbonate oligomer It is preferable to further blend (E) a polycarbonate oligomer in the resin composition of the present invention. The molded product obtained from the resin composition formed by blending the above-described (A) aromatic polycarbonate resin, (B) glass-based inorganic filler, and (C) flame retardant is excellent in combustibility, impact resistance, and the like. However, the appearance defect peculiar to the reinforced resin material (floating of the inorganic filler) is likely to occur. By blending the (E) polycarbonate oligomer in the resin composition of the present invention, such poor appearance can be suppressed.

  The (E) polycarbonate oligomer of the present invention has a repeating structural unit represented by the following general formula (E-1), has a viscosity average molecular weight of 1,000 to 10,000, more preferably 2,000 to 8,000. Are preferred. When the viscosity average molecular weight is less than 1,000, the mechanical strength decreases, and when it exceeds 10,000, the appearance improving effect tends to be small.

(In General Formula (E-1), R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 3 carbon atoms. X is 1 carbon atom. -5 alkylene group or alkylidene group, oxygen atom, sulfur atom or sulfonyl group, which may have a substituent.

  (E) Polycarbonate oligomers are 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis ( 4-hydroxy-3,5-dibromophenyl) reaction of aromatic dihydric phenolic compound represented by propane and carbonate precursor represented by phosgene, aromatic dihydric phenolic compound, diphenyl carbonate, etc. It can be obtained by transesterification reaction. Among these, a polycarbonate oligomer having a viscosity average molecular weight of 2,000 to 8,000 obtained by reacting bisphenol A with phosgene or carbonic acid diester is most preferable. Aromatic dihydric phenol compounds may be used alone or in combination.

  (E) In order to adjust the degree of polymerization of the polycarbonate oligomer, in the case of the interfacial polymerization method using phosgene, phenol and / or alkyl-substituted phenol may be added to the polymerization system to end-capping. Moreover, the compounding quantity of (E) polycarbonate oligomer is 1-50 weight part with respect to 100 weight part of (A) aromatic polycarbonate resin, although it depends also on the kind of (B) glass-type inorganic filler to mix | blend, Preferably it is 2-30 weight part, More preferably, it is 4-20 weight part. (E) When the compounding quantity of a polycarbonate oligomer exceeds 50 weight part, intensity | strength and heat resistance will become inadequate, and when it is less than 1 weight part, there exists a tendency for the external appearance improvement effect to become small.

  The blending ratio (weight ratio) of (B) glass-based inorganic filler and (E) polycarbonate oligomer to be blended in the resin composition of the present invention is (B) :( E) and is 5000: 1 to 1: 1. Further, 3000: 1 to 50: 1, particularly 1000: 1 to 100: 1 are preferable. The blending ratio (weight ratio) of (C) flame retardant and (E) polycarbonate oligomer blended in the resin composition of the present invention is (C) :( E), and is 1000: 1 to 1: 1000. Further, 100: 1 to 1: 100, particularly 10: 1 to 1:10 are preferable. Furthermore, the blending ratio (weight ratio) of (D) fluorinated polyolefin and (E) polycarbonate oligomer blended in the resin composition of the present invention is (D) :( E), and is 1: 1 to 1: 2000. Yes, and more preferably 1: 5 to 1: 1000, particularly 1:20 to 1: 500.

(F) Phosphorus compound In the present invention, it is preferable to blend (F) a phosphorus compound as a stabilizer, particularly when heat stability is required. (F) As a phosphorus compound, a well-known phosphite type or a phosphate type compound can be used. For example, the product names PEP-36, PEP-8, 2112 and HP-10 by Asahi Denka Co., Ltd. A phosphate compound such as AX-71 can be used.

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, and tris (tridecyl). ) Phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite Hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4'-butylidene-bis (3-methyl-6-te t-butylphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4′-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, di Lauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Phytopolymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphos Aito, 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

Among these, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl) -4-methylphenyl) pentaerythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite Particularly preferred.
The phosphate compound is preferably a compound having a P—OH structure. For example, AX-71 manufactured by Asahi Denka Kogyo Co., Ltd. having the following structure (wherein n is 1 to 1) 2) is particularly preferred.

  (F) The compounding quantity of a phosphorus compound is 0.01-2 weight part with respect to 100 weight part of (A) aromatic polycarbonate resin, Furthermore, 0.02-1.5 weight part, Especially 0.1. 02 to 1 part by weight is preferred. If the phosphorus compound is less than 0.01 parts by weight, the effect of improving the heat stability is not sufficient, and if it exceeds 2 parts by weight, gas is generated, which is not preferable. With such a small amount of blending, the mechanical strength of the molded product will not decrease.

Other Additional Components The polycarbonate resin composition of the present invention may be blended with other additional components as needed within a range that does not significantly impair the performance, if necessary. As other additional components, for example, stabilizers such as UV absorbers and antioxidants, pigments, dyes, lubricants, flame retardants, mold release agents, additives such as slidability improvers, elastomers, etc. may be blended. it can.

  Moreover, (A) thermoplastic resins other than aromatic polycarbonate resin can also be mix | blended with the resin composition of this invention. The kind and blending amount of such a thermoplastic resin can be appropriately selected for the purpose of improving the performance such as moldability and chemical resistance. Specifically, polyester resin, polyamide resin, polyolefin resin, polyphenylene ether type Resins, styrene resins, polysulfones, polyether sulfones, polyphenylene sulfides, polyacrylates, polyamide imides, polyether imides, and the like can be given.

  Among the thermoplastic resins described above, examples of the polyester resin include polybutylene terephthalate, polyethylene terephthalate, polybutylene naphthalate, and polyethylene naphthalate. Examples of the polyolefin resin include polyethylene and polypropylene. Examples of the polyphenylene ether resins include polyphenylene ether resins and mixed resins of polyphenylene ether and polystyrene and / or HIPS (high impact polystyrene). Examples of the styrene resin include polystyrene, HIPS, AS resin, ABS resin, and the like.

  Among these, polybutylene terephthalate, polyethylene terephthalate, polyphenylene ether resin, HIPS, ABS resin and the like are preferable. The blending amount of the thermoplastic resin other than the aromatic polycarbonate resin is preferably less than 50% by weight of the total amount of the thermoplastic resin other than the (A) aromatic polycarbonate resin and the aromatic polycarbonate resin, more preferably 40% by weight or less, particularly Is preferably 30% by weight or less.

  The method for producing the polycarbonate resin composition of the present invention is not particularly limited. For example, all the components are weighed in advance and melt-kneaded together, or (B) components other than the glass-based inorganic filler are previously added. Examples of what is melt-kneaded together include (B) a method of side-feeding a glass-based inorganic filler. The polycarbonate resin composition of the present invention can be molded into various molded products by various molding methods such as injection molding and extrusion molding.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, the raw materials described below were used.

[raw materials]
(A) Aromatic polycarbonate resin (PC): poly-4,4-isopropylidenediphenyl carbonate ("Iupilon (registered trademark) S-3000" manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 21,500)
(B) Glass-based inorganic filler (a) Glass fiber chopped strand (CS): “T-571” manufactured by Nippon Electric Glass Co., Ltd., average fiber diameter 13 μm, average length 3 mm.
(B-1) Glass fiber milled fiber (MF): “JB1-20” manufactured by Asahi Fiber Glass Co., Ltd., average fiber diameter of 10 μm, average length of 30 to 100 μm.
(B-2) Glass flakes (GFL): “REFG-101” manufactured by Nippon Sheet Glass Co., Ltd., average thickness 4 μm, average particle diameter 1 mm.

(C) Flame retardant (C-1): potassium bis (perfluorobutane) disulfonimide [(C ₄ F ₉ SO ₂ ) ₂ NK] (“EF-N442” manufactured by Gemco).
(C-2): Cyclic 1,3-perfluoropropane disulfonimide potassium represented by the following formula ("EF-N302" manufactured by Gemco).

（Ｃ−３）：パーフルオロブタンスルホン酸カリウム塩（大日本インキ（株）社製「メガファックＦ１１４」

(C-3): Perfluorobutanesulfonic acid potassium salt (Dainippon Ink & Co., Ltd. "Megafac F114"

(D) Fluoropolyolefin: Polytetrafluoroethylene ("Polyflon F-201L" manufactured by Daikin Industries, Ltd.)
(E) Polycarbonate oligomer: “AL071” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 5,000.

(F) Phosphorus compound: “AX-71” manufactured by Asahi Denka Kogyo Co., Ltd. (a mixture having the following structure and n = 1 to 2).

[Examples 1-6 and Comparative Examples 1-7]
Each component is blended in the blending amounts (parts by weight) shown in Table 1 and Table 2, and melt-kneaded at a barrel temperature of 300 ° C. with a single screw extruder VS-40 (manufactured by Tanabe Plastics), and pellets of the resin composition Got. Various test pieces were molded from the obtained pellets under the injection molding conditions shown below. Using the obtained molded sample, an evaluation test of the molded product was performed, and the results are shown in Tables 1 and 2.

[L / D measurement method of inorganic filler in resin composition]
The resin composition pellets are dissolved in methylene chloride and then filtered to isolate the inorganic filler. The isolated inorganic filler was spread on a glass so as not to overlap as much as possible, and observed with an optical microscope (OLYMPUS SZH) at a magnification of 40 and photographed. For each of 1000 inorganic fillers arbitrarily selected from the obtained photographs, the fiber diameter and length in the case of glass fiber (CS, MF), and the long axis diameter in the case of glass flake (GFL) (Maximum diameter) and minor axis diameter (shortest diameter) were measured with calipers, and averaged to determine L / D.

[Molding conditions and molded product evaluation method]
(1) Flame retardance According to UL94 vertical flammability test, the pellets of the resin composition were dried at 120 ° C. for 5 hours, and then cylinder temperature was measured using a CYCAP M-2 (clamping force 75T) manufactured by Sumitomo Heavy Industries, Ltd. Under the conditions of 320 ° C., mold temperature 110 ° C., and cycle 1 min, 1.6 mm and 1.2 mm thickness test pieces were injection-molded, and each flammability test was performed.

(2) Impact resistance After the pellets of the resin composition were dried at 120 ° C. for 5 hours, a cylinder temperature of 300 ° C. and a mold temperature of 100 were used using a Saicap M-2 manufactured by Sumitomo Heavy Industries, Ltd. (clamping force 75T). A test piece having the same shape as the multi-purpose test piece (type A) was molded with a two-point gate under the conditions of 0 ° C. and a cycle of 1 min, and injection molded so that a weld could be formed at the center. The test piece was subjected to a Charpy impact test without a notch in accordance with ISO179.

(3) Dimensional stability (anisotropic shrinkage of molded product)
After drying the pellets of the resin composition at 120 ° C. for 5 hours, a cylinder temperature of 300 ° C., a mold temperature of 100 ° C., and a cycle of 1 min are used using a CYCAP M-2 manufactured by Sumitomo Heavy Industries, Ltd. Then, a plate of 80 mm × 40 mm × 3.2 mm (thickness) was formed. The shrinkage rate in the flow direction (MD) and the vertical direction (TD) was measured, and the values of [(shrinkage rate in the flow direction (MD)) − (shrinkage rate in the vertical direction (TD))] are shown in Tables 1 and 2. displayed.

(4) Appearance In the same manner as the evaluation of dimensional stability, a plate of 80 mm × 40 mm × 3.2 mm (thickness) was formed, the appearance of the plate was visually observed, and judged based on the following criteria.
○: No lifting of the inorganic filler is seen Δ: Slight lifting of the inorganic filler is seen

(5) Flexural modulus After drying the pellets of the resin composition at 120 ° C. for 5 hours, a cylinder temperature of 300 ° C. and a mold temperature of 100 using a Saicap M-2 (clamping force 75T) manufactured by Sumitomo Heavy Industries, Ltd. A multi-purpose test piece (type A) was injection-molded under the conditions of 0 ° C. and a cycle of 1 min, a three-point bending test was performed in accordance with ISO178, and the flexural modulus was measured.
(6) Heat resistance (deflection temperature under load: DTUL)
Similarly to the evaluation of the flexural modulus, a multipurpose test piece (type A) was injection-molded, and the heat distortion temperature at a load of 1.80 MPa was measured according to ISO75.

(7) Stability thermal stability The molecular weight of the molded multipurpose test piece (type A) is measured in the same manner as in the evaluation of the flexural modulus. This molding is referred to as “normal molding” (cylinder temperature 300 ° C., cycle 1 min), and the molecular weight at this time is referred to as “normal molding molecular weight”.
On the other hand, a multi-purpose test piece (type A) is injection-molded and the molecular weight is measured in the same manner as normal molding except that the cylinder temperature is 320 ° C. and the condition of cycle 5 min is used. This molding is referred to as “retention molding”, and the molecular weight at this time is referred to as “retention molding molecular weight”.
The residence heat stability was expressed as a molecular weight reduction value obtained by [normal molding molecular weight−retention molding molecular weight]. The smaller this value, the better the residence heat stability.

（１）実施例１と比較例１、実施例２と比較例２、実施例３及び実施例４と比較例３とを各々比べると、（Ｂ）無機充填剤として、ＣＳと共に、ＭＦ又はＧＦＬを併用した実施例においては、難燃性、耐衝撃性及び寸法安定性に優れ、また、曲げ弾性率、耐熱性、滞留熱安定性、外観を含めて総合的にバランスの良い性能を示すことがわかる。
（２）オリゴマーを配合した実施例３〜６においては、更に外観が優れることがわかる。
（３）リン系化合物（ＡＸ７１）を配合した実施例５及び６においては、更に滞留熱安定性が優れることが分かる。

(1) When comparing Example 1 and Comparative Example 1, Example 2 and Comparative Example 2, Example 3 and Example 4 and Comparative Example 3, respectively, (B) MF or GFL as an inorganic filler together with CS In the examples in combination, the flame retardancy, impact resistance and dimensional stability are excellent, and the performance is well balanced including bending elastic modulus, heat resistance, residence heat stability and appearance. I understand.
(2) In Examples 3 to 6 in which the oligomer is blended, it can be seen that the appearance is further excellent.
(3) In Example 5 and 6 which mix | blended phosphorus type compound (AX71), it turns out that the residence heat stability is further excellent.

(4) In Comparative Example 4 using perfluoroalkane sulfonate (F114) as a flame retardant, it can be seen that the flame retardancy is poor (1.2 mm).
(5) In Comparative Example 5 in which the blending amount of (B) inorganic filler is less than 1 part by weight, it can be seen that the flexural modulus is low and the intended mechanical strength cannot be obtained.

Claims (7)

(A) For 100 parts by weight of the aromatic polycarbonate resin,
(B) (a) Glass fiber chopped strand (CS) was combined with at least one (b) selected from (b-1) glass fiber milled fiber (MF) and (b-2) glass flake (GFL). 1 to 150 parts by weight of a glass-based inorganic filler,
(C) Perfluoroalkanedisulfonimide alkali metal salt represented by the following general formulas (C-1) and (C-2), and at least one flame retardant selected from alkaline earth metal salts 0.001 to 0.001 5 parts by weight,
A polycarbonate resin composition comprising:

(In General Formula (C-1), R ₁ and R ₂ each independently represent a perfluoroalkyl group having 1 to 8 carbon atoms, M represents an alkali metal or an alkaline earth metal, and n represents M. It is a valence.)

(In General Formula (C-2), Rf represents a linear or branched perfluoroalkylene group having 2 to 12 carbon atoms, which may be substituted with a 4 to 7 carbon perfluorocycloalkyl group. M ′ represents an alkali metal or an alkaline earth metal, and n is the valence of M ′.)   (A) Polycarbonate resin composition of Claim 1 formed by mix | blending 0.01-5 weight part of fluorinated polyolefin with respect to 100 weight part of aromatic polycarbonate resin.   (B) Glass-based inorganic fillers are (a) glass fiber chopped strands (CS) having an average fiber diameter of 1 to 25 μm and an average length of 1 mm to 10 mm, and (b-1) an average fiber diameter of 1 to 25 μm, The polycarbonate resin composition according to claim 1 or 2, comprising glass fiber milled fiber (MF) having an average length of 1 to 500 µm in a range of CS / MF (weight ratio) of 5/95 to 95/5. .   (B) Glass-based inorganic fillers are (a) glass fiber chopped strands (CS) having an average fiber diameter of 1 to 25 μm and an average length of 1 mm to 10 mm, and (b-2) an average thickness of 1 to 10 μm, 3. The polycarbonate resin composition according to claim 1, comprising glass flakes (GFL) having an average particle diameter of 2000 μm or less in a range of CS / GFL (weight ratio) of 5/95 to 95/5.   The polycarbonate resin composition according to any one of claims 1 to 4, wherein (B) the glass-based inorganic filler in the polycarbonate resin composition has an L / D (aspect ratio) of 5 to 40.   (A) The polycarbonate resin composition in any one of Claims 1-5 formed by mix | blending (E) polycarbonate oligomer 1-50 weight part with respect to 100 weight part of aromatic polycarbonate resin.   A molded article obtained by melt-molding the polycarbonate resin composition according to claim 1.