JP2012116915A - Glass fiber-reinforced resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition which has excellent mechanical strength, reduced anisotropy in a mold shrinkage, and high impact properties with a resin composition as a substrate comprising a polycarbonate resin reinforced with flat cross-sectional glass fiber.SOLUTION: The glass fiber-reinforced resin composition contains: (A) 40 to 99 pts.wt. of a resin component (A component) comprising a polycarbonate-polyorganosiloxane copolymer (A-1 component) composed of a carbonate constituting unit represented by general formula [1] and a carbonate constituting unit represented by general formula [3] and a polycarbonate resin (A-2 component) composed of the carbonate constituting unit represented by the general formula [1], wherein the weight ratio between the A-1 component and the A-2 component (A-1 component/A-2 component) is 10/90 to 100/0; and (B) 1 to 60 pts.wt. of a reinforcing filler (B component) comprising the flat cross-sectional glass fiber (B-1 component), in which the average value of the major axis in the fiber cross-section is 10 to 50 μm and the average value between the major axis and the minor axis (major axis/minor axis) is 1.5 to 8.0, and a filler (B-2 component) other than the B-1 component, wherein the weight ratio between the B-1 component and the B-2 component (B-1 component/B-2 component) is 5/95 to 100/0.

Description

  The present invention relates to a glass fiber reinforced resin composition having improved impact characteristics. More specifically, a thermoplastic resin containing a polycarbonate-organosiloxane copolymer resin reinforced with flat cross-section glass fibers is used as a base, has excellent mechanical strength, and has a small anisotropy in molding shrinkage, and further has high impact characteristics. The present invention also relates to a glass fiber reinforced resin composition.

  Thermoplastic resins reinforced with glass fibers are widely used because of their excellent mechanical strength and processability. In particular, polycarbonate resins are used in many applications such as mechanical parts, automobile parts, electrical / electronic parts, and office equipment parts because of their excellent properties such as mechanical strength, dimensional stability and flame retardancy. On the other hand, although the resin composition which mix | blended glass fiber with the polycarbonate resin is excellent in mechanical strength and rigidity, it has the fault that the anisotropy of the mold shrinkage ratio by fiber orientation will arise. In recent years, when used for molded parts such as precision machine parts such as camera parts and office equipment parts, a glass fiber reinforced thermoplastic resin having good mechanical strength, low anisotropy, and flame retardancy is required.

  For example, a resin composition (see Patent Document 1) comprising an aromatic polycarbonate resin, a glass filler having a specific cross-sectional shape, and various fillers is known. However, such publications have insufficient good mechanical strength. Moreover, a resin composition comprising a resin combined with a specific polycarbonate copolymer and a polycarbonate-polyorganosiloxane copolymer and a flat cross-section glass fiber is known (see Patent Document 2). However, such publications have insufficient good mechanical strength and flame retardant properties.

JP 2007-186571 A JP 2009-280636 A

  In view of the above, an object of the present invention is to use a resin composition containing a polycarbonate resin reinforced with flat cross-section glass fibers as a base, a resin having excellent mechanical strength, small anisotropy of molding shrinkage, and high impact characteristics. It is to provide a composition. As a result of earnest studies as a result of achieving the above object, the present inventors have found that such an object can be achieved by using a glass fiber having a specific cross-sectional shape and a polycarbonate-polyorganosiloxane copolymer resin, The present invention has been completed through further investigation.

  According to the present invention, the above-described problem is solved by: (A) a polycarbonate-polyorganosiloxane copolymer comprising a carbonate structural unit represented by the following general formula [1] and a carbonate structural unit represented by the following general formula [3]. (A-1 component) and a polycarbonate resin (A-2 component) comprising a carbonate structural unit represented by the following general formula [1], and the weight ratio of the A-1 component to the A-2 component (A-1 (Component / A-2 component) is 10/90 to 100/0 resin component (component A) 40 to 99 parts by weight, and (B) the average value of the major axis of the fiber cross section is 10 to 50 μm, the major axis and the minor axis It consists of a flat cross-section glass fiber (B-1 component) having an average ratio (major axis / minor axis) of 1.5 to 8.0 and a filler (B-2 component) other than the B-1 component, and B- Weight ratio of 1 component to B-2 component (B-1 component Is accomplished by component B-2) is 5/95 to / 0 a is reinforcing filler (B component) glass fiber reinforced resin composition containing 1 to 60 parts by weight.

［上記一般式〔１〕において、Ｒ^１及びＲ^２は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１８のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数３〜１４のアリール基、炭素原子数３〜１４のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、それぞれ複数ある場合はそれらは同一でも異なっていても良く、ｅ及びｆは夫々１〜４の整数であり、Ｗは単結合もしくは下記一般式〔２〕で表される基からなる群より選ばれる少なくとも一つの基である。］

[In General Formula [1], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]. . ]

［上記一般式〔２〕においてＲ^１１，Ｒ^１２，Ｒ^１３，Ｒ^１４，Ｒ^１５，Ｒ^１６，Ｒ^１７及びＲ^１８は夫々独立して水素原子、炭素原子数１〜１８のアルキル基、炭素原子数３〜１４のアリール基及び炭素原子数７〜２０のアラルキル基からなる群から選ばれる基を表し、Ｒ^１９及びＲ^２０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１８のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のシクロアルキル基、炭素原子数６〜２０のシクロアルコキシ基、炭素原子数２〜１０のアルケニル基、炭素原子数３〜１４のアリール基、炭素原子数６〜１０のアリールオキシ基、炭素原子数７〜２０のアラルキル基、炭素原子数７〜２０のアラルキルオキシ基、ニトロ基、アルデヒド基、シアノ基及びカルボキシル基からなる群から選ばれる基を表し、複数ある場合はそれらは同一でも異なっていても良く、ｇは１〜１０の整数、ｈは４〜７の整数である。］

[In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and It represents a group selected from the group consisting of carboxyl groups, and when there are a plurality thereof, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7. ]

［上記一般式〔３〕において、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、各々独立に水素原子、炭素数１〜１２のアルキル基又は炭素数６〜１２の置換若しくは無置換のアリール基であり、Ｒ^９及びＲ^１０は夫々独立して水素原子、ハロゲン原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基であり、ｐは自然数であり、ｑは０又は自然数であり、ｐ＋ｑは３００未満の自然数である。Ｘは炭素原子数２〜８の二価脂肪族基である。］

[In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number less than 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]

Hereinafter, the details of the present invention will be described.
(A component)
(A-1 component: Polycarbonate-polyorganosiloxane copolymer)
The polycarbonate-polyorganosiloxane copolymer used as the component A-1 of the present invention comprises a carbonate structural unit represented by the above general formula [1] and a carbonate structural unit represented by the above general formula [3]. Polycarbonate copolymer.

  Examples of the dihydric phenol (I) for deriving the carbonate structural unit represented by the general formula [1] include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis ( 4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methyl) Phenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3′-biphenyl) propane, 2,2-bis ( 4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4 Hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxy) Phenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9,9 -Bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) ) Cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'- Hydroxy-3,3′-dimethyldiphenyl ether, 4,4′-sulfonyldiphenol, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide, 2,2′-dimethyl-4,4 '-Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'- Sulfonyldiphenol, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) Propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} Benzene, 1,4-bis (4-hydroxyphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6 Decane, 4,4 ′-(1,3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the like.

  Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-biphenyl. (4-hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

In the carbonate structural unit represented by the general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or carbon. A substituted or unsubstituted aryl group having 6 to 12 carbon atoms, preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, a hydrogen atom, carbon An alkyl group of 1 to 6 or a phenyl group is particularly preferable. R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably a hydrogen atom or 1 to 10 carbon atoms. An alkyl group, particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate structural unit represented by the above formula [3], for example, a compound represented by the following general formula (I) is preferably used.

  The dihydroxyaryl-terminated polydiorganosiloxane (II) is a phenol having an olefinically unsaturated carbon-carbon bond, preferably vinylphenol, 2-allylphenol, isopropenylphenol, or 2-methoxy-4-allylphenol. It is easily produced by hydrosilylation reaction at the end of a polysiloxane chain having a degree of polymerization of. Of these, (2-allylphenol) -terminated polydiorganosiloxane, (2-methoxy-4-allylphenol) -terminated polydiorganosiloxane are preferred, and (2-allylphenol) -terminated polydimethylsiloxane and (2-methoxy-) are particularly preferred. 4-Allylphenol) -terminated polydimethylsiloxane is preferred.

  Here, p + q (degree of diorganosiloxane polymerization) is preferably 2 to 290, more preferably 5 to 100. Above the lower limit of the preferred range, the impact resistance and flame retardancy are excellent, and below the upper limit of the suitable range, the surface appearance of the molded product is excellent. A copolymer having the above lower limit or more has a high effect of modifying rheological properties due to the introduction of a polydiorganosiloxane moiety having a low cohesive force, and tends to increase the structural viscosity index. As a result, it is possible to obtain a highly flame-retardant resin molded article in which drip during combustion is suppressed while maintaining high fluidity during shear flow. Such a copolymer below the upper limit tends to reduce the average size and normalized dispersion of the polydiorganosiloxane domain. As a result, a resin molded product having an excellent surface appearance can be obtained. The number of moles per unit weight of the polydiorganosiloxane unit below the upper limit is increased, and the unit is easily incorporated into the polycarbonate evenly. When the degree of polymerization of the diorganosiloxane is large, the incorporation of polydiorganosiloxane units into the polycarbonate becomes uneven and the proportion of polydiorganosiloxane units in the polymer molecule increases. Polycarbonate is likely to occur, and the compatibility with each other tends to decrease. As a result, large polydiorganosiloxane domains are likely to occur. On the other hand, from the viewpoint of fluidity, impact resistance, and flame retardancy, it is advantageous that the polydiorganosiloxane domain is somewhat large, and therefore there is a preferred range of polymerization degree as described above.

The polydiorganosiloxane component content in the total weight of the polycarbonate-polydiorganosiloxane copolymer used as the component A-1 of the present invention is preferably 0.1 to 40% by weight. The polydiorganosiloxane component content is more preferably 0.5 to 20% by weight, further preferably 1 to 15% by weight, and most preferably 2 to 10% by weight. Above the lower limit of the preferable range, the impact resistance and flame retardancy are excellent, and when it is lower than the upper limit of the preferable range, an excellent surface appearance that is hardly affected by the molding conditions is easily obtained. Such diorganosiloxane polymerization degree and polydiorganosiloxane content can be calculated by ¹ H-NMR measurement.

  In the present invention, the dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate constituent unit represented by the general formula [3] may be used alone or in combination of two or more. Moreover, the carbonate structural unit other than the general formulas [1] and [3] can be used in combination within a range of 10% by weight or less with respect to the total weight of the component A-1 within the range not hindering the present invention.

Next, a method for producing a polycarbonate-polydiorganosiloxane copolymer will be described below.
By reaction of dihydric phenol (I) with a chloroformate-forming compound such as chloroformate of phosgene or dihydric phenol (I) in a mixture of an organic solvent insoluble in water and an aqueous alkali solution in advance. A mixed solution of a chloroformate compound of divalent phenol (I) and / or a carbonate oligomer of dihydric phenol (I) having a terminal chloroformate group is prepared. As the chloroformate-forming compound, phosgene is preferred.

  In producing the chloroformate compound from the dihydric phenol (I), all the dihydric phenol (I) derived from the carbonate structural unit represented by the general formula [1] can be converted to the chloroformate compound at once. Alternatively, a part thereof may be added as a reaction raw material to a subsequent interfacial polycondensation reaction as a post-added monomer. The post-added monomer is added to allow the subsequent polycondensation reaction to proceed rapidly, and it is not necessary to add it when it is not necessary.

  The method for this chloroformate compound formation reaction is not particularly limited, but usually a method of carrying out in a solvent in the presence of an acid binder is preferred. Furthermore, if desired, a small amount of an antioxidant such as sodium sulfite and hydrosulfide may be added, and it is preferable to add them.

  The use ratio of the chloroformate-forming compound may be appropriately adjusted in consideration of the stoichiometric ratio (equivalent) of the reaction. Moreover, when using the phosgene which is a suitable chloroformate formation compound, the method of blowing gasified phosgene into a reaction system can be employ | adopted suitably.

  Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, organic bases such as pyridine, and mixtures thereof. Is used.

  The use ratio of the acid binder may be appropriately determined in consideration of the stoichiometric ratio (equivalent) of the reaction as described above. Specifically, 2 equivalents or slightly more than 2 equivalents per mole of dihydric phenol (I) used for forming the chloroformate compound of dihydric phenol (I) (usually 1 mole corresponds to 2 equivalents). It is preferable to use an acid binder.

  As said solvent, what is necessary is just to use a solvent inert to various reaction, such as what is used for manufacture of a well-known polycarbonate, individually or as a mixed solvent. Representative examples include hydrocarbon solvents such as xylene, and halogenated hydrocarbon solvents such as methylene chloride and chlorobenzene. In particular, a halogenated hydrocarbon solvent such as methylene chloride is preferably used.

The pressure in the formation reaction of the chloroformate compound is not particularly limited and may be any of normal pressure, pressurization, or reduced pressure, but it is usually advantageous to carry out the reaction under normal pressure. The reaction temperature is selected from the range of -20 to 50 ° C, and in many cases, heat is generated with the reaction, so it is desirable to cool with water or ice. Although the reaction time depends on other conditions and cannot be defined unconditionally, it is usually carried out in 0.2 to 10 hours.
As the pH range in the formation reaction of the chloroformate compound, known interfacial reaction conditions can be used, and the pH is usually adjusted to 10 or more.

  In the production of the polycarbonate copolymer used as the component A-1 of the present invention, the dihydric phenol (I) chloroformate and the dihydric phenol (I) carbonate having terminal chloroformate groups are thus obtained. After preparing the mixed solution of the chloroformate compound containing the oligomer, the dihydroxyaryl-terminated polydiorganosiloxane (II) for deriving the carbonate constituent unit represented by the general formula [3] while stirring the mixed solution is mixed with the mixed solution. Is added at a rate of 0.01 mol / min or less per 1 mol of the dihydric phenol (I) charged for the preparation of the dihydroxyaryl-terminated polydiorganosiloxane (II) and the chloroformate compound. Polycarbonate-polydiorganosiloxane by condensation To obtain a polymer.

  The polycarbonate copolymer used as the component A-1 of the present invention can be made into a branched polycarbonate copolymer by using a branching agent in combination with a dihydric phenol compound. Examples of the trifunctional or higher polyfunctional aromatic compound used in the branched polycarbonate resin include phloroglucin, phloroglucid, or 4,6-dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2, 2 , 4,6-trimethyl-2,4,6-tris (4-hydroxyphenyl) heptane, 1,3,5-tris (4-hydroxyphenyl) benzene, 1,1,1-tris (4-hydroxyphenyl) Ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, 4- {4- [ Trisphenol such as 1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol, tetra (4-hydride) Loxyphenyl) methane, bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acids Among them, 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferable. 1-Tris (4-hydroxyphenyl) ethane is preferred.

Even if the branched polycarbonate copolymer is produced by the interfacial polycondensation reaction after the completion of the production reaction, the branched solution may contain a branching agent in the mixed solution during the production reaction of the chloroformate compound. It may be a method in which an agent is added. The proportion of the carbonate constituent unit derived from the branching agent is preferably 0.005 to 1.5 mol%, more preferably 0.01 to 1.2 mol% in the total amount of carbonate constituent units constituting the copolymer. Especially preferably, it is 0.05-1.0 mol%. Such a branched structure amount can be calculated by ¹ H-NMR measurement.

  The pressure in the system in the polycondensation reaction can be any of reduced pressure, normal pressure, or increased pressure, but can usually be suitably performed at normal pressure or about the pressure of the reaction system. The reaction temperature is selected from the range of −20 to 50 ° C., and in many cases, heat is generated with the polymerization, so it is desirable to cool with water or ice. Since the reaction time varies depending on other conditions such as the reaction temperature, it cannot be generally specified, but it is usually performed in 0.5 to 10 hours.

In some cases, the obtained polycarbonate copolymer is appropriately subjected to physical treatment (mixing, fractionation, etc.) and / or chemical treatment (polymer reaction, crosslinking treatment, partial decomposition treatment, etc.) to obtain a desired reduced viscosity [η _SP / C] can also be obtained as a polycarbonate copolymer.
The obtained reaction product (crude product) can be recovered as a polycarbonate-polydiorganosiloxane copolymer having a desired purity (purity) by performing various post-treatments such as a known separation and purification method.

The structural viscosity index is used as an index characterizing the melt flow characteristics of the polycarbonate resin, and is represented by the following formula (1).

  In the above formula (1), D is a shear rate (1 / sec), a is a constant, σ is a shear stress (Pa), and N is a structural viscosity index. This structural viscosity index is measured according to ISO11443. The structural viscosity index can be an index of resin fluidity in molding and can be an index of anti-drip ability during combustion. When N = 1, Newtonian fluidity is exhibited, and as N increases, non-Newtonian fluidity increases. When this structural viscosity index is high, the resin has a high viscosity in a molten state, so that the resin is difficult to dripping during combustion, and when the shear rate is high, the viscosity is lowered, and thus the molding processability is excellent. The polycarbonate copolymer used as the component A-1 of the present invention preferably has a value of N of 1.60 to 2.50, more preferably 1.60 to 2.30, and even more preferably 1. 65 to 2.30. Copolymers with N of 1.60 or more exhibit excellent flame retardancy by suppressing dripping of fire types during combustion, and copolymers with N of 2.50 or less have low shear viscosity and excellent moldability. preferable.

Usually, the higher the viscosity average molecular weight (Mv) of the resin, the higher the structural viscosity index, but the aromatic polycarbonate resin is not preferable because the fluidity decreases as the viscosity average molecular weight increases. The viscosity average molecular weight of the polycarbonate copolymer used as the A-1 component of the present invention is preferably 1.6 × 10 ^{4 to} 3.0 × 10 ⁴ , more preferably 1.6 × 10 ^{4 to} 2.5. × 10 ^4, more preferably from ^{1.7 × 10 4 ~2.4 × 10 4} . If it is above the lower limit of this preferred range, practical mechanical strength can be obtained in many fields, and if it is below this upper limit, the shear viscosity at a high shear rate is low, which is suitable for various molding methods, particularly injection molding. is there.

In addition, calculation of the viscosity average molecular weight of the polycarbonate copolymer used as A-1 component of this invention is performed in the following way. First, the specific viscosity (η _SP ) calculated by the following formula was determined using an Ostwald viscometer from a solution in which 0.7 g of a polycarbonate copolymer was dissolved in 100 ml of methylene chloride at 20 ° C.,
Specific viscosity (η _SP ) = (t−t ⁰ ) / t ⁰
[T ⁰ is methylene chloride falling seconds, t is sample solution falling seconds]
From the obtained specific viscosity (η _SP ), the viscosity average molecular weight Mv is calculated by the following formula.
η _SP /c=[η]+0.45×[η] ^{2 c} (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

  The polycarbonate-polyorganosiloxane copolymer used as the A-1 component of the present invention has excellent flame retardancy while maintaining good shear fluidity, and good moldability and increased melt viscosity. It is characteristic in that it is compatible with the characteristics that are difficult to achieve, such as the anti-dripping effect. This surprising feature is that the polycarbonate-polyorganosiloxane copolymer has a high structural viscosity index, which is comparable in viscosity at high shear rates to low shear rates compared to polycarbonate homopolymers of equivalent viscosity average molecular weight. It is thought that this is due to a phenomenon in which the viscosity at is extremely high. The shear rate dependence of the melt viscosity varies greatly depending on the polymerization degree and content of the polydiorganosiloxane component constituting the polycarbonate-polyorganosiloxane copolymer, and further the method for producing the copolymer. It is extremely useful in that it has specified a range that achieves both the anti-drip effect due to the increase in melt viscosity and melt viscosity.

(A-2 component: polycarbonate resin)
The polycarbonate resin used as the component A-2 of the present invention is a polycarbonate resin composed of a carbonate constituent unit represented by the above general formula [1].
Examples of the dihydric phenol (I) for deriving the carbonate structural unit represented by the general formula [1] include 4,4′-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis ( 4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methyl) Phenyl) propane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxy-3,3′-biphenyl) propane, 2,2-bis ( 4-hydroxy-3-isopropylphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis (4- Droxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-) Hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 1,1-bis (3-cyclohexyl-4-hydroxyphenyl) cyclohexane, bis (4-hydroxyphenyl) diphenylmethane, 9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy) Phenyl) cyclopentane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydride Xy-3,3'-dimethyldiphenyl ether, 4,4'-sulfonyldiphenol, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, 2,2'-dimethyl-4,4 '-Sulfonyldiphenol, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 2,2'-diphenyl-4,4'- Sulfonyldiphenol, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-diphenyldiphenyl sulfide, 1,3-bis {2- (4-hydroxyphenyl) Propyl} benzene, 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene, 1,4-bis (4 Hydroxyphenyl) cyclohexane, 1,3-bis (4-hydroxyphenyl) cyclohexane, 4,8-bis (4-hydroxyphenyl) tricyclo [5.2.1.02,6] decane, 4,4 ′-(1 , 3-adamantanediyl) diphenol, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, and the like. Among them, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4′-sulfonyldiphenol, 2,2′-dimethyl- 4,4′-sulfonyldiphenol, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 1,3-bis {2- (4-hydroxyphenyl) propyl} benzene, and 1,4-bis {2- (4-hydroxyphenyl) propyl} benzene is preferred, especially 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis ( - hydroxyphenyl) cyclohexane (BPZ), 4,4'-sulfonyl diphenol, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene is preferred. Among them, 2,2-bis (4-hydroxyphenyl) propane having excellent strength and good durability is most preferable. Moreover, you may use these individually or in combination of 2 or more types.

Although the molecular weight of the polycarbonate resin as the component A-2 is not specified, if the viscosity average molecular weight is less than 10,000, the high temperature characteristics and the like are lowered, and if it exceeds 50,000, the moldability is lowered. The viscosity average molecular weight is preferably 10,000 to 50,000, more preferably 16,000 to 30,000, still more preferably 18,000 to 28,000, most preferably 19,000 to 26,000. It is. Further, two or more kinds of polycarbonate resins may be mixed. In this case, as long as the viscosity average molecular weight of the mixture obtained by mixing two or more kinds is in a preferable range, it is naturally possible to mix with a polycarbonate resin having a viscosity average molecular weight outside the above range.
The polycarbonate resin which is the component A-2 of the present invention is preferably substantially free of halogen atoms. The phrase “substantially free of halogen atoms” means that the molecule does not contain halogen-substituted dihydric phenols, etc., and also covers trace amounts of chlorinated solvents, carbonate precursors, etc. that remain in the polycarbonate resin production method. It is not a thing.

  A polycarbonate-polyorganosiloxane copolymer comprising a carbonate constituent unit represented by the general formula [1] and a carbonate constituent unit represented by the general formula [3], which is the resin component (component A) of the present invention ( (A-1 component) and the polycarbonate resin (A-2 component) which consists of a carbonate structural unit represented by the general formula [1] is 10/90 to 100/0, preferably 20/80 to 100. / 0, more preferably 50/50 to 100/0, still more preferably 70/30 to 100/0. When the content of the A-1 component is less than 10% by weight, impact characteristics and flame retardancy are deteriorated.

(B component: reinforcing filler)
(B-1 component: flat cross-section glass fiber)
The glass fiber used as B-1 component of this invention is a flat cross-section glass fiber. The flat cross-section glass fiber of the present invention has an average value of the major axis of the fiber cross section of 10 to 50 μm, preferably 15 to 40 μm, more preferably 20 to 35 μm, and an average ratio of major axis to minor axis (major axis / minor axis). A glass fiber having a value of 1.5 to 8.0, preferably 2.0 to 6.0, and more preferably 2.5 to 5.0. When using a flat cross-section glass fiber having an average ratio of the major axis to the minor axis within this range, the anisotropy and appearance are greatly improved compared to the case of using a non-circular cross-section fiber of less than 1.5. When used in combination with a flame retardant, flame retardancy can be greatly improved. Furthermore, when used together with the polycarbonate-polyorganosiloxane copolymer which is the component A-1 of the present invention, it has excellent mechanical strength compared to the combined use with other polycarbonate resins, and has a small anisotropy of molding shrinkage, and A resin composition having high impact characteristics can be provided. This improvement in flame retardancy is achieved by aligning the long side surface of the flat cross-section glass fiber parallel to the surface of the molded product on the surface of the molded product. It is considered that the blocking effect works more effectively than the circular cross-section fiber. In addition to the flat shape, the flat cross-sectional shape includes an elliptical shape, an eyebrow shape, a trefoil shape, or a similar non-circular cross-sectional shape. Of these, a flat shape is preferable from the viewpoint of improving mechanical strength and low anisotropy. The ratio of the average fiber length to the average fiber diameter (aspect ratio) of the flat cross-section glass fiber is preferably 2 to 120, more preferably 2.5 to 70, still more preferably 3 to 50, and the fiber length and the average fiber diameter. If the ratio is less than 2, the effect of improving the mechanical strength is small, and if the ratio between the fiber length and the average fiber diameter exceeds 120, the anisotropy increases and the appearance of the molded product may be deteriorated. . The average fiber diameter of such flat cross-section glass fibers refers to the number average fiber diameter when the flat cross-sectional shape is converted to a true circle of the same area. The average fiber length refers to the number average fiber length in the glass fiber reinforced resin composition of the present invention. The number-average fiber length is a value calculated by an image analyzer from an image obtained by observing the residue of the filler collected by processing such as high-temperature ashing of a molded product, dissolution with a solvent, and decomposition with a chemical, using an optical microscope. It is. Further, when calculating such a value, the fiber diameter is used as a guide and the length is less than that.

  Various glass compositions represented by A glass, C glass, E glass, etc. are applied to the glass composition of said flat cross-section glass fiber, and it is not specifically limited. Such a glass filler may contain components such as TiO2, SO3, and P2O5 as necessary. Among these, E glass (non-alkali glass) is more preferable. Such flat cross-section glass fibers are preferably subjected to a surface treatment with a known surface treatment agent such as a silane coupling agent, a titanate coupling agent, or an aluminate coupling agent from the viewpoint of improving mechanical strength. In addition, those that have been subjected to bundling treatment with olefin resin, styrene resin, acrylic resin, polyester resin, epoxy resin, urethane resin, etc. are preferable. From the viewpoint of mechanical strength, epoxy resin and urethane resin are preferred. Particularly preferred. The amount of the sizing agent attached to the flat cross-section glass fiber subjected to the bundling treatment is preferably 0.1 to 3 wt%, more preferably 0.2 to 2 wt% in 100 wt% of the flat cross-section glass fiber.

(B-2 component: Filler other than B-1 component)
As the filler other than the B-1 component used as the B-2 component in the composition of the present invention, a plate-like filler and / or a fibrous filler other than the B-1 component can be blended. As such a plate-like filler, glass flakes, mica, graphite and talc are preferably exemplified. As such a fibrous filler, glass fibers other than the B-1 component, glass milled fiber, wollastonite, and carbon-based filler are preferably exemplified. As such a fibrous filler, a filler whose surface is coated with a metal oxide such as titanium oxide, zinc oxide, cerium oxide, and silicon oxide can also be used. Examples of the carbon-based filler include carbon fiber, metal-coated carbon fiber, carbon milled fiber, vapor-grown carbon fiber, carbon nanotube, and carbon black. The carbon nanotube may be any one of a fiber diameter of 0.003 to 0.1 μm, a single layer, a double layer, and a multilayer, and a multilayer (so-called MWCNT) is preferable. Among these, carbon fiber and metal-coated carbon fiber are preferable in that they are excellent in mechanical strength and can impart good electrical conductivity.

  The fibrous filler may be surface-treated with various surface treatment agents in advance. Such surface treatment agents include silane coupling agents (including alkylalkoxysilanes and polyorganohydrogensiloxanes), higher fatty acid esters, acid compounds (for example, phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid anhydrides). Etc.) and various surface treatment agents such as wax. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.

  The reinforcing filler (component B) of the present invention is 1 to 60 parts by weight, preferably 3 to 60 parts by weight, in a total of 100 parts by weight of the resin component (component A) and the reinforcing filler (component B). Preferably it is 5-50 weight part. If the B component is less than 1 part by weight, the mechanical strength is insufficient, and if it exceeds 60 parts by weight, the molding fluidity, the appearance of the molded product, and the flame retardancy are deteriorated.

  The weight ratio of the flat cross-section glass fiber (B-1 component) which is the reinforcing filler (B component) of the present invention to the filler (B-2 component) other than the B-1 component is 5/95 to 100/0. , Preferably 40/60 to 100/0, more preferably 50/50 to 100/0. If the weight ratio of the flat cross-section glass fibers is 5% by weight or more, good bending elastic modulus and molding shrinkage anisotropy can be obtained.

(Other additives)
In the glass fiber reinforced resin composition of the present invention, various stabilizers, release agents and coloring materials can be used to stabilize the molecular weight and hue at the time of molding.

(I) Stabilizer Various known stabilizers can be blended in the glass fiber reinforced resin composition of the present invention. Examples of the stabilizer include phosphorus stabilizers, hindered phenol antioxidants, ultraviolet absorbers, and light stabilizers.

(I-1) Phosphorus stabilizer Examples of the phosphorous stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Among these, phosphorous acid, phosphoric acid, phosphonous acid, and phosphonic acid, triorganophosphate compounds, and acid phosphate compounds are particularly preferable. The organic group in the acid phosphate compound includes any of mono-substituted, di-substituted, and mixtures thereof. Any of the following exemplified compounds corresponding to the compound is similarly included.

  Triorganophosphate compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tridecyl phosphate, tridodecyl phosphate, trilauryl phosphate, tristearyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, diphenyl Examples include cresyl phosphate, diphenyl monoorthoxenyl phosphate, and tributoxyethyl phosphate. Among these, trialkyl phosphate is preferable. The carbon number of the trialkyl phosphate is preferably 1 to 22, more preferably 1 to 4. A particularly preferred trialkyl phosphate is trimethyl phosphate.

  Examples of the acid phosphate compound include methyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, behenyl acid phosphate Nonylphenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, and the like. Among these, long-chain dialkyl acid phosphates having 10 or more carbon atoms are effective for improving thermal stability, and the acid phosphate itself is preferable because of high stability.

  Examples of the phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl Monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butyl) Phenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl Taerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis ( 2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A penta Examples include erythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexylpentaerythritol diphosphite.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

  Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  Suitable phosphorus stabilizers are a triorganophosphate compound, an acid phosphate compound, and a phosphite compound represented by the following general formula (4). It is particularly preferable to add a triorganophosphate compound.

（式（４）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In Formula (4), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same as or different from each other.)

  As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and both can be used.

  Among the above formulas (4), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

(I-2) Hindered phenolic antioxidant As the hindered phenolic compound, various compounds that are usually blended in resins can be used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodie Renbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2 {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy Examples include -5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

  Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  It is preferable that either a phosphorus stabilizer or a hindered phenol antioxidant is blended. In particular, a phosphorus stabilizer is preferably blended, and a triorganophosphate compound is more blended. The blending amount of the phosphorus stabilizer and the hindered phenol antioxidant is preferably 0.005 to 1 part by weight, more preferably 0.01 to 0.3 part by weight, based on 100 parts by weight of component A, respectively. is there.

(I-3) Ultraviolet Absorber The glass fiber reinforced resin composition of the present invention can contain an ultraviolet absorber. Since the resin composition of the present invention also has a good hue, such a hue can be maintained for a long time even when used outdoors by blending an ultraviolet absorber.

  Specific examples of the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4 in the benzophenone series. -Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydro Shi-2-methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

  As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) and the like.

  Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

  Among them, benzotriazole and hydroxyphenyltriazine are preferable from the viewpoint of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable from the viewpoint of heat resistance and hue. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.02 to 2 parts by weight, still more preferably 0.03 to 1 part by weight, most preferably based on 100 parts by weight of component A. Is 0.05 to 0.5 parts by weight.

(I-4) Other Heat Stabilizers The glass fiber reinforced resin composition of the present invention may contain other heat stabilizers other than the phosphorus stabilizers and hindered phenol antioxidants. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. Examples of such other heat stabilizers include lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Is described in detail in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. In the present invention, such a premixed stabilizer can also be used. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight, based on 100 parts by weight of component A.

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. Such a stabilizer is particularly effective when the resin composition is applied to rotational molding. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, based on 100 parts by weight of component A.

(Ii) Mold Release Agent The glass fiber reinforced resin composition of the present invention is a fatty acid ester, paraffin wax in addition to a slidability imparting agent for the purpose of improving productivity during molding and improving dimensional accuracy of a molded product. In addition, a known release agent such as beeswax can be blended. Since the glass fiber reinforced resin composition of the present invention has good fluidity, a pressure propagation is good and a molded article with uniform strain can be obtained. On the other hand, since the molding shrinkage rate is low, the mold release resistance tends to increase, and as a result, the molded product tends to be deformed at the time of mold release. The compounding of the specific component solves such a problem without impairing the properties of the glass fiber reinforced resin composition.

Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, carbon number of this alcohol becomes like this. Preferably it is 3-32, More preferably, it is 5-30. On the other hand, the aliphatic carboxylic acid is preferably an aliphatic carboxylic acid having 3 to 32 carbon atoms, more preferably 10 to 30 carbon atoms. Of these, saturated aliphatic carboxylic acids are preferred. The fatty acid ester of the present invention is preferable in that all esters (full esters) are excellent in thermal stability at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less (can take substantially 0). The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value of the fatty acid ester is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.
The content of the release agent is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, and still more preferably 0.02 to 3 parts by weight based on 100 parts by weight of component A. is there.

(Iii) Dye / pigment The glass fiber reinforced resin composition of the present invention can further provide a molded product containing various dyes / pigments and exhibiting various design properties. Examples of dyes used in the present invention include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone dyes, Examples thereof include dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, aluminum powder is suitable. In addition, by blending a fluorescent brightening agent or other fluorescent dyes that emit light, a better design effect utilizing the luminescent color can be imparted.

Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.
The content of the dye / pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of component A.

(Iv) Compound having heat absorption ability The glass fiber reinforced resin composition of the present invention may contain a compound having heat absorption ability. Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, and metal boride-based near infrared rays such as lanthanum boride, cerium boride and tungsten boride. Preferred examples include various metal compounds having excellent near-infrared absorption ability such as an absorber, and carbon filler. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of the carbon filler include carbon black, graphite (including both natural and artificial) and fullerene, and carbon black and graphite are preferable. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near-infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, based on 100 parts by weight of component A, and 0.001 to 0.0. More preferred is 07 parts by weight. The content of the metal oxide near-infrared absorber, the metal boride-based near infrared absorber, and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin composition of the present invention. A range of ˜100 ppm is more preferable.

(V) Light diffusing agent The glass fiber reinforced resin composition of the present invention can be provided with a light diffusing effect by blending a light diffusing agent. Examples of such light diffusing agents include polymer fine particles, inorganic fine particles having a low refractive index such as calcium carbonate, and composites thereof. Such polymer fine particles are fine particles that are already known as light diffusing agents for polycarbonate resins. More preferably, acrylic crosslinked particles having a particle size of several μm, silicone crosslinked particles represented by polyorganosilsesquioxane, and the like are exemplified. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a column shape, and an indefinite shape. Such spheres need not be perfect spheres, but include deformed ones, and such columnar shapes include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size is. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 3 parts by weight, based on 100 parts by weight of component A. Two or more light diffusing agents can be used in combination.

(Vi) White pigment for light high reflection The glass fiber reinforced resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for light high reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight based on 100 parts by weight of the total component A. Two or more kinds of white pigments for high light reflection can be used in combination.

(Vii) Antistatic agent The glass fiber reinforced resin composition of the present invention may require antistatic performance, and in such a case, an antistatic agent is preferably included. Examples of the antistatic agent include (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less based on 100 parts by weight of component A, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and still more preferably 1 part. The range is from 5 to 3 parts by weight.

  Examples of the antistatic agent include: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less, preferably 0.001 to 0.3 parts by weight, more preferably based on 100 parts by weight of the total component A 0.005 to 0.2 part by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on 100 parts by weight of component A. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less based on 100 parts by weight of component A.

(Viii) Other additives The glass fiber reinforced resin composition of the present invention includes a thermoplastic resin other than the component A, a rubbery polymer, other flow modifiers, an antibacterial agent, a dispersant such as liquid paraffin, a photocatalyst. A system antifouling agent and a photochromic agent can be blended.

  As thermoplastic resins other than the component A, general-purpose plastics represented by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, polyamide resin, cyclic polyolefin resin, polyarylate resin (non-crystalline) And so-called super engineering plastics such as engineering plastics typified by polyarylate and liquid crystalline polyarylate), polyetheretherketone, polyetherimide, polysulfone, polyethersulfone, and polyphenylene sulfide. . Furthermore, thermoplastic elastomers such as olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers can also be used.

(Manufacture of glass fiber reinforced resin composition)
Arbitrary methods are employ | adopted in order to manufacture the glass fiber reinforced resin composition of this invention. For example, component A, component B and optionally other additives are thoroughly mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, extrusion mixer, etc., and then extruded granulated as necessary. There is a method of granulating such a premixed mixture using a vessel or a briquetting machine, then melt-kneading with a melt-kneader represented by a vent type twin screw extruder, and then pelletizing with a pelletizer.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method in which components other than the component A are premixed in advance and then mixed with the component A or directly supplied to the extruder.

  As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.
Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw extruder.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

  The glass fiber reinforced resin composition of the present invention can be obtained by injection molding the pellets produced as described above. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding. As a result, a molded article made of a glass fiber reinforced resin composition having excellent mechanical strength, small anisotropy of molding shrinkage, and good sliding properties is provided. That is, according to the present invention, (A) a polycarbonate-polyorganosiloxane copolymer (A) comprising a carbonate structural unit represented by the general formula [1] and a carbonate structural unit represented by the general formula [3] -1 component), and a polycarbonate resin (A-2 component) composed of the carbonate structural unit represented by the above general formula [1], the weight ratio of the A-1 component and the A-2 component (A-1 component / A component (A-2) is 10/90 to 100/0 resin component (component A) 40 to 99 parts by weight, and (B) the average value of the major axis of the fiber cross section is 10 to 50 μm, the ratio of major axis to minor axis ( It consists of a flat cross-section glass fiber (B-1 component) whose average value of major axis / minor axis is 1.5 to 8.0 and a filler (B-2 component) other than the B-1 component, and the B-1 component And B-2 component weight ratio (B-1 component / B- A component obtained by melt-molding a glass fiber reinforced resin composition containing 1 to 60 parts by weight of a reinforcing filler (component B) having a component (5/95 to 100/0), particularly a component used in communication equipment, is provided. The Furthermore, various surface treatments can be performed on the molded article made of the resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary polycarbonate resin is applicable. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation).

  According to the present invention, a molded article comprising the glass fiber reinforced resin composition of the present invention has excellent mechanical strength, a small anisotropy in molding shrinkage, and high flame retardancy. It is effective for various uses such as electrical / electronic parts, office equipment parts, communication equipment, etc., and its industrial effect is extremely large.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

  The present invention will be described more specifically with reference to examples and comparative examples. Unless otherwise specified, parts in the examples are parts by weight, and% is% by weight. The evaluation was performed according to the following method.

1. Evaluation of polycarbonate-polyorganosiloxane copolymer (1) Viscosity average molecular weight (Mv)
Using a Ostwald viscometer, a specific viscosity (η _SP ) calculated by the following formula was determined from a solution obtained by dissolving a polycarbonate-polydiorganosiloxane copolymer in 100 ml of methylene chloride at 20 ° C.,
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight Mv was calculated from the obtained specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ Mv ^0.83
c = 0.7

(2) Polydiorganosiloxane component content Using JNM-AL400 manufactured by JEOL Ltd., the ¹ H-NMR spectrum of the polycarbonate-polydiorganosiloxane copolymer was measured, and the integration of the peak derived from dihydric phenol (I) was performed. Ratio and the integral ratio of the peak derived from dihydroxyaryl-terminated polydiorganosiloxane (II) were calculated and calculated from the following formula.
Polyorganosiloxane component content (% by weight) = [A / (A + B)] × 100
A: [Integral ratio of ¹ H peak of dihydroxyaryl-terminated polydiorganosiloxane (II)] × [Molecular weight of polydiorganosiloxane moiety]
B: [Integral ratio of ¹ H peak of dihydric phenol (I)] × [Molecular weight of dihydric phenol]

2. Evaluation of Resin Composition (1) Flame Retardancy Pellets obtained from each composition of the examples were dried with a hot air dryer at 120 ° C. for 5 hours, and then injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. A test piece for flame retardancy evaluation was molded at a cylinder temperature of 320 ° C. and a mold temperature of 80 ° C. Using this test piece, a vertical combustion test of UL standard 94 was performed at a thickness of 2.0 mm, and the grade was evaluated. When the determination fails to satisfy any of the criteria of V-0, V-1, and V-2, “notV” is indicated.

(2) Impact characteristics The pellets obtained from each composition of the examples were dried in a hot air dryer at 120 ° C for 5 hours, dried, and then cylinder temperature was measured by an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. Test pieces for Charpy impact evaluation were molded at 320 ° C. and a mold temperature of 80 ° C. Using the test piece, a notched Charpy impact test was performed according to ISO179. The notched Charpy impact value needs to be 8 MPa or more.

(3) Anisotropy Pellets obtained from the compositions of the examples were dried in a hot air dryer at 120 ° C. for 5 hours, dried, and then cylindered by an injection molding machine [Toshiba Machine Co., Ltd. IS150EN-5Y]. At a temperature of 320 ° C. and a mold temperature of 80 ° C., a flat plate having a short side of 50 mm, a long side of 100 mm, and a thickness of 4 mm having a film gate having a thickness of 1.5 mm on one short side was formed. After conditioning at 23 ° C., 50% RH for 24 hours, the flow direction and the perpendicular direction of the flow of the flat plate were measured using a three-dimensional measuring machine (MICROPAK 550, manufactured by Mitoyo Seisakusho Co., Ltd.). The molding shrinkage ratio in the direction was determined, and the ratio of the molding shrinkage ratio in the direction perpendicular to the flow direction was determined as anisotropy. The anisotropy value is preferably closer to 1. The anisotropy needs to be 0.25 or more.

[Examples 1 to 18 and Comparative Examples 1 to 7]
After mixing the polycarbonate resin and various additives shown in Tables 1 to 3 in respective blending amounts in a blender, the mixture was melt-kneaded using a vent type twin screw extruder to obtain pellets. Various additives to be used were prepared in advance by premixing with a polycarbonate resin with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. The vent type twin-screw extruder used was TEX-30XSST (completely meshing, rotating in the same direction, two-thread screw) manufactured by Nippon Steel Works. The extrusion conditions are a discharge rate of 20 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 270 ° C. from the first supply port to the second supply port and 280 ° C. from the second supply port to the die part. did. The reinforcing filler was supplied from the second supply port using the side feeder of the extruder, and the remaining polycarbonate resin and additives were supplied to the extruder from the first supply port. The first supply port here is a supply port farthest from the die, and the second supply port is a supply port located between the die of the extruder and the first supply port. The obtained pellets were dried with a hot air circulation dryer at 120 ° C. for 5 hours, and then a test piece for evaluation was molded using an injection molding machine. The evaluation results are shown in Tables 1 to 3.

In addition, the detail of each used component is as follows.
(A component)
(A-1 component)
PC-1: Polycarbonate-polydiorganosiloxane copolymer produced in Production Example 1.
PC-2: Polycarbonate-polydiorganosiloxane copolymer produced in Production Example 2.
PC-3: Polycarbonate-polydiorganosiloxane copolymer produced in Production Example 3.
PC-4: Polycarbonate-polydiorganosiloxane copolymer produced in Production Example 4.
PC-5: Polycarbonate-polydiorganosiloxane copolymer produced in Production Example 5.

Production Example 1: Method for producing PC-1 In a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 21915 parts of ion-exchanged water and 3675 parts of a 48.5% aqueous sodium hydroxide solution are placed and expressed by the above formula [1]. After dissolving 3880 parts of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) and 7.6 parts of hydrosulfite as the dihydroxy compound (I) constituting the carbonate structural unit, 14565 parts of methylene chloride ( 14 mol) was added to 1 mol of the dihydroxy compound (I), and 1900 parts of phosgene was blown in for 60 minutes at 22-30 ° C. with stirring. Next, a solution obtained by dissolving 1131 parts of 48.5% aqueous sodium hydroxide and 108 parts of p-tert-butylphenol in 800 parts of methylene chloride is added, and the carbonate constituent unit represented by the above formula [3] is formed with stirring. As a dihydroxyaryl-terminated polydiorganosiloxane (II) having an average number of dimethylsiloxane units of 40, a solution obtained by dissolving 204 parts of a polydiorganosiloxane compound represented by the following formula [5] in 1600 parts of methylene chloride, Polydiorganosiloxane (II) was added at a rate of 0.0008 mol / min per 1 mol of dihydric phenol (I) to obtain an emulsified state, and then vigorously stirred again. Under such stirring, 4.3 parts of triethylamine was added while the reaction solution was at 26 ° C., and stirring was continued for 1 hour at a temperature of 26 to 31 ° C. to complete the reaction. After completion of the reaction, the organic phase is separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid, washed with water, and poured into a kneader filled with warm water when the conductivity of the aqueous phase is almost the same as that of ion-exchanged water. Then, methylene chloride was evaporated while stirring to obtain a polycarbonate-polydiorganosiloxane copolymer powder. After dehydration, it was dried at 120 ° C. for 12 hours using a hot air circulating dryer.

Production Example 2: PC-2 Production Method A polycarbonate-polydiorganosiloxane copolymer powder was produced in the same manner as in Example 1 except that 430 parts of a dihydroxyaryl-terminated polydiorganosiloxane having a dimethylsiloxane unit repeating number of 40 was used. Got.

Production Example 3: Production method of PC-3 A polycarbonate-polydiorganosiloxane copolymer powder was produced in the same manner as in Example 1 except that 204 parts of dihydroxyaryl-terminated polydiorganosiloxane having a dimethylsiloxane unit repeating number of 90 was used. Got.

Production Example 4: Production method of PC-4 Powder of polycarbonate-polydiorganosiloxane copolymerization was carried out in the same manner as in Example 1 except that 204 parts of dihydroxyaryl-terminated polydiorganosiloxane having a dimethylsiloxane unit repeating number of 150 was used. Got.

Production Example 5: Production method of PC-5 A polycarbonate-polydiorganosiloxane copolymer powder was prepared in the same manner as in Example 1 except that 204 parts of a dihydroxyaryl-terminated polydiorganosiloxane having 400 repeating dimethylsiloxane units was used. Got.
Table 4 shows the viscosity average molecular weight and polydiorganosiloxane component content of each polycarbonate-polydiorganosiloxane copolymer obtained by the above production method.

(A-2 component)
PC-6: PC: Linear polycarbonate resin powder having a viscosity average molecular weight of 19700 (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WX)
(B component)
(B-1 component)
B-1: Flat section chopped glass fiber (manufactured by Nitto Boseki Co., Ltd .: CSG 3PA-830, major axis 27 μm, minor axis 4 μm, cut length 3 mm, epoxy sizing agent)
(B-2 component)
B-2-1: Circular cross-section chopped glass fiber (manufactured by Nippon Electric Glass Co., Ltd .; ECS-03T-511, diameter 13 μm, cut length 3 mm, aminosilane treatment and urethane sizing agent)
B-2-2: Glass milled fiber (PFE-301 manufactured by Nitto Boseki Co., Ltd., fiber diameter 9 μm, average fiber length 30 μm, silane coupling agent treatment)
(Other ingredients)
F114P: perfluorobutanesulfonic acid potassium salt (manufactured by Dainippon Ink and Chemicals, Inc., MegaFuck F-114P)
PTFE: Polytetrafluoroethylene having fibril forming ability (Daikin Industries, Ltd.)
"Polyflon MPA FA500" (trade name))
TMP: Trimethyl phosphate (TMP manufactured by Daihachi Chemical Industry Co., Ltd.)
CB: 30 parts by weight of carbon black (carbon black MA-10 manufactured by Mitsubishi Chemical Corporation)
0) 3 parts by weight of white mineral oil (Crystol N35 manufactured by ExxonMobil)
2), 0.2 parts by weight of a montanic acid ester wax (Ricorb WE-1 powder manufactured by Clariant Japan Co., Ltd.), and 66.8 parts by weight of a bisphenol A type polycarbonate resin (CM-1000 manufactured by Teijin Chemicals Ltd.) Carbon black master pellets produced by melt-mixing 100 parts by weight of 4 components with a viscosity average molecular weight of 16,000) using a twin screw extruder

Claims (7)

(A) A polycarbonate-polyorganosiloxane copolymer (component A-1) composed of a carbonate structural unit represented by the following general formula [1] and a carbonate structural unit represented by the following general formula [3], and the following general It consists of polycarbonate resin (A-2 component) which consists of a carbonate structural unit represented by Formula [1], and the weight ratio (A-1 component / A-2 component) of A-1 component and A-2 component is 10 /. 40 to 99 parts by weight of resin component (component A) of 90 to 100/0, and (B) the average value of the major axis of the fiber cross section is 10 to 50 μm, the average value of the ratio of major axis to minor axis (major axis / minor axis) It consists of a flat cross-section glass fiber (B-1 component) and 1.5 to 8.0 fillers (B-2 component) other than the B-1 component, and the weight ratio of the B-1 component to the B-2 component (B-1 component / B-2 component) is 5/95 to 1 0/0 at a reinforcing filler (B component) glass fiber reinforced resin composition containing 1 to 60 parts by weight.

[In General Formula [1], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 6 to 6 carbon atoms. 20 cycloalkyl groups, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, aryl groups having 3 to 14 carbon atoms, aryloxy groups having 3 to 14 carbon atoms, carbon atoms Represents a group selected from the group consisting of an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, a nitro group, an aldehyde group, a cyano group, and a carboxyl group. E and f are each an integer of 1 to 4, and W is a single bond or at least one group selected from the group consisting of groups represented by the following general formula [2]. . ]

[In the above general formula [2], R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, carbon Represents a group selected from the group consisting of an aryl group having 3 to 14 atoms and an aralkyl group having 7 to 20 carbon atoms, and R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, or a carbon atom having 1 to 18 carbon atoms. Alkyl groups, alkoxy groups having 1 to 10 carbon atoms, cycloalkyl groups having 6 to 20 carbon atoms, cycloalkoxy groups having 6 to 20 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and 3 carbon atoms. -14 aryl group, aryloxy group having 6 to 10 carbon atoms, aralkyl group having 7 to 20 carbon atoms, aralkyloxy group having 7 to 20 carbon atoms, nitro group, aldehyde group, cyano group and It represents a group selected from the group consisting of carboxyl groups, and when there are a plurality thereof, they may be the same or different, g is an integer of 1 to 10, and h is an integer of 4 to 7. ]

[In the above general formula [3], R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a substitution having 6 to 12 carbon atoms. Or an unsubstituted aryl group, R ⁹ and R ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and p is a natural number Q is 0 or a natural number, and p + q is a natural number less than 300. X is a divalent aliphatic group having 2 to 8 carbon atoms. ]   The A-1 component is a polycarbonate-polyorganosiloxane copolymer having a polydiorganosiloxane component content of 0.1 to 40% by weight based on the total weight of the polycarbonate-polydiorganosiloxane copolymer. Glass fiber reinforced resin composition.   The glass fiber reinforced resin composition according to claim 1 or 2, wherein the B-2 component is a plate-like filler and / or a fibrous filler other than the B-1 component.   The B-2 component plate-like filler is at least one filler selected from the group consisting of glass flakes, mica, graphite and talc, and the fibrous filler is a glass fiber other than the B component, glass milled fiber, wax The glass fiber reinforced resin composition according to claim 3, wherein the glass fiber reinforced resin composition is at least one filler selected from the group consisting of rustonite and carbon-based fillers.   The glass fiber reinforced resin composition according to any one of claims 1 to 4, wherein an average value of a ratio of major axis to minor axis (major axis / minor axis) of component B-1 is 2.5 to 5.0.   The resin molded product formed by shape | molding the glass fiber reinforced resin composition in any one of Claims 1-5.   The component used for the communication apparatus formed by shape | molding the glass fiber reinforced resin composition in any one of Claims 1-5.