JP2000119499A - Aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a compsn. having a remained catalyst activity index of less than a specific value and being excellent in the rigidity, wet heat fatigue resistance, and surface impact resistance, by blending an aromatic polycarbonate resin which is obtained by reacting a divalent phenol with a carbonate precursor in a fusion process, with a fibrous filler of a specific amt. SOLUTION: 100 pts.wt. of an aromatic polycarbonate resin having a remained catalyst activity index of 2% or less is blended with 5-200 pts.wt. of a fibrous filler. The remained catalyst activity index is defined as a change of molten viscosity per minute calculated from the formula, the molten viscosity being measured with a revolution-type rheometer at a definite temp. of the resin melting and by revolving a sample to a determined direction along with a fixed angular speed. The carbonate precursor used is a carbonate ester, a haloformate, etc., pref. a biphenyl carbonate. The fibrous filler preferable above all is a glass fiber, wollastonite, a carbon fiber, and an electrically conductive metallic fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polycarbonate resin composition containing a fibrous filler excellent in wet heat fatigue resistance and surface impact resistance. More specifically, while making use of the inherent properties of the aromatic polycarbonate resin, and improving the properties such as rigidity by adding a fibrous filler,
The present invention relates to an aromatic polycarbonate resin composition containing a fibrous filler excellent in wet heat fatigue and surface impact properties.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are widely used because they have excellent mechanical properties such as impact resistance, and also have excellent heat resistance and transparency. As a method for producing such an aromatic polycarbonate resin, a method of directly reacting phosgene with a dihydric phenol such as bisphenol A (interfacial polymerization method) or a method of melting a dihydric phenol such as bisphenol and a diallyl carbonate such as diphenyl carbonate is used. There is known a method of performing a transesterification reaction in a state and performing polymerization (hereinafter, sometimes referred to as a melting method). Among such production methods, the method of transesterifying a dihydric phenol with diallyl carbonate has no problem in using a halogen compound such as phosgene or methylene chloride, as compared with the production by an interfacial polymerization method, and is more environmentally friendly. This is a promising technology because it has the advantages of low load and inexpensive manufacturing.

An aromatic polycarbonate resin composition using an aromatic polycarbonate resin and a glass filler is described in Japanese Patent No. 2683662. This aromatic polycarbonate resin is an aromatic polycarbonate resin produced substantially by a melting method. It is disclosed that this composition has better Izod impact resistance than the solution-processed aromatic polycarbonate resin composition. However, the melt-processed aromatic polycarbonate resin used in such a composition has not been subjected to deactivation treatment of the catalyst, and has a drawback of poor wet heat fatigue properties and surface impact properties.

An aromatic polycarbonate resin composition containing an aromatic polycarbonate resin containing an aromatic polycarbonate resin or another thermoplastic resin, an inorganic reinforcing filler and a phosphonium salt is disclosed in Japanese Patent Application Laid-Open No. 10-602.
No. 48 publication. The role of the phosphonium salt of the aromatic polycarbonate resin composition is to suppress a problem that occurs when an inorganic reinforcing filler is added to the polycarbonate resin, that is, to suppress a decrease in molecular weight, poor appearance, and the like. Polycarbonate resin of polymerization method is used.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to make use of the inherent properties of an aromatic polycarbonate resin, to improve properties such as rigidity by adding a fibrous filler, and to improve wet heat fatigue resistance and surface area. An object of the present invention is to provide an aromatic polycarbonate resin composition containing a fibrous filler excellent in impact properties. As a result of intensive studies on such a resin composition, the present inventors have completed the present invention by deactivating a polymerization catalyst remaining in an aromatic polycarbonate resin obtained by a melting method and using this aromatic polycarbonate resin.

[0006]

The present invention relates to an aromatic polycarbonate resin (A) having a residual catalytic activity index of 2% or less and obtained by reacting a dihydric phenol with a carbonate precursor by a melting method. The present invention relates to an aromatic polycarbonate resin composition comprising 100 parts by weight and (B) 5 to 200 parts by weight of a fibrous filler.

The aromatic polycarbonate resin used in the present invention is generally obtained by reacting a dihydric phenol with a carbonate precursor by a melting method. Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane , 1,1-bis (4-hydroxyphenyl)
-1-phenylmethane, bis {(4-hydroxy-3,
5-dimethyl) phenyl} methane, 1,1-bis (4-
(Hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, bis (4-hydroxyphenyl) ) -1-Naphthylmethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2- (4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, , 2-
Bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis} (3,5-dibromo-4
-Hydroxy) phenyl} propane, 2,2-bis {(3,5-dichloro-4-hydroxy) phenyl} propane, 2,2-bis {(3-bromo-4-hydroxy) phenyl} propane, 2,2 -Bis {(3-chloro-4-hydroxy) phenyl} propane, 4-bromoresorcinol, 2,2-bis} (3-isopropyl-4
-Hydroxy) phenyl {propane, 2,2-bis {(3-phenyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-ethyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-n-propyl-4-hydroxy) phenyl} propane, 2,2-bis {(3-sec-butyl-4-hydroxy) phenyl}
Propane, 2,2-bis} (3-tert-butyl-4
-Hydroxy) phenyl {propane, 2,2-bis {(3-cyclohexyl-4-hydroxy) phenyl}
Propane, 2,2-bis {(3-methoxy-4-hydroxy) phenyl} propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-dibromo-2,2-bis (4- (Hydroxyphenyl) ethylene, 1,1-dichloro-2,2-bis {(3-phenoxy-4-hydroxy) phenyl} ethylene, ethylene glycol bis (4-hydroxyphenyl) ether,
2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3
-Dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) isobutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2- Bis (4-hydroxyphenyl) -4-methylpentane, 3,3-bis (4
-Hydroxyphenyl) pentane, 1,1-bis (4-
(Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl)-
3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 9,9-
Bis (4-hydroxyphenyl) fluorene, 9,9-
Bis {(4-hydroxy-3-methyl) phenyl} fluorene, α, α′-bis (4-hydroxyphenyl)-
o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene,
α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-
Dihydroxydiphenylsulfone, bis {(3,5-dimethyl-4-hydroxy) phenyl} sulfone, 4,
4'-dihydroxydiphenylsulfoxide, 4,4 '
-Dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester and the like, and these can be used alone or in combination of two or more.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(3,5-dibromo-4-hydroxy) phenyl} propane, ethylene glycol Screw (4
-Hydroxyphenyl) ether, 2,2-bis (4-
Hydroxyphenyl) hexafluoropropane, 2,2
-Bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1
-Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfone, bis {(3,5-dimethyl-4-hydroxy) phenyl} sulfone, 4,4'-dihydroxy Homopolymers or copolymers obtained from at least one bisphenol selected from the group consisting of diphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfide, and 4,4'-dihydroxydiphenyl ketone are preferred, and bisphenol A is particularly preferred. Homopolymers are preferably used.

As the carbonate precursor, carbonate ester or haloformate is used. Specifically, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc. may be mentioned. However, the present invention is not limited to these. Preferably, diphenyl carbonate or dihaloformate of dihydric phenol is used, and more preferably, diphenyl carbonate is used. These carbonates may be used alone or in combination of two or more.

In producing the polycarbonate resin by reacting the dihydric phenol with the carbonate precursor by a melting method, a catalyst, a terminal stopper, an antioxidant for the dihydric phenol, and the like may be used as necessary. Is also good. Further, even if the polycarbonate resin is a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound,
A polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid may be used,
A mixture of two or more of the obtained polycarbonate resins may be used.

[0011] Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 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- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, or trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their acid chlorides, 2- (4-hydroxyphenyl) -2-
(3′-phenoxycarbonyl-4′-hydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2
-(3'-carboxy-4'-hydroxyphenyl) propane and the like, and among them, 1,1,1-tris (4-
Hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane are preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

The reaction by the melting method is usually a transesterification reaction between a dihydric phenol and a carbonate ester,
The method is carried out by a method in which a dihydric phenol and a carbonate ester are mixed while heating in the presence of an inert gas to distill off the produced alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C.
In the latter half of the reaction, the pressure of the system is reduced to about 10 to 0.1 Torr to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

In the melting method, a polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include a catalyst comprising (i) an alkali metal compound and / or (ii) a nitrogen-containing basic compound. To be condensed.

The alkali metal compound used as a catalyst includes, for example, hydroxides, hydrocarbons, carbonates, acetates, nitrates, nitrites, sulfites, cyanates, thiocyanates, stearic acids of alkali metals. Salts, borohydride salts, benzoates, hydrogen phosphates, bisphenols, salts of phenols and the like can be mentioned.

As specific examples, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate,
Potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, sodium nitrate, potassium nitrate, lithium nitrate, sodium nitrite, potassium nitrite, lithium nitrite, sodium sulfite, potassium sulfite, lithium sulfite, sodium cyanate, potassium cyanate , Lithium cyanate, sodium thiocyanate,
Potassium thiocyanate, lithium thiocyanate, sodium stearate, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride, potassium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, benzoic acid Lithium, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt, dipotassium salt, dilithium salt of bisphenol A, sodium salt, potassium salt, lithium salt of phenol and the like can be mentioned.

The alkali metal compound as a catalyst can be used in a range of 10 ^-8 to 10 ^-5 mol per mol of dihydric phenol. If the amount is outside the above range, the properties of the obtained polycarbonate are adversely affected, and the transesterification reaction does not sufficiently proceed to obtain a high-molecular-weight polycarbonate, which is not preferable.

Examples of the nitrogen-containing basic compound as a catalyst include, for example, tetramethylammonium hydroxide (Me ₄ NOH), tetraethylammonium hydroxide (Et ₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH), benzyl Ammonium hydroxides having alkyl, aryl, alkylaryl groups, such as trimethylammonium hydroxide (φ-CH ₂ (Me) ₃ NOH) and hexadecyltrimethylammonium hydroxide, triethylamine, tributylamine, dimethylbenzylamine, hexadecyl Tertiary amines such as dimethylamine, or tetramethylammonium borohydride (Me ₄ NB
H _4), tetrabutylammonium borohydride (Bu ₄ NBH _4), tetrabutylammonium tetraphenylborate (Bu ₄ NBPh _4), tetramethylammonium tetraphenylborate (Me ₄ NBPh _4), and the like basic salts such as Can be. Among them, tetramethylammonium hydroxide (Me ₄ N
OH), tetraethylammonium hydroxide (Et
₄ NOH), tetrabutylammonium hydroxide (Bu ₄ NOH) are preferable, and tetramethylammonium hydroxide (Me ₄ NOH) is preferred.

The nitrogen-containing basic compound is preferably used in such a ratio that the amount of ammonium nitrogen atoms in the nitrogen-containing basic compound is 1 × 10 ⁻⁵ to 1 × 10 ⁻³ equivalent per mole of dihydric phenol. A more desirable ratio is 2 ×
The ratio is 10 ^{-5 to} 7 × 10 ^-4 equivalent. A particularly desirable ratio is a ratio that is 5 × 10 ^{−5 to} 5 × 10 ⁻⁴ equivalents with respect to the same standard. In the present invention, if desired, alkoxides of alkali metals and alkaline earth metals, organic acid salts of alkali metals and alkaline earth metals, zinc compounds,
Normal esterification of boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds, zirconium compounds, etc. And a catalyst used in a transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, per 1 mol of the dihydric phenol used as the raw material. Selected by range.

In the polymerization reaction, to reduce the number of phenolic terminal groups, for example, phenol, pt-butylphenol, pt-butylphenylphenyl carbonate,
pt-butylphenyl carbonate, p-cumylphenol, p-cumylphenylphenyl carbonate, p
-Cumylphenyl carbonate, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate, bis (phenylphenyl) carbonate, chlorophenylphenylcarbonate, bromophenylphenylcarbonate,
Nitrophenylphenyl carbonate, diphenyl carbonate, methoxycarbonylphenylphenyl carbonate, 2,2,4-trimethyl-4- (4-hydroxyphenyl) chroman 2,4,4-trimethyl-2-
It is preferred to add compounds such as (4-hydroxyphenyl) chroman and ethoxycarbonylphenylphenyl carbonate. Of these, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred, and 2-methoxycarbonylphenylphenyl carbonate is particularly preferred.

In the present invention, it is preferable to block the terminal of the aromatic polycarbonate resin using a terminal blocking agent. Also, the hydroxyl group terminal of the aromatic polycarbonate resin before the addition of the terminal blocking agent is at least 20 mol%, preferably at least 30 mol%, more preferably at least 40 mol%, based on all terminals.
It is preferable to control it to at least mol%. By doing so, a specific terminal group can be introduced at a high ratio, and the effect of modifying the aromatic polycarbonate resin can be enhanced. Usually, it is advantageous to use a terminal blocking agent for the aromatic polycarbonate resin in which the proportion of hydroxyl group terminals in the aromatic polycarbonate resin is within the range of 30 to 95 mol% of the total terminals. The terminal ratio of hydroxyl groups of the aromatic polycarbonate resin before the addition of the terminal blocking agent can be controlled by the charging ratio of dihydric phenol and diphenyl carbonate as raw materials. Here, the number of moles of terminal hydroxyl groups in a fixed amount of the aromatic polycarbonate resin can be determined by ¹ H-NMR by a conventional method.

The hydroxyl terminal of the aromatic polycarbonate resin of the present invention is 0 to 40 mol%, preferably 0 to 18 mol%, more preferably 0 to 9 mol%, and most preferably 0 to 7 mol% with respect to all terminals. % Is preferably controlled.
Here, 0 mol% means that it cannot be detected when measured by ¹ H-NMR method. When the hydroxyl group terminal is in such a range, wet heat fatigue resistance and surface impact resistance are further improved.

In the present invention, it is preferable to use a deactivator for neutralizing the activity of the catalyst in the aromatic polycarbonate resin. Specific examples of this deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonic acid, ethylbenzenebenzenesulfonic acid, butylbenzenesulfonic acid, octylbenzenesulfonic acid, phenylbenzenebenzenesulfonic acid, p-toluenesulfonic acid. Methyl acid, p-
Sulfonates such as ethyl toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; and trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene, and methyl acrylate. Sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonate, 2-phenyl-2-butyl dodecylbenzenesulfonate, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, benzene Tetrabutylphosphonium sulfonic acid salt, Tetraethylphosphonium dodecylbenzenesulfonic acid salt, Tetrabutylphosphonium dodecylbenzenesulfonic acid salt, Tetrahexyl dodecylbenzenesulfonic acid salt Phosphonium salt, tetraoctylphosphonium dodecylbenzenesulfonate, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl dimethyl ammonium methyl Sulfate,
Tetramethyl ammonium hexyl sulfate, decyl trimethyl ammonium hexadecyl sulfate,
Examples thereof include, but are not limited to, compounds such as tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, and tetramethylammonium dodecylbenzyl sulfate. Two or more of these compounds can be used in combination.

Among the deactivators, phosphonium or ammonium salt type deactivators are themselves particularly stable even at 200 ° C. or higher. When the deactivator is added to the aromatic polycarbonate resin, the polycondensation reaction catalyst can be immediately neutralized to obtain the desired aromatic polycarbonate resin. That is, the deactivator is preferably used in an amount of 0.01 to 500 p with respect to the polycarbonate formed after the polymerization sealing reaction.
pm, more preferably 0.01 to 300 pp
m, particularly preferably 0.01 to 100 ppm.

The deactivator is used in an amount of 0.5 to 5 per mole of the polycondensation reaction catalyst.
It is preferably used in a proportion of 0 mol. The method for adding the deactivator to the aromatic polycarbonate resin after terminal blocking is not particularly limited. For example, they may be added while the aromatic polycarbonate resin as a reaction product is in a molten state, or may be added after the aromatic polycarbonate resin is pelletized once and then remelted. In the former, the aromatic polycarbonate resin, which is a reaction product in a reactor or an extruder in a molten state obtained after the end-blocking reaction is completed, is added while the aromatic polycarbonate resin is in a molten state. After forming, may be pelletized through an extruder, or, while the aromatic polycarbonate resin obtained by polymerization blocking reaction is pelletized from the reactor through the extruder, adding a quenching agent By kneading, an aromatic polycarbonate resin can be obtained.

In the melt-polymerized aromatic polycarbonate resin of the present invention, a polymerization catalyst is used to accelerate the reaction, and thus the polymerization catalyst often remains after the polymerization reaction. If the remaining catalyst is left as it is after the completion of the polymerization reaction, the aromatic polycarbonate resin may be decomposed or re-reacted due to the catalytic activity of the polymerization catalyst. Further, in the aromatic polycarbonate resin composition of the aromatic polycarbonate resin having the residual catalytic activity and the fibrous filler, the effect is increased, and new problems such as a decrease in surface impact property occur.

In the present invention, it is necessary to suppress such residual catalyst activity. It is measured in the following manner using the residual catalyst activity index as an index for suppressing the residual catalyst activity. As a measuring device, a rotating rheometer that can measure the melt viscosity range of the sample to be measured is used, and the resin to be measured is melted in a sufficient nitrogen flow so that the sample is not oxidized by external oxygen. Under a condition of temperature, the sample is rotated at a constant direction and a constant angular velocity, and a change in melt viscosity at that time is observed. The jig of the viscoelasticity measuring device used for measuring the sample is a conical disk-shaped jig so that the distortion of the entire sample is constant, that is, the shear rate is constant. That is, the change in melt viscosity per minute calculated by the following equation (i) was defined as the residual catalyst activity index.

[0027]

(Equation 1)

This residual catalyst activity index is 2% or less, preferably 1% or less, more preferably 0.5% or less, and most preferably 0.2% or less. If the residual catalyst activity index exceeds this range, the aromatic polycarbonate resin changes with time, which is not preferable.

The molecular weight of the aromatic polycarbonate resin is as follows:
The viscosity average molecular weight (M) is preferably from 12,000 to 30,000, more preferably from 14,000 to 27,000, and particularly preferably from 15,000 to 25,000. An aromatic polycarbonate resin having such a viscosity average molecular weight is preferable because sufficient strength can be obtained as a composition, the melt flowability during molding is good, and molding distortion does not occur.
The viscosity average molecular weight in the present invention is 100 mL of methylene chloride.
The specific viscosity (ηsp) obtained from a solution of 0.7 g of a polycarbonate resin dissolved at 20 ° C. was inserted into the following equation. ηsp / c = [η] + 0.45 × [η] ² c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 ^-4 M ^0.83 c = 0.7

The fibrous filler used in the aromatic polycarbonate resin composition of the present invention includes glass fiber, glass milled fiber, wollastonite, carbon fiber, metallic conductive fiber, potassium whisker titanate, and aluminum whisker borate. Whiskers and the like. Among them, glass fiber, wollastonite, carbon fiber and metal conductive fiber are preferable, and glass fiber, wollastonite and carbon fiber are most preferable.

The glass fiber used in the present invention does not particularly limit the glass composition such as A glass, C glass, and E glass. In some cases, TiO ₂ , Zr ₂ O, BeO, C
It may contain components such as eO ₂ , SO ₃ and P ₂ O ₅ . However, E glass (alkali-free glass) is more preferable because it does not adversely affect the aromatic polycarbonate resin. The same applies to the glass milled fiber described below for such a glass composition.
The glass fiber of the present invention is obtained by quenching molten glass while stretching it by various methods to form a predetermined fiber. The quenching and stretching conditions in such a case are not particularly limited. In addition to the general round shape,
You may use the thing of various irregular-shaped cross-sections represented by what made the perfect circular fiber overlap in parallel. Further, a glass fiber mixed with a perfect circular shape and an irregular cross-sectional shape may be used. Such glass fibers have an average fiber diameter of 1 to 25 μm,
Preferably it is 5 to 17 μm. If glass fibers having an average fiber diameter of less than 1 μm are used, molding processability is impaired, and if glass fibers having an average fiber diameter of more than 25 μm are used, the appearance is impaired and the reinforcing effect is not sufficient.

In order to impart conductivity or the like to the glass fiber, a metal coat can be applied to the surface of the fiber. The diameter of the metal-coated glass fiber is particularly preferably from 6 to 20 μm. The metal-coated glass fiber is obtained by coating a glass fiber with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a known plating method, vapor deposition method, or the like. Such a metal is preferably one or more metals selected from nickel, copper and cobalt from the viewpoints of conductivity, corrosion resistance, productivity and economy.

These fibers are currently known epoxy type,
Focusing treatment can be performed with various compounds such as urethane-based and acrylic-based compounds, and those that have been surface-treated with a silane coupling agent described later or the like are preferable. The average fiber length of these fibers in a molded product is about 200 to 400 μm.

The glass milled fiber used in the present invention has an L / D ≦ 10, and is obtained by cutting a glass fiber roving or chopped strand by a ball mill or the like to a predetermined length. It can be preferably used when the appearance of a molded article obtained from the composition of the present invention is to be improved. Here, L represents the length of the milled fiber in the fiber axis direction, and D represents the fiber diameter in the cross-sectional direction. The same glass fibers as those described above can be used as the glass fibers. These powders are preferably surface-treated with a silane coupling agent or the like, similarly to glass fibers. The glass milled fiber has an average fiber diameter of 6 to 23 μm and an average fiber length of 0.02 to 0.1.
mm is preferred.

In the present invention, wollastonite is a natural white mineral having acicular crystals in which the fibrous inorganic filler mainly composed of calcium silicate has a chemical formula of CaSiO _3.
And usually contains about 50% by weight of SiO ₂ , about 47% by weight of CaO, Fe ₂ O ₃ , Al ₂ O _3, etc., and has a specific gravity of about 2.9. As the wollastonite used in the present invention, those having a particle size distribution of 75% or more in 3 μm or more and 5% or less in 10 μm or more and having an aspect ratio L / D of 3 or more, particularly preferably L / D of 8 or more are preferable. . When the particle size distribution is 3 μm or more and 75% or more, the reinforcing effect is sufficient, and the rigidity tends to be higher. When the thickness is 10 μm or more and 5% or less, while having good impact strength, the surface appearance of the obtained molded article tends to be more favorable. In particular, when the aspect ratio is 8 or more, the reinforcing effect is sufficient, and higher rigidity can be obtained. However, considering the working environment, those having an aspect ratio of 50 or less are more preferable. The wollastonite may be subjected to a surface treatment with a normal surface treatment agent, for example, a coupling agent such as a silane coupling agent or a titanate coupling agent described below.

The carbon fiber used in the present invention is not particularly limited, and may be various known carbon fibers, for example, carbonaceous fibers and graphite fibers produced using polyacrylonitrile, pitch, rayon, lignin, hydrocarbon gas and the like. In particular, a polyacrylonitrile-based carbon fiber having excellent fiber strength is preferable. The carbon fiber can be oxidized on the fiber surface by a currently known method represented by ozone, plasma, nitric acid, electrolysis and the like, and is preferably used to increase the adhesion to the resin component. The carbon fibers are usually in the form of chopped strands, roving strands, milled fibers and the like.

In order to impart conductivity or the like to the carbon fiber, a metal coat can be applied to the fiber surface. The diameter of the metal-coated carbon fiber is particularly preferably from 6 to 20 μm. The metal-coated carbon fiber is obtained by coating a carbon fiber with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a known plating method or vapor deposition method.
Such a metal is preferably one or more metals selected from nickel, copper, and cobalt from the viewpoints of conductivity, corrosion resistance, productivity, and economic efficiency, and particularly preferably nickel-coated carbon fibers.

These carbon fibers are made of epoxy resin,
Those bundled with various sizing agents such as urethane resin and acrylic resin can be suitably used, and preferably, epoxy resin and / or urethane resin are used.

The metal-based conductive fibers used in the present invention need not be particularly limited, and include metal fibers and metal-coated fibers, such as metal fibers such as stainless steel fibers, aluminum fibers, copper fibers, and brass fibers. Can be These may be used in combination of two or more. Metal fiber diameter is 4-8
0 μm is preferred, and 6 to 60 μm is particularly preferred. Such conductive fibers may be surface-treated with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, or the like. In addition, the convergence treatment may be performed with an olefin resin, a styrene resin, a polyester resin, an epoxy resin, a urethane resin, or the like. These fibrous fillers may be used alone or in combination of two or more.

The fibrous filler preferably has been surface-treated with a silane coupling agent or the like. By this surface treatment, decomposition of the aromatic polycarbonate resin is suppressed, and the adhesiveness is further improved, so that the wet heat fatigue property and the surface impact property, which are the objects of the present invention, can be improved. The silane coupling agent referred to here is the following formula

[0041]

Embedded image

[Where Y is a group having reactivity or affinity with the resin matrix such as an amino group, an epoxy group, a carboxylic acid group, a vinyl group, a mercapto group, and a halogen atom;
^1, R ^2, R ³ represents respectively a single bond or an alkylene group having 1 to 7 carbon atoms, in the alkylene molecular chain, an amide bond, an ester bond, may be an ether bond or an imino bond is interposed, X ¹ , X ² and X ³ each represent an alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom], and specifically include vinyltrichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane Γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-
Examples include aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and the like.

The mixing ratio of the fibrous filler in the present invention is 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the aromatic polycarbonate resin. If the amount is less than 5 parts by weight, the rigidity of the composition is insufficient, and if it exceeds 200 parts by weight, extrusion of the obtained composition is difficult and not practical.

The aromatic polycarbonate resin composition of the present invention may be blended with a heat stabilizer in order to prevent a decrease in molecular weight and deterioration of hue during molding. Such heat stabilizers include phosphorous acid, phosphoric acid, phosphonous acid,
Examples thereof include phosphonic acid and esters thereof. Specific examples include triphenyl phosphite, tris (nonylphenyl) phosphite, and tris (2,4-di-tert).
-Butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl Phosphite, monooctyldiphenyl phosphite, bis (2,6-di-ter
t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite,
Bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate , Diphenyl monoorthoxenyl phosphate, dibutyl phosphate,
Dioctyl phosphate, diisopropyl phosphate, tetrakis (4,4'-biphenylenediphosphosphinate) (2,4-di-tert-butylphenyl), dimethyl benzenephosphonate, diethyl benzenephosphonate, dipropyl benzenephosphonate and the like can be mentioned. Of these, tris nonylphenyl phosphite, trimethyl phosphate, tris (2,4-di-tert-butylphenyl) phosphite and dimethyl benzenephosphonate are preferably used. These heat stabilizers may be used alone or in combination of two or more. The amount of the heat stabilizer is 100 parts of the aromatic polycarbonate resin.
0.0001 to 1 part by weight with respect to parts by weight is preferable,
0.0005 to 0.5 part by weight is more preferable,
More preferred is 1 to 0.1 part by weight.

The aromatic polycarbonate resin composition of the present invention may contain a generally known antioxidant for the purpose of preventing oxidation. Examples of such antioxidants include pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3
-Laurylthiopropionate), glycerol-3-
Stearyl thiopropionate, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-
4-hydroxyphenyl) propionate], 1,6-
Hexanediol-bis [3- (3,5-di-tert)
-Butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis [3- (3,
5-di-tert-butyl-4-hydroxyphenyl)
Propionate], octadecyl-3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene Screw (3,5
-Di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-) (Hydroxybenzyl) isocyanurate, tetrakis (2,4-di-tert) 4,4′-biphenylenediphosphosphinate
-Butylphenyl), 3,9-bis {1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl}
-2,4,8,10-tetraoxaspiro (5,5) undecane and the like. The compounding amount of these antioxidants is preferably 0.0001 to 0.05 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin.

A release agent may be added to the aromatic polycarbonate resin composition of the present invention in a range that does not impair the object of the present invention in order to further improve the releasability from the mold during melt molding. It is possible. Examples of the release agent include olefin wax, silicone oil, organopolysiloxane, higher fatty acid ester of monohydric or polyhydric alcohol, paraffin wax, beeswax and the like. The compounding amount of the release agent is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin as the component A.

As the olefin wax, use of a polyethylene wax and / or a 1-alkene polymer is particularly preferred, and a very good releasing effect can be obtained. As the polyethylene wax, those generally widely known at present can be used, and examples thereof include those obtained by polymerizing ethylene under high temperature and high pressure, those obtained by thermally decomposing polyethylene, and those obtained by separating and purifying a low molecular weight component from a polyethylene polymer. The molecular weight and the degree of branching are not particularly limited, but the number average molecular weight is preferably 1,000 or more. Further, a polyethylene wax modified with maleic acid and / or maleic anhydride may be used. As the 1-alkene polymer, 1-alkene polymer having 5 to 40 carbon atoms is used.
A polymer obtained by polymerizing an alkene can be used, and a type obtained by simultaneously copolymerizing maleic acid and / or maleic anhydride can also be used. The type in which maleic acid and / or maleic anhydride is copolymerized at the same time has a feature of improving the slidability and the impact strength. The number average molecular weight of the 1-alkene polymer is preferably 1,000 or more. In such a case, good releasability can be obtained while maintaining strength.

As the higher fatty acid ester, monohydric or polyhydric alcohols having 1 to 20 carbon atoms and 10 to 10 carbon atoms can be used.
It is preferably a partial ester or a total ester with 30 saturated fatty acids. Examples of such partial or total esters of monohydric or polyhydric alcohols and saturated fatty acids include stearic acid monoglyceride, stearic acid diglyceride,
Stearic acid triglyceride, stearic acid monosorbitate, behenic acid monoglyceride, pentaerythritol monostearate, pentaerythritol tetrastearate, pentaerythritol tetraperargonate, propylene glycol monostearate, stearyl stearate, palmityl palmitate, butyl stearate , Methyl laurate, isopropyl palmitate, biphenyl biphenate, sorbitan monostearate, 2-ethylhexyl stearate and the like,
Of these, stearic acid monoglyceride, stearic acid triglyceride, and pentaerythritol tetrastearate are preferably used.

A light stabilizer can be added to the aromatic polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. Such light stabilizers include, for example, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 2- (3-tert-
Butyl-5-methyl-2-hydroxyphenyl) -5
Chlorobenzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl)
Phenyl] -2H-benzotriazole, 2,2′-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2′-p-phenylenebis (1,3-benzoxazin-4-one) and the like. Can be The amount of the light stabilizer is preferably 0.01 to 2 parts by weight based on 100 parts by weight of the aromatic polycarbonate resin.

An antistatic agent can be added to the aromatic polycarbonate resin composition of the present invention as long as the object of the present invention is not impaired. As such an antistatic agent,
Examples include polyetheresteramide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, monoglyceride maleic anhydride, diglyceride maleic anhydride, and the like.

The aromatic polycarbonate resin composition of the present invention may contain a flame retardant in an amount that does not impair the object of the present invention. Examples of the flame retardant include a halogenated bisphenol A polycarbonate type flame retardant, an organic salt type flame retardant, an aromatic phosphate ester type flame retardant, and a halogenated aromatic phosphate ester type flame retardant. The above can be blended. Specifically, the polycarbonate type flame retardant of halogenated bisphenol A is a polycarbonate type flame retardant of tetrachlorobisphenol A, tetrachlorobisphenol A and bisphenol A
And a polycarbonate-type flame retardant of tetrabromobisphenol A, a polycarbonate-type flame retardant of tetrabromobisphenol A and bisphenol A, and the like. Specifically, organic salt-based flame retardants include dipotassium diphenylsulfone-3,3'-disulfonate, potassium diphenylsulfon-3-sulfonate, sodium 2,4,5-trichlorobenzenesulfonate, 2,4,5-trisulfonate. Potassium chlorobenzenesulfonate, bis (2,6-dibromo-4-cumylphenyl)
Potassium phosphate, sodium bis (4-cumylphenyl) phosphate, potassium bis (p-toluenesulfone) imide, potassium bis (diphenylphosphate) imide, potassium bis (2,4,6-tribromophenyl) phosphate,
Potassium bis (2,4-dibromophenyl) phosphate, potassium bis (4-bromophenyl) phosphate, potassium diphenylphosphate, sodium diphenylphosphate, potassium perfluorobutanesulfonate, sodium or potassium lauryl sulfate, sodium hexadecyl sulfate Or potassium and the like. Specifically, halogenated aromatic phosphate ester type flame retardants include tris (2,4,6-tribromophenyl) phosphate, tris (2,4-dibromophenyl) phosphate, tris (4-bromophenyl) phosphate and the like. is there. Specifically, aromatic phosphate ester-based flame retardants include triphenyl phosphate, tris (2,6-xylyl) phosphate, tetrakis (2,
6-xylyl) resorcinol diphosphate, tetrakis (2,6-xylyl) hydroquinone diphosphate, tetrakis (2,6-xylyl) -4,4′-biphenol diphosphate, tetraphenylresorcin diphosphate, tetraphenylhydroquinone diphosphate,
Tetraphenyl-4,4'-biphenol diphosphate, aromatic polyphosphate whose aromatic ring source is resorcinol and phenol and does not contain phenolic OH group, aromatic whose aromatic ring source is resorcinol and phenol and contains phenolic OH group Polyphosphate, aromatic polyphosphate whose aromatic ring source is hydroquinone and phenol and does not contain phenolic OH group, similar aromatic polyphosphate containing phenolic OH group, ("aromatic polyphosphate" shown below is phenolic (Aromatic polyphosphate containing an aromatic polyphosphate containing an acidic OH group and aromatic polyphosphate not containing an aromatic OH group) An aromatic polyphosphate in which the aromatic ring source is bisphenol A and phenol, and an aromatic ring source in the form of tetrabromobisphenol A
And phenol as an aromatic polyphosphate, as aromatic ring sources as resorcinol and 2,6-xylenol, as aromatic polyphosphate as hydroquinone and 2,
Aromatic polyphosphate which is 6-xylenol, aromatic polyphosphate whose aromatic ring source is bisphenol A and 2,6-xylenol, aromatic polyphosphate whose aromatic ring source is tetrabromobisphenol A and 2,6-xylenol, etc. It is.

Among these flame retardants, polycarbonate-type flame retardants of halogenated bisphenol A, polycarbonate-type flame retardants of tetrabromobisphenol A,
A copolymerized polycarbonate of tetrabromobisphenol A and bisphenol A is preferable, and a polycarbonate type flame retardant of tetrabromobisphenol A is more preferable. As organic salt-based flame retardants, diphenyl sulfone-3,
3'-dipotassium disulfonic acid, diphenyl sulfone-
Potassium 3-sulfonate and sodium 2,4,5-trichlorobenzenesulfonate are preferred. As aromatic phosphate ester flame retardants, triphenyl phosphate,
Tricresyl phosphate, cresyl diphenyl phosphate, resulcinol bis (dixylenyl phosphate), bis (2,3 dibromopropyl) phosphate,
Tris (2,3 dibromopropyl) phosphate is preferred. Among these, triphenyl phosphate, which is an aromatic phosphate ester flame retardant that does not destroy the ozone layer,
Most preferred are tricresyl phosphate and resulcinol bis (dixylenyl phosphate).

The aromatic polycarbonate resin composition of the present invention may contain other resins and elastomers in a range that does not impair the object of the present invention, that is, in an extremely small proportion.

Examples of such other resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyamide resins, polyimide resins, and the like.
Polyetherimide resin, polyurethane resin, polyphenylene ether resin, polyphenylene sulfide resin,
Polysulfone resin, polyolefin resin such as polyethylene and polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, epoxy resin, etc. Is mentioned.

Examples of the elastomer include, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, silicone rubber, polyester elastomer, polyamide elastomer, and MBS (methacrylic acid) which is a core-shell type elastomer. Methyl / styrene / butadiene) rubber, MAS (methyl methacrylate / acrylonitrile / styrene) rubber and the like.

For producing the aromatic polycarbonate resin composition of the present invention, any method is employed. For example, a method of mixing with a tumbler, a V-type blender, a super mixer, a Nauta mixer, a Banbury mixer, a kneading roll, an extruder or the like is appropriately used. The aromatic polycarbonate resin composition thus obtained may be pelletized as it is or once by a melt extruder, and then formed into a molded article by a generally known method such as an injection molding method, an extrusion molding method, or a compression molding method. it can. In order to increase the dispersion of the components in the aromatic polycarbonate resin and obtain stable release properties and various physical properties, it is preferable to use a twin-screw extruder in melt extrusion. Further, the fibrous filler of the present invention is a method of directly charging the extruder hopper mouth or the middle of the extruder,
Either a method of previously mixing with an aromatic polycarbonate resin, a method of previously mixing with a part of aromatic polycarbonate resin to prepare and put in a master, or a method of putting the master in the middle of an extruder can be adopted.

The thus obtained aromatic polycarbonate resin composition of the present invention can be used for housings and chassis of OA equipment such as personal computers, word processors, fax machines, copiers and printers, CD-ROM trays, chassis, turntables and pickup chassis. OA for various gears
Internal parts, TV, video, electric washing machine, electric dryer,
Housing and parts for household appliances such as vacuum cleaners, electric tools such as electric saws and electric drills, telescope barrels, microscope barrels, camera bodies, camera housings, optical equipment parts such as camera barrels, door handles, pillars , Bumpers, instrument panels, and other automotive parts.

Among them, the aromatic polycarbonate resin composition comprising the aromatic polycarbonate resin and glass fiber of the present invention is suitable for personal computers, word processors, fax machines, copiers, printers and the like in terms of strength, rigidity and good dimensional accuracy.
Housing and chassis of A equipment, OA internal parts such as CD-ROM tray, chassis, turntable, etc., housing and parts of home appliance products such as TV, video, electric washing machine, electric dryer, vacuum cleaner, electric drill It is useful for optical tools such as electric tools, telescope barrels, microscope barrels, camera bodies, camera housings, camera barrels, etc.

Further, the aromatic polycarbonate resin composition of the present invention comprising an aromatic polycarbonate resin and carbon fiber has a high rigidity, a light weight (low specific gravity) and a high dimensional accuracy as compared with a glass fiber. It is useful for housings and chassis of OA equipment such as fax machines, copiers, and printers, optical equipment parts such as camera bodies, camera barrels, and internal parts of laser beam printers.

Further, the aromatic polycarbonate resin composition comprising the aromatic polycarbonate resin and wollastonite of the present invention is suitable for personal computers in terms of moderate rigidity, dimensional stability, and surface appearance (smoothness) as compared with glass fibers. ,word processor,
Housing for OA equipment such as fax machines, copiers, printers, OA internal parts such as CD-ROM trays, chassis, turntables, etc., and household appliances such as televisions, videos, electric washing machines, electric dryers, and vacuum cleaners. Housing and parts, telescope barrel, microscope barrel, camera body,
It is useful for optical equipment parts such as camera housings and camera barrels, and automotive parts such as door handles, pillars, bumpers, and instrument panels.

[0061]

EXAMPLES Examples will be further described below with reference to examples. "Parts" or "%" in the examples indicates parts by weight or% by weight,
The symbols for the evaluation items and each component in the composition mean the following.

(I) Evaluation Items (1) Index of residual catalyst activity The amount of residual catalyst activity was measured as follows. The sample was dried at 120 ° C. for 4 hours under reduced pressure before measurement, and used for measurement. RDA-I manufactured by Rheometrics Co., Ltd.
Using a type I viscoelasticity measuring instrument, a conical disk-shaped jig having a diameter of 25 mm was mounted, and the measurement temperature was set to 270 ° C. in a nitrogen stream satisfying the appropriate conditions of the sample during measurement. The measurement temperature was set by measuring the temperature in the oven. Then set the dried sample for measurement,
After the sample was allowed to stand at a sufficiently high measurement temperature, the measurement was started by rotating the sample at an angular velocity of 1 rad / sec. The measurement was continued for 30 minutes, and a change in melt viscosity was observed during the measurement. From these measurements, the melt viscosities at 5 minutes and 30 minutes after the start of rotation were determined, and the values were calculated from the following formula (i) to express the change in melt viscosity per minute as the residual catalyst activity index.

[0063]

(Equation 2)

(2) Terminal hydroxyl group concentration 0.02 g of a sample was dissolved in 0.4 ml of chloroform, and subjected to 1H-NMR (EX-27 manufactured by JEOL Ltd.) at 20 ° C.
The terminal hydroxyl group and the terminal phenyl group were measured using 0), and the terminal hydroxyl group concentration was measured by the following formula (ii). Terminal hydroxyl group concentration (mol%) = (number of terminal hydroxyl groups / number of all terminals) × 100 (ii)

(3) Wet Heat Fatigue Using the so-called C-type measurement sample shown in FIG.
80 ° C, 90% RH atmosphere, sine wave, frequency 1H
Under the conditions of z and a maximum load of 5 kg, the following fatigue tester [Shimadzu Servo Pulser EHF- manufactured by Shimadzu Corporation]
EC5], the number of times until the measurement sample was broken was measured.

(4) Surface Impact Resistance Using a measurement square plate having a length of 15 cm, a width of 15 cm, and a thickness of 2 mm, measurement was performed under the following conditions in accordance with the test method of JIS K-7221. Weight: spherical with a diameter of about 63 mm and weight of 1 kg Test temperature: 40 ° C. The height at which the weight was dropped was increased at 5 cm intervals, and the weight (cm) at which cracks occurred in the test piece was measured by dropping the weight onto the square plate for measurement.

(5) Rigidity The flexural modulus was measured according to ASTM D790.

(6) Tensile Strength According to ASTM D638, a tensile test was performed to measure the tensile strength at break.

(7) Notched Impact Value According to ASTM D256, a 3.2 mm thick test piece was used to strike a weight from the notch side to measure the impact value.

(8) Specific gravity The specific gravity was measured according to JIS K7112.

(II) Symbol of each component in the composition (a) Aromatic polycarbonate resin EX-PC [Reference Example 1] Production of aromatic polycarbonate resin of the present invention 2 in a reactor equipped with a stirrer and a distillation column. , 2-bis (4-
228 parts (about 1 mol) of (hydroxyphenyl) propane,
220 parts (about 1.03 mol) of diphenyl carbonate (manufactured by Bayer) and sodium hydroxide 0.0 as a catalyst.
00024 parts (about 6 × 10 ^-7 mol / bisphenol A1
Mol) and tetramethylammonium hydroxide 0.0
073 parts (about 8 × 10 ⁻⁵ mol / 1 mol of bisphenol A) were charged and purged with nitrogen. This mixture was heated to 200 ° C. and dissolved with stirring. Next, most of the phenol was distilled off in 1 hour while heating at a reduced pressure of 30 Torr, the temperature was further raised to 270 ° C., and the polymerization reaction was performed for 2 hours at a reduced pressure of 1 Torr. 3.1 parts of carbonylphenylphenyl carbonate were added. Then 270 ° C,
The terminal blocking reaction was performed at 1 Torr or less for 5 minutes. Next, in the molten state, 0.0035 parts of dodecylbenzenesulfonic acid tetrabutylphosphonium salt (about 6 × 10 ⁻⁶ mol / bisphenol A1 mol) was added as a catalyst neutralizing agent, and the reaction was continued at 270 ° C. and 10 Torr or less. Thus, an aromatic polycarbonate resin having a viscosity average molecular weight of 23,300, a terminal hydroxyl group concentration of 5 mol%, and a residual catalytic activity index of 0.01% was obtained. This aromatic polycarbonate resin was sent to an extruder by a gear pump. 0.003% by weight of trisnonylphenyl phosphite in the middle of the extruder,
Trimethyl phosphate was added at 0.05% by weight to obtain aromatic polycarbonate resin pellets.

CEX-PC Reference Example 2 Production of aromatic polycarbonate resin for comparison Except that 2-methoxycarbonylphenylphenyl carbonate was used as a terminal stopper and tetrabutylphosphonium dodecylbenzenesulfonate was used as a catalyst deactivator. Produced an aromatic polycarbonate resin under the same conditions as in Reference Example 1. The aromatic polycarbonate resin had a viscosity average molecular weight of 23,000, a terminal hydroxyl group concentration of 52 mol%, and a residual catalytic activity index of 2.5.

(B) Filler Glass fiber: chopped strand ECS-03T-
511; urethane convergence treatment, manufactured by Nippon Electric Glass Co., Ltd., fiber diameter 13 μm. Carbon fiber: Vesfite HTA-C6-U; manufactured by Toho Rayon Co., Ltd .; Wollastonite: Psycatek NN-4; manufactured by Tomoe Kogyo Co., Ltd., average particle size D = 4 μm, particle system distribution of 3 μm or more is 82.5%, and particle system distribution of 10 μm or more is 0.7.
%, Aspect ratio L / D = 20

[Examples 1 to 3, Comparative Examples 1 and 2] The aromatic polycarbonate resin obtained above and the components shown in Table 1 were uniformly mixed using a tumbler.
Twin screw extruder with mmφ vent (KTX manufactured by Kobe Steel Ltd.)
According to −30), the cylinder temperature is 270 ° C. and 10 mmH
The pellets were dried at 120 ° C. for 5 hours while degassing at a vacuum of 5 g, and the cylinder temperature was 330 ° C. using an injection molding machine (SG150U type manufactured by Sumitomo Heavy Industries, Ltd.). A molded plate for measurement was prepared at a mold temperature of 100 ° C.

As is clear from Table 1, the aromatic polycarbonate resin composition comprising the aromatic polycarbonate resin having the residual catalytic activity index and the glass fiber, which is an example of the present invention, is the aromatic resin having the residual catalytic activity of the comparative example. Compared to those using an aromatic polycarbonate resin, the resin composition containing glass fibers has excellent properties originally expected, and furthermore has particularly excellent wet heat fatigue properties and surface impact properties.

[0076]

[Table 1]

[Examples 4 to 6, Comparative Examples 3 and 4] The aromatic polycarbonate resin obtained above and the components shown in Table 2 were uniformly mixed using a tumbler. A molded plate for measurement was prepared in the same manner. As is clear from Table 2, the aromatic polycarbonate resin composition comprising an aromatic polycarbonate resin having a residual catalytic activity index and carbon fiber, which is an example of the present invention, is an aromatic polycarbonate resin having a residual catalytic activity of a comparative example. Compared with the resin composition using the resin composition, the resin composition containing carbon fibers has excellent properties originally expected, and furthermore has particularly excellent wet heat fatigue resistance and surface impact resistance.

[0078]

[Table 2]

[Examples 7 to 9 and Comparative Examples 5 and 6] The aromatic polycarbonate resin obtained above and the components shown in Table 3 were uniformly mixed using a tumbler. A molded plate for measurement was prepared in the same manner. As is clear from Table 3, the aromatic polycarbonate resin composition comprising the aromatic polycarbonate resin having the residual catalytic activity index and wollastonite, which is an example of the present invention, is the aromatic polycarbonate resin having the residual catalytic activity of the comparative example. Compared to the resin-based resin composition, the resin composition containing wollastonite has excellent properties originally expected, and further has particularly excellent wet heat fatigue resistance and surface impact resistance.

[0080]

[Table 3]

[0081]

According to the aromatic polycarbonate resin composition of the present invention, the properties such as rigidity are improved by adding the fibrous filler to the properties inherent in the aromatic polycarbonate resin, and the wet heat fatigue resistance and the like are improved. It is possible to provide an aromatic polycarbonate resin composition containing a fibrous filler having excellent surface impact properties.

[Brief description of the drawings]

FIG. 1 is a front view of a so-called C-type sample used for evaluating wet heat fatigue resistance. The thickness of the sample is 3 mm. The test is performed by passing a jig of a test machine through the hole indicated by reference numeral 6 and applying a predetermined load in the vertical direction indicated by reference numeral 7.

[Explanation of symbols]

1 Center of C-shaped double circle 2 Radius of inner circle of double circle (20 mm) 3 Radius of outer circle of double circle (30 mm) 4 Center angle (60 °) indicating position of jig mounting hole 5 Gap between sample end faces (13 mm) 6 Jig mounting hole (circle 4 mm in diameter, located at center of sample width) 7 Direction of load imposed on sample during fatigue test

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J002 CG011 CG021 CG031 CG041 DA016 DA076 DA096 DC006 DE186 DJ006 DK006 DL006 FA046 FA066 FB076 FB086 FB096 FB106 FB136 FB146 FB156 FB166 FB276 FD016 FD060 FD070 00G01 010130 AGC BB04A BB05A BB10A BB12A BB13A BC05A BC06A BD09A BE04 BF14A BF20 BG04X BG08X BG08Y BH02 DB07 DB11 DB13 HC01 HC03 HC04A HC05A JC353 JC363 JC633 KE05 KH08

Claims (5)

[Claims] 1. An aromatic polycarbonate resin (A) having a residual catalytic activity index of 2% or less and obtained by reacting a dihydric phenol with a carbonate precursor by a melting method.
An aromatic polycarbonate resin composition comprising 00 parts by weight and (B) 5 to 200 parts by weight of a fibrous filler. 2. The aromatic polycarbonate resin composition according to claim 1, wherein the carbonate precursor is diphenyl carbonate. 3. The aromatic polycarbonate resin composition according to claim 1, wherein the fibrous filler is glass fiber. 4. The aromatic polycarbonate resin composition according to claim 1, wherein the fibrous filler is a carbon fiber. 5. The aromatic polycarbonate resin composition according to claim 1, wherein the fibrous filler is wollastonite.