JP2003147189A - Flame-retardant aromatic polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant aromatic polycarbonate resin composition which is excellent in tracking resistance and antistatic properties and exhibits an excellent drip prevention property when burned. SOLUTION: This flame-retardant aromatic polycarbonate resin composition is prepared by compounding 100 pts.wt. polycarbonate resin (A) with 0.1-10 pts.wt. specific silicone compound (B) containing Si-H bonds. A molded item obtained therefrom is also provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polycarbonate resin composition. More specifically, it relates to a flame-retardant aromatic polycarbonate resin composition having excellent tracking resistance and antistatic property, and further having excellent anti-drip property of resin during combustion.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are formed into various molded products by a simple and highly productive processing method such as injection molding and are used in a wide variety of industrial fields. Also,
A flame-retardant aromatic polycarbonate-based resin composition obtained by adding a halogen-based compound or a phosphorus-based compound to an aromatic polycarbonate-based resin is used for a relay case, a capacitor case, and the like, which are strongly demanded to be flame-retardant. In this application, in addition to the flame retardancy of the resin composition, the resin composition which is originally an insulating material has tracking resistance of the resin composition itself in order to prevent ignition or short circuit of an electronic circuit due to tracking,
The antistatic property of the resin composition itself is emphasized in order to prevent dust and the adhesion of dust, which are the base points of tracking. However, on the other hand, flame-retardant aromatic polycarbonate resin compositions that replace these flame retardants have been developed and are being used in the products listed above. The purpose of changing the flame retardant is to suppress the generation of corrosive gas during molding or to improve the recyclability of the product.

Examples of the flame retardant instead of the above flame retardants include silicone compounds. A flame-retardant resin composition prepared by blending a silicone compound with an aromatic polycarbonate resin has been vigorously studied in recent years and various proposals have been made.

For example, a method of blending an alkali (earth) metal salt of perfluoroalkanesulfonic acid with a polycarbonate resin and an organic siloxane having an alkoxy group, a vinyl group and a phenyl group (JP-A-6-306265), and a polycarbonate resin A method of blending an alkali metal salt or an alkaline earth metal salt of perfluoroalkanesulfonic acid with an organopolysiloxane containing an organooxysilyl group bonded to a silicon atom via a divalent hydrocarbon group (JP-A-6-336547). Gazette) is proposed.

Further, a method of blending a specific petroleum heavy oil or pitch with a silicone compound as a resin component (JP-A-9-169914), and a non-silicone resin having an aromatic ring are represented by the formula R ₂ SiO _1.0. Unit and RS
It has a unit of iO _1.5 and a weight average molecular weight of 1
A method of blending a silicone resin in the range of 10,000 to 270,000 (Japanese Patent Laid-Open No. 10-139964)
Have been proposed.

However, the above-mentioned proposed polycarbonate resin composition is not sufficient in tracking resistance and antistatic property. For example, the above-mentioned proposed polycarbonate resin composition has the same antistatic property as the aromatic polycarbonate resin, and dust and dirt adhere to it, so that the tracking resistance after long-term use deteriorates. Also,
The flame retardancy of the above proposed polycarbonate resin composition was not sufficient. For example, in the case of thin wall, drip may occur and the V-0 rank of UL standard 94 cannot be achieved,
And so on.

On the other hand, Japanese Patent Publication No. 60-38419 discloses concretely a resin composition comprising an aromatic polycarbonate resin, an organic alkali metal salt, and poly (methylhydrogen siloxane). However, such a resin composition causes poor dispersion such as peeling on the surface of the molded product, and the dispersion of tracking resistance becomes extremely large.
It wasn't enough.

[0008]

An object of the present invention is to provide an aromatic polycarbonate resin composition.
More specifically, it has excellent tracking resistance and antistatic properties,
Another object of the present invention is to provide a flame-retardant aromatic polycarbonate resin composition having excellent drip-preventing property of resin during combustion.

The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, aromatic polycarbonate resin,
It was found that by combining a specific amount of a specific silicone compound, an aromatic polycarbonate resin composition having excellent target tracking resistance and antistatic property, and further excellent anti-dripping property of resin during combustion can be obtained. Has reached the present invention.

[0010]

The present invention has an acid value of -0.
A silicone compound containing a Si—H group and an aromatic group in a molecule, relative to 100 parts by weight of an aromatic polycarbonate resin (A) having a concentration of 5 to 5.0 (mg equivalent acid / 10 kg PC), wherein Si— The amount containing H groups (Si-H amount) is 0.1 to
1.2 mol / 100 g, the ratio (aromatic group amount) containing the aromatic group represented by the following general formula (1) is 10 to 70% by weight,

[0011]

[Chemical 5]

(In the formula (1), X is independently OH
Shows a monovalent organic residue having 1 to 20 carbon atoms. n is 0
Represents an integer of 5. Further, in the formula (1), when n is 2 or more, different types of X can be taken. )

0.1 to 10 parts by weight of at least one silicone compound (B) selected from the silicone compounds having a volatilization amount of not more than 18% by a heat loss method at 105 ° C./3 hours are blended. And a flame-retardant aromatic polycarbonate resin composition.

The aromatic polycarbonate resin used as the component (A) of the present invention is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, or a carbonate. It is obtained by polymerizing a prepolymer by a solid-state transesterification method, or by a ring-opening polymerization method of a cyclic carbonate compound.

Typical examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl} methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3-methyl)
Phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl}
Propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 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, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 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′-dihydroxydiphenyl sulfone, 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-
Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, which may 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 (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane and a homopolymer obtained from at least one bisphenol selected from the group consisting of α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene or Copolymers are preferred, especially homopolymers of bisphenol A and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane with bisphenol A, 2,2-bis {(4-hydroxy- A copolymer with 3-methyl) phenyl} propane or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene is preferably used.

As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples thereof include phosgene, diphenyl carbonate or dihaloformate of dihydric phenol.

When a polycarbonate resin is produced by reacting the above dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, if necessary, a catalyst, an end terminating agent, and oxidation of the dihydric phenol are used. You may use an inhibitor etc. Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic difunctional carboxylic acid, It may also be a mixture of two or more of the obtained polycarbonate resins.

Examples of trifunctional or higher polyfunctional aromatic compounds include phloroglucin, phloroglucide, or 4,6-
Dimethyl-2,4,6-tris (4-hydrodiphenyl) 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) )
Examples thereof include ketones, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides thereof, among which 1,1,1-tris. (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferable, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferable.

When a polyfunctional compound which produces such a branched polycarbonate resin is contained, such a proportion is 0.001 to 1 mol%, preferably 0.005 to 0.5 mol%, and particularly preferably, the total amount of the aromatic polycarbonate. 0.01
Is about 0.3 mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction, and the amount of the branched structure is 0.001 to 1 mol%, preferably 0.005 to 5 mol% in the total amount of the aromatic polycarbonate.
0.5 mol%, particularly preferably 0.01 to 0.3 mol%
Are preferred. The ratio is ¹ H
-It can be calculated by NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, which is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used.
As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. It is also possible to use a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound for accelerating the reaction. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably 10 minutes to 5 hours, and the pH during the reaction is preferably 9 or more.

In addition, in such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such an end terminator. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, such monofunctional phenols typically being phenol or lower alkyl substituted phenols,
The monofunctional phenols represented by the following general formula (5) can be shown.

[0023]

[Chemical 6]

(In the formula, A is a hydrogen atom or 1 to 9 carbon atoms.
Is a linear or branched alkyl group or a phenyl group-substituted alkyl group, and r is an integer of 1 to 5, preferably 1 to 3. )

Specific examples of the above monofunctional phenols include phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

As other monofunctional phenols,
Phenols or benzoic acid chlorides having a long-chain alkyl group or aliphatic polyester group as a substituent, or long-chain alkylcarboxylic acid chlorides can also be shown. Among these, phenols having a long-chain alkyl group represented by the following general formulas (6) and (7) as a substituent are preferably used.

[0027]

[Chemical 7]

[0028]

[Chemical 8]

(In the formula, X is -R-O-, -R-CO-O.
-Or-RO-CO-, wherein R represents a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 5, and n represents an integer of 10 to 50. Show. )

The substituted phenols of the general formula (6) are preferably those in which n is 10 to 30, particularly 10 to 26. Specific examples thereof include decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, Examples thereof include octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol.

As the substituted phenols of the general formula (7), compounds in which X is —R—CO—O— and R is a single bond are suitable, and n is 10 to 30, particularly 10 to 26.
Are preferred, and specific examples thereof include decyl hydroxybenzoate, dodecyl hydroxybenzoate,
Mention may be made of tetradecyl hydroxybenzoate, hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. Moreover, you may use a terminal terminator individually or in mixture of 2 or more types.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, which is produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. It is carried out by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system was set at 1.33 × 10 ³ -1.
The alcohol or phenol produced by reducing the pressure to about 3.3 Pa is easily distilled. Reaction time is usually 1 to 4
It's about time.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specific examples include diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like, with diphenyl carbonate being preferred.

A polymerization catalyst may be used to accelerate the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium salt and potassium salt of dihydric phenol, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals and alkaline earth metals , Organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds manganese Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more kinds. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁸ to 1 × with ^respect to 1 mol of the dihydric phenol as a raw material.
It is selected in the range of 10 ⁻³ equivalent, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalent.

In the polymerization reaction, in order to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate may be added after or at the end of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenyl phenyl carbonate,
Compounds such as bromophenylphenyl carbonate, nitrophenylphenyl carbonate, phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate and ethoxycarbonylphenylphenyl carbonate can be added. Among them, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferable,
In particular, 2-methoxycarbonylphenylphenyl carbonate is preferably used.

Further, it is preferable to use a deactivator that neutralizes the activity of the catalyst in the polymerization reaction. Specific examples of the quenching agent include benzene sulfonic acid, p-toluene sulfonic acid, methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-toluene sulfone. Sulfonic acid esters such as methyl acidate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; and further, trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene. , Methyl acrylate-sulfonated styrene copolymer, dodecylbenzenesulfonic acid-2-phenyl-2-propyl, dodecylbenzenesulfonic acid-2-
Phenyl-2-butyl, octylsulfonic acid tetrabutylphosphonium salt, decylsulfonic acid tetrabutylphosphonium salt, benzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetraethylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfone Acid tetrahexylphosphonium salt, dodecylbenzenesulfonic acid tetraoctylphosphonium salt, 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 Chill sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds may be used in combination.

Among the deactivators, those of phosphonium salt type or ammonium salt type are preferable. The amount of the deactivator is preferably 0.5 to 50 mol based on 1 mol of the remaining catalyst, and 0.01 to 500 ppm based on the polycarbonate resin after polymerization, and more preferably Is used in an amount of 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

Although the molecular weight of the polycarbonate resin is not specified, when the viscosity average molecular weight is less than 10,000, the high temperature characteristics and the like are deteriorated, and when it exceeds 50,000, the molding processability is deteriorated. Is 10, 0
It is preferably from 00 to 50,000, and from 14,000.
It is more preferably 30,000 and more preferably 14,000 to 24,000. Also, two or more polycarbonate resins may be mixed. In this case, it is naturally possible to mix with a polycarbonate resin having a viscosity average molecular weight outside the above range.

A mixture with a polycarbonate resin having a viscosity average molecular weight of more than 50,000 is particularly preferable because it has a high drip-preventing ability and more efficiently exhibits the effects of the present invention. More preferably, the viscosity average molecular weight is 8
It is a mixture with a polycarbonate resin of 10,000 or more, and more preferably a mixture with a polycarbonate resin having a viscosity average molecular weight of 100,000 or more.
That is, those having a clear distribution of two peaks by a method such as GPC (gel permeation chromatography) can be preferably used.

The viscosity average molecular weight referred to in the present invention is determined by using an Ostwald viscometer from a solution prepared by dissolving 0.7 g of a polycarbonate resin in 20 ml of 100 ml of methylene chloride at the specific viscosity calculated by the following formula. η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of methylene chloride drop and t is the number of seconds of drop of sample solution] The calculated specific viscosity is inserted by the following equation to obtain a viscosity average molecular weight M.
Ask for.

Η _SP /c=[η]+0.45×[η] ² c
(However, [η] is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

The aromatic polycarbonate as the component (A) of the present invention is the above-mentioned aromatic polycarbonate resin and contains substantially no halogen atom. Substantially not containing a halogen atom indicates that the molecule does not contain a halogen-substituted dihydric phenol, etc., and a trace amount of chlorine-based solvent remaining in the method for producing the aromatic polycarbonate, and even a carbonate precursor. Not something to do.

In the present invention, further, in the aromatic polycarbonate resin, the aromatic polycarbonate resin has an acid value of -0.5 to 5.0 (mg equivalent acid / 10 kg PC).
It is preferably in the range of. Acid value is -0.5 to 5.0
When it is in the range of (mg equivalent acid / 10 kg PC), the silicone compound of the present invention effectively acts, and tracking resistance, antistatic property, and anti-drip property of resin during combustion are easily exhibited. Become. More preferably, it is an aromatic polycarbonate resin having an acid value in the range of 0.0 to 3.0 (mg equivalent acid / 10 kg PC). The acid value is −0.
If it is less than 5 (mg equivalent acid / 10 kg PC), the aromatic polycarbonate resin itself becomes highly alkaline, and the thermal stability of the composition is lowered. 5.0 (mg equivalent acid / 10k
gPC), the free acid or phenolic end group in the aromatic polycarbonate resin will bond with the Si-H group in the silicone compound, resulting in tracking resistance, antistatic property, and resin drip during combustion. It becomes difficult to develop preventiveness.

The acid value referred to here means the amount of acid or base contained in 10 kg of polycarbonate resin (expressed as 10 kg PC), and is 100 methylene chloride.
To a solution prepared by adding 3 ml of methanol to ml and adding 10.0 g of polycarbonate resin as a sample and dissolving at 20 ° C., C ₁₅ H ₁₇ CN ₄ —C ₁₆ H ₁₈ CIN ₃ S.nH
Add 1 ml of ₂ O as an indicator and titrate with 0.01 mol / l sodium methylate (CH ₃ ONa). Insert the titration amount with and without sample into the following formula. And ask.

V = N × k × (X−Y) × 10000 / W V: Acid value (mg equivalent acid / 10 kg PC) N: Mol / sodium methylate (CH ₃ ONa) mol /
l k: 0.01 mol / l CH ₃ ONa factor X: Titration amount with sample (ml) Y: Titration amount without sample (ml) W: Sample amount (g)

The acid value is -0.5 to 5.0 (mg equivalent acid / 1
The aromatic polycarbonate resin of 0 kg PC) may use hydrochloric acid or the like to remove the catalyst such as triethylamine used for accelerating the reaction in the method for producing the aromatic polycarbonate resin by the interfacial polycondensation method. The acid value is adjusted to -0.5 to 5.0 by a method of adding an appropriate amount of an alkali component for neutralizing the acid component derived from hydrochloric acid or a method of enhancing the purification step such as washing with water.
It can be in the range of (mg equivalent acid / 10 kg PC). Further, in the method for producing an aromatic polycarbonate resin by an interfacial polycondensation method without using a catalyst, a method of adding an appropriate amount of an acid component to neutralize an alkali component derived from an acid binder such as sodium hydroxide or washing with water. The acid value is adjusted to -0.5 to 5.0 by a method for enhancing the purification process such as
It can be in the range of (mg equivalent acid / 10 kg PC).

The silicone compound used as the component (B) of the present invention is a silicone compound having a specific Si--H bond. That is, in a silicone compound containing a Si-H group and an aromatic group in the molecule, the amount of Si-H group contained (Si-H amount) is 0.1 to 0.1.
1.2 mol / 100 g, the ratio (aromatic group amount) containing the aromatic group represented by the following general formula (1) is 10 to 70% by weight,

[0048]

[Chemical 9]

(In the formula (1), X is independently OH.
Shows a monovalent organic residue having 1 to 20 carbon atoms. n is 0
Represents an integer of 5. Further, in the formula (1), when n is 2 or more, different types of X can be taken. )

It is at least one silicone compound (B) selected from the silicone compounds having a volatilization amount of 18% or less by the heating weight loss method at 105 ° C./3 hours.

The Si—H bond-containing unit is preferably selected from silicone compounds containing at least one constitutional unit represented by the following general formulas (2) and (3). It is at least one or more silicone compounds.

[0052]

[Chemical 10]

[0053]

[Chemical 11]

(In formulas (2) and (3), Z ^{1 to} Z ³ are each independently represented by a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a general formula (4) below. Compounds α1 to α3 each independently represent 0 or 1.
m1 represents an integer of 0 or more. Further, in the formula (3), the repeating unit when m1 is 2 or more can be a plurality of different repeating units. )

[0055]

[Chemical 12]

(In the formula (4), Z ^{4 to} Z ⁸ each independently represent a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms.
4 to α8 each independently represent 0 or 1. m2 represents an integer of 0 or more. Further, in the formula (4), when m2 is 2 or more, the repeating units can be a plurality of different repeating units. )

More preferably, when M is a monofunctional siloxane unit, D is a bifunctional siloxane unit, and T is a trifunctional siloxane unit, the silicone compound is composed of MD units or MDT units.

Z ^{1 to} Z ^{8 of} the structural units represented by the general formulas (2), (3) and (4), and X in the general formula (1).
Examples of the monovalent organic residue having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an alkyl group such as a decyl group, a cycloalkyl group such as a cyclohexyl group, a vinyl group, and an allyl group. Examples thereof include alkenyl groups such as groups, phenyl groups, aryl groups such as tolyl groups, and aralkyl groups. Further, these groups include various functional groups such as epoxy groups, carboxyl groups, carboxylic acid anhydride groups, amino groups, and mercapto groups. It may contain a group. More preferably, an alkyl group having 1 to 8 carbon atoms,
It is an alkenyl group or an aryl group, and particularly preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, a vinyl group, or a phenyl group.

Among the constitutional units represented by the general formulas (2) and (3), when the silicone compound containing at least one constitutional unit represented by the formula has plural repeating units of siloxane bonds, Can take any form of random copolymerization, block copolymerization, and tapered copolymerization.

In the present invention, in the silicone compound as the component (B), S in the silicone compound is
It is required that the i-H amount be in the range of 0.1 to 1.2 mol / 100 g. Si-H amount is 0.1-1.2m
By being in the range of ol / 100g, hydrophilic Si-H
The silicone compound having a bond acts as a surfactant, exhibits antistatic performance, and easily prevents dust and dirt from adhering. More preferably, the amount of Si-H is 0.2 to 1.0 m.
It is a silicone compound in the range of ol / 100 g.
When the amount of Si-H is less than 0.1 mol / 100 g, the antistatic performance of silicone becomes insufficient, and 1.2 mol /
When it is more than 100 g, the thermal stability of the composition is lowered.

The amount of Si-H as used herein means the m of the Si-H structure contained per 100 g of the silicone compound.
The ol number, which can be determined by measuring the volume of hydrogen gas generated per unit weight of the silicone compound by the alkali decomposition method. For example, 25
When 122 ml of hydrogen gas is generated per 1 g of the silicone compound at 0 ° C., the amount of Si—H is 0.5 mol / 100 g according to the following calculation formula. 122 × 273 / (273 + 25) ÷ 22400 × 10
0 ≈ 0.5

On the other hand, in an aromatic polycarbonate resin composition prepared by blending an aromatic polycarbonate resin with a silicone compound, the dispersed state of the silicone compound is important in order to prevent ignition of the molded article or adhesion of dust or dirt. is there. This is because when the silicone compound is unevenly distributed, the difference in tracking resistance of the molded product becomes large depending on the measurement location, and it becomes difficult to obtain a molded product having good tracking resistance. An important factor that determines the dispersion state is the amount of aromatic groups in the silicone compound.

From this point of view, the silicone compound of the present invention has an aromatic group content of 10 to 10 in the silicone compound.
It is required to be in the range of 70% by weight. More preferably, it is a silicone compound having an aromatic group content of 15 to 60% by weight. If the amount of the aromatic group in the silicone compound is less than 10% by weight, the silicone compound is unevenly distributed, resulting in poor dispersion, and it becomes difficult to obtain a molded article having good tracking resistance. The amount of aromatic groups is 70
If the amount is more than 10% by weight, the rigidity of the molecule of the silicone compound itself becomes high, so that the silicone compound is also unevenly distributed, resulting in poor dispersion, and it becomes difficult to obtain a molded article having good tracking resistance.

The amount of aromatic group means the proportion of the aromatic group represented by the following general formula (1) in the silicone compound, which can be calculated by the following formula.

[0065]

[Chemical 13]

Amount of aromatic group = [A / M] × 100 (% by weight) Here, A and M in the above formula represent the following numerical values, respectively.

A = total molecular weight of all aromatic group moieties represented by the general formula (1) contained in one molecule of silicone compound M = molecular weight of silicone compound

Further, the silicone compound of the present invention is required to have a volatilization amount of not more than 18% by the heating loss method at 105 ° C./3 hours. More preferably, it is a silicone compound having a volatilization amount of 10% or less. When the volatilization amount is larger than 18%, the volatilization amount of the silicone compound during the production of the resin composition also increases, and it becomes difficult to economically supply the resin composition of the present invention.

The silicone compound containing the structural unit represented by the above general formula may have a linear or branched structure as long as it satisfies the above conditions, and may have a Si--H group. It is possible to use various compounds having any of a side chain, a terminal, a branch point, or a plurality of sites in the molecular structure.

Generally, the structure of the silicone compound is constituted by arbitrarily combining the following four kinds of siloxane units. M unit: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ Si
O _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ =
CH) SiO _1/2 , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 ,
1 such as (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2
Functional siloxane unit D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ S
_{iO, H (C 6 H 5} ) SiO, (CH 3) (CH 2 = CH)
Bifunctional siloxane units such as SiO and (C ₆ H ₅ ) ₂ SiO T units: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 ,
HSiO _3/2 , (CH ₂ = CH) SiO _3/2 , (C ₆ H ₅ ).
_{Trifunctional} siloxane unit such as SiO _3/2 Q unit: Tetrafunctional siloxane unit represented by SiO ₂

The structure of the silicone compound used in the present invention is specifically represented by D _n , T _p , M _m as a rational formula.
_{D n, M m T p,} M m Q q, M m D n T p, M m D n Q q, M m T p
_Examples include Q _q , M _m D _n T _p Q _q , D _n T _p , D _n Q _q , and D _n T _p Q _q . Among these, the structure of the preferred silicone compound is
M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are M _m D _n and M _m D _n T _p . (Here, the coefficients m, n, p, and q in the above-mentioned rational formula are integers representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each rational formula is the average degree of polymerization of the silicone compound. In the invention, the average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80. Further, when any of m, n, p and q is a numerical value of 2 or more. The siloxane unit having the coefficient can be two or more kinds of siloxane units having different hydrogen atoms or organic residues to be bonded.) The above silicone compounds may be used alone or in combination of two or more kinds. May be used in combination.

The silicone compound having such Si--H bond can be produced by a method known per se. For example, the desired product can be obtained by co-hydrolyzing the corresponding organochlorosilanes according to the structure of the desired silicone compound and removing hydrochloric acid and low-boiling components produced as by-products. Further, in the case where a starting material is a silicone oil having an Si—H bond, an aromatic group represented by the general formula (1) or other organic residue in the molecule, or a cyclic siloxane or an alkoxysilane, hydrochloric acid or sulfuric acid is used. ,
By using an acid catalyst such as methanesulfonic acid, and optionally adding water for hydrolysis to allow the polymerization reaction to proceed, and then similarly removing the used acid catalyst and low boiling components, The silicone compound can be obtained.

The silicone compound as the component (B) is
The amount is 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight, and more preferably 1.2 to 5 parts by weight with respect to 100 parts by weight of the aromatic polycarbonate resin as the component (A).

The resin composition of the present invention may further contain, as the component (C), at least one compound selected from a radical generator, an organic alkali metal salt and an organic alkaline earth metal salt. By blending the component (C), the flame retardancy can be further improved, and especially the drip prevention property is improved. The compounding amount of the component (C) is 0.001 to 0.3 parts by weight, preferably 0.005, relative to 100 parts by weight of the aromatic polycarbonate resin (component A).
The range is preferably 0.3 to 0.3 parts by weight, and more preferably 0.005 to 0.2 parts by weight.

The radical generator used as the component (C) of the present invention includes organic peroxides such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and dicumyl peroxide. Oxide, 2,3-dimethyl-2,
3-diphenylbutane (dicumyl) and the like can be mentioned, and these are commercially available under the trade names of Perhexin 25B, Perkmill D, Nofmer BC and the like manufactured by NOF CORPORATION, and are easily available. In particular, it is preferable to generate radicals as little as possible during melt-kneading and to generate radicals that are stable to some extent during combustion. Therefore, 2,3-dimethyl-2,3-
Diphenylbutane (dicumyl) can be mentioned as a more preferable radical generator.

As the alkali metal salt and the alkaline earth metal salt used as the component (C) of the present invention, various metal salts conventionally used for making the polycarbonate resin flame-retardant can be used. In particular, mention may be made of metal salts of organic sulfonic acids or metal salts of sulfuric acid esters. These may be used alone or in combination of two or more. The alkali metal of the present invention includes lithium, sodium, potassium, rubidium, and cesium, and the alkaline earth metal includes beryllium, magnesium, calcium, strontium, and barium, and particularly preferably lithium and sodium. It is potassium.

Examples of the metal salt of organic sulfonic acid include alkali metal salt of aliphatic sulfonic acid, alkaline earth metal salt of aliphatic sulfonic acid, alkali metal salt of aromatic sulfonic acid, and alkaline earth metal salt of aromatic sulfonic acid. Examples thereof include metal salts. Preferable examples of the aliphatic sulfonic acid metal salt include alkali alkane sulfonic acid (earth) metal salts, and alkali sulfonic acid in which a part of the alkyl groups of the alkane sulfonic acid alkali (earth) metal salt is substituted with fluorine atoms (Earth) metal salts and perfluoroalkane sulfonic acid alkali (earth) metal salts can be mentioned, and these can be used alone or in combination of two or more (wherein alkali (earth) The term "metal salt" is used to include both alkali metal salts and alkaline earth metal salts).

Preferred examples of the alkanesulfonic acid used for the alkali (earth) alkanesulfonic acid metal salt include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, Heptane sulfonic acid, octane sulfonic acid, etc. are mentioned, and these can be used 1 type or in combination of 2 or more types. Further, a metal salt in which a part of the alkyl group is substituted with a fluorine atom can also be mentioned.

On the other hand, preferred examples of perfluoroalkanesulfonic acid include perfluoromethanesulfonic acid and
Perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, perfluorobutanesulfonic acid, perfluoromethylbutanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, etc. are mentioned, especially the carbon number. Is 1
The thing of -8 is preferable. These can be used alone or in combination of two or more.

As the alkali (earth) alkane sulfonic acid metal salt, sodium ethane sulfonate can be used as the alkali (earth) perfluoroalkane sulfonate.
Preferred examples of the metal salt include potassium perfluorobutane sulfonate.

The aromatic sulfonic acid used for the alkaline (earth) metal salt of aromatic sulfonic acid may be a sulfonic acid of a monomeric or polymeric aromatic sulfide, a sulfonic acid of an aromatic carboxylic acid and an ester, a monomeric or Polymeric aromatic ether sulfonic acid, aromatic sulfonate sulfonic acid, monomeric or polymeric aromatic sulfonic acid, monomeric or polymeric aromatic sulfonesulfonic acid, aromatic ketone sulfonic acid, heterocyclic Examples thereof include at least one acid selected from the group consisting of sulfonic acids, sulfonic acids of aromatic sulfoxides, and condensation products of methylene type bonds of aromatic sulfonic acids. These can be used alone or in combination of two or more. Can be used.

The sulfonic acid alkali (earth) metal salt of monomeric or polymeric aromatic sulfide is described in JP-A No. 50-98539.
For example, diphenyl sulfide-4,4'-disodium disulfonate, diphenyl sulfide-4,4 '
And dipotassium disulfonate.

Alkaline (earth) metal salts of sulfonic acids of aromatic carboxylic acids and esters are described in JP-A-50-9.
It is described in Japanese Patent No. 8540, and examples thereof include potassium 5-sulfoisophthalate, sodium 5-sulfoisophthalate, and polysodium polyethylene terephthalate polysulfonate.

Alkali (earth) metal sulfonates of monomeric or polymeric aromatic ethers are described in JP-A-50-98542, for example, calcium 1-methoxynaphthalene-4-sulfonate. ,
4-sodium dodecylphenyl ether disulfonate, sodium poly (2,6-dimethylphenylene oxide) polysulfonate, sodium poly (1,3-phenylene oxide) polysulfonate, poly (1,
4-phenylene oxide) polysodium polysulfonate, poly (2,6-diphenylphenylene oxide) polypotassium polysulfonate, poly (2-fluoro-6-)
Butylphenylene oxide) lithium polysulfonate and the like.

Examples of the alkali (earth) metal sulfonates of aromatic sulfonates are described in JP-A-50-98544, and examples thereof include potassium sulfonate of benzene sulfonate.

The monomeric or polymeric alkali (earth) aromatic sulfonic acid metal salt is described in JP-A-50-
98546, for example, sodium benzenesulfonate, strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, dipotassium naphthalene-2,6-disulfonate, biphenyl-3,3′-disulfone. Calcium acid etc. can be mentioned.

The monomeric or polymeric alkali (earth) aromatic sulfone sulfonic acid metal salt is described in JP-A-52-54746, for example, sodium diphenylsulfone-3-sulfonate and diphenylsulfone. Examples thereof include potassium-3-sulfonate, diphenylsulfone-3,3′-dipotassium disulfonate, and diphenylsulfone-3,4′-dipotassium disulfonate.

Alkali sulfonate (earth) metal salts of aromatic ketones are described in JP-A-50-98547, for example, sodium α, α, α-trifluoroacetophenone-4-sulfonate, Examples thereof include benzophenone-3,3′-dipotassium disulfonate.

The heterocyclic sulfonic acid alkali (earth) metal salt is described in JP-A-50-116542, for example, disodium thiophene-2,5-disulfonate and thiophene-2,5-. Dipotassium disulfonate, calcium thiophene-2,5-disulfonate,
Examples thereof include sodium benzothiophene sulfonate.

The alkaline (earth) sulfonate metal salt of aromatic sulfoxide is described in JP-A-52-54745, and examples thereof include potassium diphenyl sulfoxide-4-sulfonate. .

Examples of the condensate of an aromatic (sulfonate) aromatic sulfonic acid metal salt by a methylene type bond include a formalin condensate of sodium naphthalene sulfonate and a formalin condensate of sodium anthracene sulfonate.

On the other hand, as the alkali (earth) metal salt of sulfuric acid ester, there may be mentioned, in particular, the alkali (earth) metal salt of sulfuric acid ester of monohydric and / or polyhydric alcohols. Or, as the sulfuric acid ester of polyhydric alcohols, methyl sulfuric acid ester, ethyl sulfuric acid ester, lauryl sulfuric acid ester, hexadecyl sulfuric acid ester, sulfuric acid ester of polyoxyethylene alkyl phenyl ether, mono of pentaerythritol,
Examples thereof include di-, tri-, tetra-sulfate esters, lauric acid monoglyceride sulfates, palmitic acid monoglyceride sulfates, stearic acid monoglyceride sulfates, and the like. Preferable examples of the alkali (earth) metal salt of these sulfates include alkali (earth) metal salts of lauryl sulfate.

Examples of other alkali (earth) metal salts include alkali (earth) metal salts of aromatic sulfonamides such as saccharin and N- (p-tolylsulfonyl) -p-toluenesulfo. Imide, N-
Examples thereof include (N′-benzylaminocarbonyl) sulfanylimide, and an alkali (earth) metal salt of N- (phenylcarboxyl) sulfanylimide.

Of the above-mentioned alkali (earth) metal salts, more preferred components include alkali (earth) metal salts of aromatic sulfonic acids and perfluoroalkanesulfonic acid alkali (earth) metal salts. You can

The flame-retardant aromatic polycarbonate resin composition of the present invention may contain various thermoplastic resins and additives within the range where the effects of the present invention are exhibited.

As the thermoplastic resin other than the polycarbonate resin, for example, polyethylene resin, polypropylene resin, polystyrene resin, polyacrylstyrene resin, ABS resin, AS resin, AES resin, ASA resin,
General-purpose plastics such as SMA resin and polyalkylmethacrylate resin, polyphenylene ether resin, polyacetal resin, aromatic polyester resin,
Engineering plastics such as polyamide resin, cyclic polyolefin resin, polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate),
Examples include so-called super engineering plastics such as polyether ether ketone, polyether imide, polysulfone, polyether sulfone, and polyphenylene sulfide. Further, a thermoplastic elastomer such as a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, a polyamide-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, or a polyurethane-based thermoplastic elastomer can also be used.

Other various additives include, for example, reinforcing agents (talc, mica, clay, wollastonite, calcium carbonate, glass fibers, glass beads, glass balloons,
Milled fiber, glass flake, carbon fiber, carbon flake, carbon beads, carbon milled fiber,
Metal flakes, metal fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica,
Ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black, various whiskers, etc.), flame retardants (halogen-based, phosphate ester-based, red phosphorus, metal hydrate-based, etc.), Heat stabilizer, ultraviolet absorber, light stabilizer, release agent, lubricant, sliding agent (PTFE particles etc.), colorant (carbon black, pigment such as titanium oxide, dye), light diffuser (acrylic crosslinked particles, Silicon cross-linked particles, ultra-thin glass flakes, calcium carbonate particles, etc.), optical brighteners, phosphorescent pigments, fluorescent dyes, antistatic agents, flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents. Agents (particulate titanium oxide, particulate zinc oxide, etc.), impact modifiers typified by graft rubber, infrared absorbers, and photochromic agents can be added.

The flame-retardant aromatic polycarbonate resin composition of the present invention preferably contains a phosphorus stabilizer as a heat stabilizer. As the phosphorus-based stabilizer, any of phosphite-based, phosphonite-based, and phosphate-based stabilizers can be used.

Various kinds of phosphite stabilizers can be used in the present invention. Specifically, for example, the general formula (8)

[0100]

[Chemical 14]

[In the formula, R ⁸ represents a hydrogen atom or a carbon number of 1 to
An alkyl group having 20 carbon atoms, an aryl group or an alkaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a halo or alkylthio thereof (wherein the alkyl group has 1 carbon atom).
~ 30) or a hydroxy substituent, and three R ^{8 s} may be the same or different from each other, and a cyclic structure can be selected by being derived from dihydric phenols. ] It is a phosphite compound represented by these.

Further, the general formula (9)

[0103]

[Chemical 15]

[Wherein R ⁹ and R ¹⁰ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and 4 carbon atoms]. ~ 20 cycloalkyl groups, 1 carbon atoms
5 to 25 are 2- (4-oxyphenyl) propyl-substituted aryl groups. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group and those substituted with an alkyl group. ]
The phosphite compound represented by

Further, the general formula (10)

[0106]

[Chemical 16]

[In the formula, R ¹¹ and R ¹² are alkyl groups having 12 to 15 carbon atoms. It should be noted that R ¹¹ and R ¹² can be selected whether they are the same or different. ] The phosphite compound represented by these can be mentioned.

Examples of the phosphonite stabilizer include phosphonite compounds represented by the following general formula (11) and phosphonite compounds represented by the following general formula (12).

[0109]

[Chemical 17]

[0110]

[Chemical 18]

[In the formula, Ar ¹ and Ar ² are an aryl group or an alkylaryl group having 6 to 20 carbon atoms, or 1 carbon atom.
5 to 25 represents a 2- (4-oxyphenyl) propyl-substituted aryl group, and four Ar ^{1 s} may be the same or different from each other. Alternatively, the ^two Ar ² can be selected to be the same or different from each other. Specific preferred examples of the phosphite compound corresponding to the general formula (8) include diphenylisooctylphosphite and 2,2′-methylenebis (4,6-di-t).
ert-Butylphenyl) octylphosphite, diphenylmono (tridecyl) phosphite, phenyldiisodecylphosphite, phenyldi (tridecyl) phosphite.

Preferred specific examples of the phosphite compound corresponding to the above general formula (9) include distearyl pentaerythritol diphosphite and bis (2,4-
Di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite And bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-ter).
Mention may be made of t-butyl-4-methylphenyl) pentaerythritol diphosphite. Such phosphite compounds may be used alone or in combination of two or more.

Preferred specific examples of the phosphite compound corresponding to the above general formula (10) include 4,4′-
Mention may be made of isopropylidene diphenol tetratridecyl phosphite.

A preferred specific example of the phosphonite compound corresponding to the above general formula (11) is tetrakis (2,4-di-iso-propylphenyl) -4,4 '.
-Biphenylene diphosphonite, tetrakis (2,4-
Di-n-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4-di-) tert-butylphenyl) -4,3′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,
3'-biphenylene diphosphonite, tetrakis (2,
6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-n)
-Butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl) Phenyl)-
4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3 '
-Biphenylene diphosphonite and the like, tetrakis (di-tert-butylphenyl) -biphenylene diphosphonite is preferable, and tetrakis (2,4-di-t).
More preferred is ert-butylphenyl) -biphenylenediphosphonite. This tetrakis (2,4-di-te
rt-Butylphenyl) -biphenylene diphosphonite is preferably a mixture of two or more kinds, specifically, tetrakis (2,4-di-tert-butylphenyl) -4,
4'-biphenylene diphosphonite (E2-1 component),
Tetrakis (2,4-di-tert-butylphenyl)
One of -4,3'-biphenylenediphosphonite (E2-2 component) and tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite (E2-3 component) Alternatively, two or more kinds can be used in combination, but a mixture of such three kinds is preferable. In the case of a mixture of three types, the mixing ratio is E2-1.
Component, E2-2 component and E2-3 component in a weight ratio of 10
The range of 0:37 to 64: 4 to 14 is preferable, and 100:
The range of 40-60: 5-11 is more preferable.

Preferred specific examples of the phosphonite compound corresponding to the above general formula (12) include bis (2,4-di-iso-propylphenyl) -4-phenyl-phenylphosphonite and bis (2,4-diphenyl). -N-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-te)
rt-Butylphenyl) -3-phenyl-phenylphosphonite bis (2,6-di-iso-propylphenyl) -4-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)-
Examples thereof include 3-phenyl-phenylphosphonite, and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite is preferable, and bis (2,4-di-te).
More preferred is rt-butylphenyl) -phenyl-phenylphosphonite. This bis (2,4-di-tert
-Butylphenyl) -phenyl-phenylphosphonite is preferably a mixture of two or more kinds, specifically, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite and bis (2 , 4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite may be used alone or in combination of two, but a mixture of such two is preferable. In the case of a mixture of two kinds, the mixing ratio is 5: 1 by weight.
The range of 4 to 4 is preferable, and the range of 5: 2 to 3 is more preferable.

On the other hand, as the phosphate-based stabilizer, tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, Examples thereof include dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like, and trimethyl phosphate is preferable.

Examples of more preferable phosphorus-based stabilizers for the above-mentioned phosphorus-based stabilizers include compounds represented by the following general formulas (13) and (14).

[0118]

[Chemical 19]

(In the formula (13), R ¹³ and R ¹⁴ each represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group.)

[0120]

[Chemical 20]

(In the formula (14), R ¹⁵ , R ¹⁶ , R ¹⁷ ,
R ¹⁸ , R ²¹ , R ²² and R ²³ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and R ¹⁹ represents a hydrogen atom or 1 to 12 carbon atoms. 4 represents an alkyl group of 4 and R ²⁰
Represents a hydrogen atom or a methyl group. In the formula (13), R ¹³ and R ¹⁴ are preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples of the compound of formula (13) include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite. Fight, Tris (2,4-di-te
rt-Butylphenyl) phosphite, tris (2,6)
-Di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite and the like, and particularly tris (2,6-di-ter).
t-Butylphenyl) phosphite is preferred.

On the other hand, the phosphorus compound of formula (14) can be produced by a known method. For example, a bisphenol compound represented by the following general formula (15) is reacted with phosphorus trichloride to obtain the corresponding phosphoric acid chloride, and then the corresponding general formula (1)
There is a method of reacting with the phenol shown in 6).

[0123]

[Chemical 21]

(In the formula (15), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group; ¹⁹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ²⁰ represents a hydrogen atom or a methyl group.)

[0125]

[Chemical formula 22]

(In the formula (16), R ²¹ , R ²² , and R ²³
Each represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. )

Specific examples of the compound of the above general formula (15) include 2,2'-methylenebisphenol and 2,2'-.
Methylenebis (4-methylphenol), 2,2'-methylenebis (6-methylphenol), 2,2'-methylenebis (4,6-dimethylphenol), 2,2'-
Ethylidene bisphenol, 2,2'-ethylidene bis (4-methylphenol), 2,2'-isopropylidene bisphenol, 2,2'-methylene bis (4-methyl-6-tert-butylphenol), 2,2'-methylene bis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4,6-di-ter)
t-butylphenol), 2,2'-methylenebis (4
-Methyl-6-cyclohexylphenol), 2,2 '
-Dihydroxy-3,3'-di (α-methylcyclohexyl) -5,5'-dimethylphenylmethane, 2,2 '
-Methylenebis (6-α-methyl-benzyl-p-cresol), 2,2'-ethylidene-bis (4,6-di-
(tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), and the like, which can be preferably used.

More preferably, the compound of the general formula (15) is 2,2'-methylenebis (4-methyl-6-te).
rt-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol),
2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidene-bis (4,6
-Di-tert-butylphenol), and 2,2 '
-Butylidene-bis (4-methyl-6-tert-butylphenol) may be mentioned.

On the other hand, specific examples of the compound of the general formula (16) include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2 -Te
rt-butyl-4-methylphenol, 2,4-di-t
ert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-
Methylphenol, 2,4-dimethyl-6-tert-
Butylphenol, 2,6-di-tert-butyl-4
-Ethylphenol, 2,4,6-tri-tert-butylphenol, 2,6-di-tert-butyl-4-s-butylphenol and the like can be mentioned and can be preferably used. More preferred as a specific example of the compound of general formula (16) is the case where it has two or more alkyl substituents.

The flame-retardant aromatic polycarbonate resin composition of the present invention may contain a phenolic antioxidant. The phenolic antioxidant can suppress discoloration during heat exposure and, at the same time, exhibits some effect on the improvement of flame retardancy. Various compounds can be used as the phenolic antioxidant.

Specific examples of such phenolic antioxidants include vitamin E and n-octadecyl-β-
(4'-Hydroxy-3 ', 5'-di-tert-butylfell) propionate, 2-tert-butyl-6
-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) phenol, 3,5-di-ter
t-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-t)
ert-butylphenol), triethyleneglycol-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-te
rt-Butyl-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-ter
t-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-ter
t-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-te
rt-butylanilino) -1,3,5-triazine,
N, N'-hexamethylenebis- (3,5-di-ter
t-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) isocyanurate, tris (3,5-di-ter)
t-Butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-)
Hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris 2 [3 (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane and the like can be mentioned, It can be preferably used.

More preferably, n-octadecyl-β-
(4'-Hydroxy-3 ', 5'-di-tert-butylfell) propionate, 2-tert-butyl-6
-(3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy] -1,1, -dimethylethyl} -2,4,8,
10-tetraoxaspiro [5,5] undecane, and tetrakis [methylene-3- (3 ′, 5′-di-te]
rt-Butyl-4-hydroxyphenyl) propionate] methane and further n-octadecyl-β-
(4'-Hydroxy-3 ', 5'-di-tert-butylfel) propionate is preferred.

The flame-retardant aromatic polycarbonate resin composition of the present invention may contain a sulfur antioxidant. It is particularly suitable when the molding is used for rotational molding or compression molding. Specific examples of such sulfur-based antioxidants include:
Dilauryl-3,3'-thiodipropionic acid ester,
Ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-thiodipropionic acid ester, distearyl-3,3'-thiodipropionic acid ester, laurylstearyl-3,3'-thiodiester Propionic acid ester, pentaerythritol tetra (β-laurylthiopropionate) ester, bis [2-methyl-4- (3-laurylthiopropionyloxy) -5
-Tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole, 2-
Mercapto-6-methylbenzimidazole, 1,1 '
-Thiobis (2-naphthol) and the like can be mentioned. More preferably, pentaerythritol tetra (β
-Lauryl thiopropionate) esters may be mentioned.

The above-mentioned phosphorus-based stabilizers, phenol-based antioxidants, and sulfur-based antioxidants can be used alone or in combination of two or more. The case where a phosphorus-based stabilizer is essential is more preferable, and it is particularly preferable to include the compound of the general formula (13) as the phosphorus-based stabilizer.

The proportion of these stabilizers in the composition is, based on 100 parts by weight of the flame-retardant aromatic polycarbonate resin composition of the present invention, a phosphorus-based stabilizer, a phenol-based antioxidant, or a sulfur-based antioxidant. Is 0.00
It is preferably from 0 to 1 part by weight. More preferably, per 100 parts by weight of the polycarbonate resin composition, 0.
It is 0005 to 0.5 parts by weight. More preferably 0.
001 to 0.2 parts by weight.

If desired, a release agent can be added to the flame-retardant aromatic polycarbonate resin composition of the present invention. Since the present invention has good flame retardancy, good flame retardancy can be achieved even when a mold release agent, which usually tends to adversely affect flame retardancy, is added. As such a release agent, known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-
Alkene polymers, etc. Those modified with a functional group-containing compound such as acid modification can also be used), silicone compounds (other than the component (B) of the present invention. For example, linear or cyclic polydimethylsiloxane oil or polymethylphenyl silicone oil) Etc., those modified with a functional group-containing compound such as acid modification can also be used), fluorine compounds (fluorine oil represented by polyfluoroalkyl ether, etc.), paraffin wax,
Beeswax etc. can be mentioned. Among these, saturated fatty acid esters, linear or cyclic polydimethylsiloxane oil, polymethylphenyl silicone oil, and the like, and fluorine oil can be mentioned. The amount of the releasing agent is preferably 0.01 to 0.3 parts by weight based on 100 parts by weight of the total of the components (A) to (C).

Preferred releasing agents include saturated fatty acid esters, for example, monoglycerides such as stearic monoglyceride, polyglycerin fatty acid esters such as decaglycerin decastearate and decaglycerin tetrastearate, stearic acid stearate. Lower fatty acid esters, higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used.

Since the flame-retardant aromatic polycarbonate resin composition of the present invention is often used in the case of OA equipment, it is preferable that it contains an ultraviolet absorber. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy. -4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2 '-Dihydroxy-4,4'-dimethoxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxy-5-
Examples thereof include benzophenone-based ultraviolet absorbers typified by sodium sulfoxybenzophenone and bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane.

Examples of the UV absorber include 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert)
-Butylphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'
-Di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-ter
t-amylphenyl) benzotriazole, 2- (2 ′)
-Hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-bis (α, α'-dimethylbenzyl) phenyl) benzotriazole, 2- [2'-hydroxy-
3 '-(3 ", 4", 5 ", 6" -tetraphthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl ) -5-Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-te
rt-Butylphenyl) -5-chlorobenzotriazole, 2,2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl -3- [3-ter
A benzotriazole-based ultraviolet absorber represented by a condensate with t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol can be mentioned.

Further, as the ultraviolet absorber, for example, 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-hexyloxy-phenol, 2- (4,
6-bis- (2,4-dimethylphenyl-1,3,5-
Examples thereof include hydroxyphenyltriazine compounds such as triazin-2-yl) -5-hexyloxy) -phenol.

Further, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2n-butylmalonate, 1,
Condensation product of 2,3,4-butanecarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, 1,2,3,4-butanedicarboxylic acid and 1,2,2 , 6,6-Pentamethyl-4-piperidinol and tridecyl alcohol condensate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)-
1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-Tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2 , 2,6,6-Tetramethylpiperidyl) imino]}, poly {[6-morpholino-s-triazine-2,4-diyl] [(2,2,6,
6-Tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetra Methyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,2
Condensate of 4,8,10-tetraoxaspiro [5,5] undecane) diethanol, N, N′-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-
Butyl-N- (1,2,2,6,6-pentamethyl-4
-Piperidyl) amino] -chloro-1,3,5-triazine condensate, 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-4-piperidinol and β , Β, β ', β'-tetramethyl-3,9
-(2,4,8,10-Tetraoxaspiro [5,5]
A condensate of undecane) diethanol and a hindered amine-based light stabilizer typified by polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane can also be incorporated.

The ratio of such an ultraviolet absorber and a light stabilizer is
0.1 parts per 100 parts by weight of the total of the components (A) to (C).
The amount is 01 to 5 parts by weight, more preferably 0.02 to 1 part by weight.

A bluing agent may be added to the flame-retardant aromatic polycarbonate resin composition of the present invention in order to cancel the yellow tint due to an ultraviolet absorber or the like. As the bluing agent, any bluing agent that can be used in polycarbonate resins can be used without any particular problem. Generally, anthraquinone dyes are easily available and preferred. As a specific bluing agent, for example, a common name SolventViolet13 [CA. No
(Color index No) 60725; Trade name Bayer's "Macrolex Violet B", Mitsubishi Chemical Co., Ltd. "Dialesin Blue G", Sumitomo Chemical Co., Ltd. "Sumiplast Violet B"], general name S
event Violet31 [CA. No6821
0; Trade name "Mitsubishi Resin Co., Ltd." Dialesin Violet D "], general name Solvent Violet33
[CA. No. 60725; Trade name "Mitsubishi Resin Co., Ltd." Dialesin Blue J "", general name Solvent
Blue94 [CA. No61500; Trade name "Mitsubishi Resin Co., Ltd." Dialesin Blue N "], general name Sol
Vent Violet 36 [CA. No68210;
Trade name Bayer "Macrolex Violet 3
R ”], general name Solvent Blue 97 [trade name“ Macrolex Blue RR ”manufactured by Bayer Co.] and general name Solvent Blue 45 [CA. No611
10; Trade name "Tetrazol Blue RL" manufactured by Sand Co.
S ”], Macrolex Violet, Triazole Blue RLS and the like manufactured by Ciba Specialty Chemicals, and particularly Macrox Blue RR, Macrolex Violet B and Triazole Blue RLS are preferable.

Any method may be used to produce the flame-retardant aromatic polycarbonate resin composition of the present invention. For example, the components a to c and optionally other components are respectively V
After thoroughly mixing using a pre-mixing means such as a mold blender, a Henschel mixer, a mechanochemical device, and an extrusion mixer, granulation may be performed by an extrusion granulator or a briquetting machine, if necessary, and then a vented twin-screw Examples thereof include a method of melt-kneading with a melt-kneader represented by a ruder and pelletizing with a device such as a pelletizer.

In addition, a method of supplying the components (A), (B), (C) and optionally other components independently to a melt-kneader represented by a vent type twin-screw ruder, (A) and ( A method in which a part of the component C) is pre-mixed and then supplied to the melt kneader independently of the remaining components, and the component (B) is diluted and mixed with water or an organic solvent and then supplied to the melt kneader, or such dilution is performed. A method of pre-mixing the mixture with other components and then supplying the mixture to a melt-kneader may be used. When the components to be blended are liquid, a so-called liquid injection device or liquid addition device can be used for supplying to the melt kneader.

The flame-retardant polycarbonate resin composition of the present invention can be manufactured into various products by injection molding such pellets to obtain molded products. In such injection molding, not only a usual cold runner molding method, but also a hot runner that enables runnerless manufacturing can be used. Also in the injection molding, not only the usual molding method but also gas-assisted injection molding, injection compression molding, ultra-high speed injection molding and the like can be used.

Further, the flame-retardant aromatic polycarbonate resin composition of the present invention is produced by extrusion molding into various shaped extrusion molded articles,
It can also be used in the form of sheets, films and the like. Also, the inflation method and the
A casting method or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the flame-retardant aromatic polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding without melt-kneading.

[0148]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. The following items were evaluated. (1) Material characteristics (1-) Drip prevention property A test was conducted based on UL standard 94 using a 1.6 mm-thick test piece prepared according to UL standard. At that time, the time to reach the drip after the primary ignition and the secondary ignition was measured, and the shortest time (second) was evaluated. (1-) Tracking resistance The tracking resistance of a rectangular plate-shaped molded product having a size of 150 mm × 150 mm and a thickness of 5.0 mm is IEC 60112: 7.
Comparative tracking index (CTI) obtained by measuring in 9
And the guaranteed tracking index (P
It was evaluated by TI). (1-) Antistatic property 1-The rectangular plate-shaped molded product used for measurement is left standing for 24 hours in an environment of a temperature of 25 ° C and a humidity of 50% and then placed horizontally, and 0.5 g of tobacco ash is added to the molded product. After falling down and leaving it for 5 minutes, the molded product was vertically leaned. The amount of cigarette ash attached to the surface of the molded product was visually evaluated in the state where the molded product was vertically leaned against the following criteria.

<Adhesion amount> High: Large amount of adhesion. Small: Small amount of adhesion. Very small: Almost no adhesion.

Examples 1 to 14 and Comparative Examples 1 to 10 The resin compositions shown in Tables 1 to 3 were prepared in the following manner.
The description will be given according to the symbols in the table below.

The respective components in the proportions shown in Tables 1 to 3 were weighed, and a phosphite antioxidant (IRG manufactured by Ciba-Geigy Japan Co.
AFOS168) 0.01 part by weight, phenolic antioxidant (IRGANOX1076 manufactured by Ciba-Geigy Japan)
0.01 parts by weight, ultraviolet absorber (Kemipro Chemicals Co., Ltd., Chemisorb 79) 0.3 parts by weight, mold release agent (Rikenmal SL900, Riken Vitamin Co., Ltd.)
0.3 part by weight was weighed and uniformly mixed using a tumbler, and the mixture was put into an extruder to prepare a resin composition.

As the extruder, a vent type twin-screw extruder having a diameter of 30 mmφ (KTX-30, Kobe Steel, Ltd.) was used. Before the vent position, the screw configuration was designed so that the kneading zone of the first stage (composed of feed kneading disc x 2, feed rotor x 1, return rotor x 1 and return kneading disc x 1) After that, the second stage kneading zone (feeding rotor ×
1 and a return rotor × 1) were provided. Cylinder-Die temperature 280
The strand was extruded under conditions of a temperature of ℃ and a vent suction degree of 3000 Pa, cooled in a water bath, and then strand cut with a pelletizer to pelletize.

The pellets thus obtained were dried at 110 ° C. for 5 hours by a hot air circulation dryer, and were then subjected to an injection molding machine [FANUC T-150D] at a cylinder temperature of 290 ° C.
A test piece was molded at a mold temperature of 70 ° C.

Raw materials used in Tables 1 to 3 are as follows. (A) Component Synthesis Example-1 219.4 parts of ion-exchanged water and 40.2% aqueous solution of sodium hydroxide in a reactor equipped with a thermometer, a stirrer and a reflux condenser.
Parts and 0.12 parts of hydrosulfite were added, 57.5 parts of bisphenol A was dissolved with stirring, 181 parts of methylene chloride was added, and phosgene 28.
A polycarbonate oligomer was obtained by blowing and reacting 3 parts over about 40 minutes. After the temperature of this reaction mixture was adjusted to 30 ° C., 1.24 parts of p-tert-butylphenol and 4
After emulsifying by adding 7.2 parts of 8% sodium hydroxide aqueous solution,
The reaction was completed by adding 0.064 parts of triethylamine and stirring for 1 hour. After the completion of the reaction, 246 parts of methylene chloride was added to dilute the solution to obtain a methylene chloride solution having a concentration of 14% by weight of a polycarbonate resin, and then a centrifugal extractor with a perforated plate (KCC centrifugal extractor manufactured by Kawasaki Engineering Co., Ltd.) was used to Flow rate of 0.5% sodium hydroxide aqueous solution of 100
0 ml / min, flow rate of organic phase is 1,000 ml / min
At a rate of 3,500 rpm and treated under the conditions of 3,500 rpm to obtain an organic phase. Hydrochloric acid of ph3 was added to the organic phase in the same volume as the organic phase, and the mixture was separated after mixing. The operation of adding the same volume of ion-exchanged water to the organic phase and mixing and separating was repeated 8 times to obtain a purified methylene chloride solution of the polycarbonate resin. Methylene chloride was evaporated in a kneader to give a viscosity average molecular weight of 23,000.
A polycarbonate resin powder (hereinafter, abbreviated as PC-1) having an acid value of 0 and an acid value of 0.1 (mg equivalent acid / 10 kg PC) was obtained.

Synthetic Example-2 The same operation as in Synthetic Example-1 was repeated except that the same amount of ion-exchanged water was added to the organic phase and mixed and separated 5 times, and the viscosity average molecular weight was 23,000 and the acid value was 2. 8 (mg equivalent acid /
10 kg PC) polycarbonate resin powder (hereinafter PC)
-2).

Synthetic Example-3 The same operation as in Synthetic Example-1 was repeated except that the same amount of ion-exchanged water was added to the organic phase and the mixture was separated three times. The viscosity average molecular weight was 23,000 and the acid value was 7. 0 (mg equivalent acid /
10 kg PC) polycarbonate resin powder (hereinafter PC)
-3). (B) component

Synthesis Example-4 577.1 g of water and 130 g of toluene were charged into a 1 L flask equipped with a stirrer, a cooling device and a thermometer, and the internal temperature was 5
Cooled to ° C. A dropping funnel was charged with a mixture of 23.6 g of trimethylchlorosilane, 75.0 g of methyldichlorosilane and 55.0 g of diphenyldichlorosilane,
The mixture was dropped into the flask over 2 hours while stirring. During this time, cooling was continued so that the internal temperature was maintained at 20 ° C. or lower.
After completion of the dropping, the mixture was stirred at an internal temperature of 20 ° C. for 4 hours for aging, and then left standing to remove the separated hydrochloric acid aqueous layer to obtain 10%.
An aqueous solution of sodium carbonate was added and the mixture was stirred for 5 minutes, then left standing and the separated aqueous layer was removed. Then, it was further washed with ion-exchanged water three times, and it was confirmed that the toluene layer became neutral. This toluene solution was heated under reduced pressure to an internal temperature of 120 ° C. to remove toluene and low-boiling components, and insoluble materials were removed by filtration to obtain Silicone Compound B-1.

Synthesis Example-5 1,3-diphenyl-1,1,3,3-tetramethyldisiloxane 49.9 g, 1,3,5,7 was placed in a 1 L flask equipped with a stirrer, a cooling device and a thermometer. 104.6 g of tetramethylcyclotetrasiloxane and 425.2 g of diphenyldimethoxysilane were charged, and 25.0 g of concentrated sulfuric acid was added with further stirring. After cooling to an internal temperature of 10 ° C., 31.9 g of water was dropped into the flask over 30 minutes while stirring. During this time, cooling was continued so that the internal temperature was maintained at 20 ° C. or lower. After completion of dropping, stirring was continued at an internal temperature of 10 to 20 ° C. for 5 hours for aging, followed by water 8.
After adding 5 g and 300 g of toluene and stirring for 30 minutes, it left still and the separated water layer was removed. Then, it was further washed with a 5% sodium sulfate aqueous solution four times, and it was confirmed that the toluene layer became neutral. After heating the toluene solution under reduced pressure to an internal temperature of 120 ° C. to remove toluene and low boiling points,
Insoluble matter is removed by filtration to remove the silicone compound B-2.
Got

Synthesis Example-6 Hexamethyldisiloxane 40.6 g, 1,3,5,7
-Charging 60.1 g of tetramethylcyclotetrasiloxane, 69.0 g of octamethylcyclotetrasiloxane, 359.2 g of diphenyldimethoxysilane and 59.5 g of phenyltrimethoxysilane, and further adding concentrated sulfuric acid 2
A silicone compound B-3 was obtained in the same manner as in Synthesis Example-5 except that 5.0 g was added and 35.3 g of water was added dropwise.

Synthesis Example-7 27.1 g of hexamethyldisiloxane, 167.8 g of diethoxymethylsilane, 269.3 g of octamethylcyclotetrasiloxane and 158.4 g of diphenyldimethoxysilane were charged, and further 25.0 g of concentrated sulfuric acid was added. A silicone compound B-4 was obtained in the same manner as in Synthesis Example-5 except that 34.8 g of water was added dropwise.

Synthesis Example-8 500.2 g of water and 120 g of toluene were charged, and 47.3 g of dimethylchlorosilane and 52.
A silicone compound B-5 was obtained in the same manner as in Synthesis Example-4 except that a mixture of 9 g and 63.5 g of phenyltrichlorosilane was added dropwise.

Synthesis Example-9 101.5 g of hexamethyldisiloxane, 1,1,3
3-tetramethyldisiloxane 84.0 g, 1,3
5,7-Tetramethylcyclotetrasiloxane 75.2
g, octamethylcyclotetrasiloxane 1.5 g, octaphenylcyclotetrasiloxane 44.2 g and phenyltrimethoxysilane 297.4 g were charged, concentrated sulfuric acid 25.0 g was added, and water 41.3 g was added dropwise. The same operation as in Synthesis Example-5 was carried out to obtain Silicone Compound B-6.

Synthesis Example-10 516.2 g of water and 120 g of toluene were charged, and 18.0 g of dimethylchlorosilane and 10 of methyldichlorosilane were charged.
A silicone compound B-7 was obtained in the same manner as in Synthesis Example-4 except that a mixture of 9.3 g and diphenyldichlorosilane 38.5 g was added dropwise.

Synthesis Example-11 490.5 g of water and 120 g of toluene were charged, and 40.7 g of trimethylchlorosilane and 4 of methyldichlorosilane were charged.
Synthesis example except that a mixture of 6.0 g, dimethyldichlorosilane 43.6 g, diphenyldichlorosilane 6.3 g and phenyltrichlorosilane 26.4 g was added dropwise.
By operating in the same manner as in 4, a silicone compound B-8 was obtained.

Synthesis Example-12 1,1,3,3-tetramethyldisiloxane 13.4
g, 1,3,5,7-tetramethylcyclotetrasiloxane 30.1 g, octamethylcyclotetrasiloxane 31.9 g and diphenyldimethoxysilane 522.
Charge 9 g, add 40.0 g concentrated sulfuric acid, and add water 3
A silicone compound B-9 was obtained in the same manner as in Synthesis Example-5 except that 9.3 g was added dropwise. B-1: The Si-H amount produced according to Synthesis Example-4 is 0.
A silicone compound having 65 mol / 100 g, an aromatic group amount of 34% by weight, and a volatilization amount of 3.2%. B-2: The amount of Si-H produced according to Synthesis Example-5 is 0.
35 mol / 100 g, 59% by weight of aromatic group, and 0.8% of volatile amount of silicone compound. B-3: The Si-H amount produced according to Synthesis Example-6 is 0.
20 mol / 100 g, an aromatic group amount of 50% by weight, and a volatilization amount of 2.2%. B-4: Si-H amount produced according to Synthesis Example-7 is 0.
25 mol / 100 g, an aromatic group amount of 20% by weight, and a volatilization amount of 3.6%. B-5: Si-H amount produced according to Synthesis Example-8 is 0.
A silicone compound having 96 mol / 100 g, an aromatic group amount of 23% by weight, and a volatilization amount of 8.4%. B-6: The Si-H amount produced according to Synthesis Example-9 is 0.
50 mol / 100 g, a silicone compound having an aromatic group amount of 30% by weight and a volatilization amount of 9.4%. B-7: Si—H amount produced according to Synthesis Example-10 was 1.14 mol / 100 g, and aromatic group amount was 23% by weight.
A silicone compound with a volatile content of 4.9%. B-8: Si—H amount produced according to Synthesis Example-11 was 0.40 mol / 100 g, aromatic group amount was 13% by weight,
A silicone compound with a volatilization amount of 15.4%. B-9: Si—H amount produced according to Synthesis Example-12 was 0.14 mol / 100 g, aromatic group amount was 66 wt%,
A silicone compound with a volatile amount of 0.5%.

Other than the component (B) Synthesis Example-13 463.6 g of water and 120 g of toluene were charged, and 47.3 g of dimethylchlorosilane and 6 of dimethyldichlorosilane were charged.
A silicone compound B-10 was obtained in the same manner as in Synthesis Example-4 except that a mixture of 8.3 g, diphenyldichlorosilane 11.7 g and phenyltrichlorosilane 35.3 g was added dropwise.

Synthesis Example-14 560.6 g of water and 130 g of toluene were charged, and 21.2 g of trimethylchlorosilane and 5 of methyldichlorosilane were charged.
A silicone compound B-11 was obtained in the same manner as in Synthesis Example-4 except that a mixture of 2.3 g, 83.9 g of dimethyldichlorosilane and 13.8 g of phenyltrichlorosilane was added dropwise.

Synthesis Example-15 3,1,3,3-tetramethyldisiloxane 39.0 g
Silicone compound B-12 was obtained in the same manner as in Synthesis example-5 except that 566.9 g of diphenyldimethoxysilane and 25.0 g of concentrated sulfuric acid were added, and 42.6 g of water was added dropwise.

Synthesis Example-16 Hexamethyldisiloxane 39.9 g, 1,3,5,7
-Synthesis example except that 14.8 g of tetramethylcyclotetrasiloxane, 200.6 g of octamethylcyclotetrasiloxane and 300.6 g of diphenyldimethoxysilane were charged, 25.0 g of concentrated sulfuric acid was further added, and 22.6 g of water was added dropwise. By operating in the same manner as in -5, a silicone compound B-13 was obtained.

Synthesis Example-17 560.6 g of water and 140 g of toluene were charged, and 18.9 g of dimethylchlorosilane and 12 of methyldichlorosilane were charged.
A silicone compound B-14 was obtained in the same manner as in Synthesis Example-4 except that a mixture of 6.5 g and diphenyldichlorosilane 25.3 g was added dropwise. B-10 (comparative): Si prepared according to Synthesis Example-13
-H amount is 0.50 mol / 100g, aromatic group amount is 20
A silicone compound having a weight% and a volatilization amount of 19.4%. B-11 (Comparison): Si prepared according to Synthesis Example-14
A silicone compound having an H amount of 0.45 mol / 100 g, an aromatic group amount of 5% by weight, and a volatilization amount of 8.8%. B-12 (comparative): Si prepared according to Synthesis Example-15
-H amount is 0.12 mol / 100 g, aromatic group amount is 72
A silicone compound with a weight percentage of 0.5%. B-13 (Comparison): Si prepared according to Synthesis Example-16
-H amount is 0.05 mol / 100g, aromatic group amount is 38
A silicone compound having a weight% and a volatilization amount of 1.8%. B-14 (Comparison): Si prepared according to Synthesis Example-17
-H amount is 1.31 mol / 100g, aromatic group amount is 16
A silicone compound having a weight% and a volatilization amount of 6.9%.

<Ratio Formula of Each Silicone Compound> B-1: M ₂ ^DH ₆ Dφ ² ₂ B-2: Mφ ₂ ^DH ₁₀ Dφ ² ₁₀ B-3: M ₅ ^DH ₁₀ D _9.3 Dφ ² _14.7 Tφ ₃ B-4: M ₂ ^DH _7.5 D _21.8 Dφ ² _3.89 B-5: ^MH ₅ ^DH _4.6 Tφ ₃ B-6: M _2.5 ^MH _2.5 ^DH _2.5 D _0.039 Dφ ² _0.445 Tφ ₃ B-7 ^{_{: M H 2 D H 10 Dφ}} 2 1.6 B-8: M 3 D H 3.2 D 2.7 Dφ 2 0.2 Tφ 1 B-9: M H 2 D H 5 D 4.3 Dφ 2 21.4 B-10: M H 3 D 3.17 Dφ ² _0.28 Tφ ₁ (Comparison) B-11: M ₃ ^DH ₇ D ₁₀ Tφ ₁ (Comparison) B-12: ^MH ₂ Dφ ² ₈ (Comparison) B-13: M ₂ ^DH ₁ D ₁₁ Dφ ² _{5 ^{(comparison) B-14: M H 2}} D H 11 Dφ 2 1 ( comparative)

Each symbol in the above-mentioned rational formula represents the following siloxane unit, and the coefficient of each symbol represents the degree of polymerization of each siloxane unit in one molecule. M: (CH ₃ ) ₃ SiO _1/2 ^MH : H (CH ₃ ) ₂ SiO _1/2 Mφ _{: (CH 3) 2 (C} 6 H 5) SiO 1/2 D: (CH 3) 2 SiO D H: H (CH 3) SiO Dφ 2: (C 6 H 5) 2 SiO Tφ : (C ₆ H ₅ ) SiO _3/2

Component (C) C-1: 2,3-dimethyl-2,3-diphenylbutane (dicumyl) (Nofmer BC manufactured by NOF CORPORATION) C-2: Perfluorobutanesulfonic acid potassium salt (Dainippon Ink Chemical Industry Co., Ltd. Megafac F-114
P) C-3: potassium salt of diphenyl sulfone sulfonic acid (KSS manufactured by UCB Japan)

[0174]

[Table 1]

[0175]

[Table 2]

[0176]

[Table 3]

From these tables it is clear that: From the comparison between the example and the comparative example, the flame-retardant polycarbonate resin composition of the present invention is excellent in tracking resistance and antistatic property, and the addition of the silicone compound of the present invention leads to drip after ignition. It can be seen that it takes a long time to reach and the resin has excellent drip prevention properties during combustion.

[0178]

As is apparent from the above, the flame-retardant aromatic polycarbonate resin composition of the present invention mainly contains a silicone compound as an anti-drip agent, has good anti-drip performance, and has anti-tracking property. It also has excellent properties and antistatic properties. Such characteristics are not present in conventional flame-retardant aromatic polycarbonate resins, and such resin compositions also have high thermal stability even when melted at high temperatures such as injection molding. Therefore, it is extremely useful not only for relay cases and capacitor cases but also for various industrial applications in the field of OA equipment and the like, and the industrial effect produced by it is extremely large.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Akinari Itagaki             Gunma Prefecture Usui District Matsuida Town             Yue chemical industry silicone electronic material technology             Inside the Institute (72) Inventor Masaaki Yamatani             Gunma Prefecture Usui District Matsuida Town             Yue chemical industry silicone electronic material technology             Inside the Institute (72) Inventor Yoshiteru Kobayashi             Gunma Prefecture Usui District Matsuida Town             Yue chemical industry silicone electronic material technology             Inside the Institute F-term (reference) 4F071 AA50 AA65 AA66 AC08 AC14                       AF47 AH19                 4J002 CG001 CP042 EJ000 EK006                       EV000 EV257 EW040 EW060                       FD050 FD060 FD070 FD137                       FD146 FD160 GT00

Claims (9)

[Claims] 1. An acid value of -0.5 to 5.0 (mg equivalent acid /
Silicone compound containing Si-H group and aromatic group in the molecule, relative to 100 parts by weight of the aromatic polycarbonate resin (A) of 10 kgPC), the amount containing Si-H group (Si-H Amount) is 0.1
1.2 mol / 100 g, the ratio of aromatic groups represented by the following general formula (1) (the amount of aromatic groups) is 10 to 70% by weight, (In the formula (1), each X independently represents an OH group and a carbon number of 1 to 1.
20 monovalent organic residues are shown. n represents an integer of 0 to 5. Further, in the formula (1), when n is 2 or more, different types of X can be taken. ) It is difficult to mix 0.1 to 10 parts by weight of at least one silicone compound (B) selected from the silicone compounds having a volatilization amount of 18% or less by a heating weight loss method at 105 ° C./3 hours. Flammable aromatic polycarbonate resin composition. 2. The component (B) is a silicone compound containing a structural unit represented by at least one of the structural units represented by the following general formulas (2) and (3). Flame-retardant aromatic polycarbonate resin composition. [Chemical 2] [Chemical 3] (In formulas (2) and (3), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (4). Α1 to α3
Each independently represent 0 or 1. m1 represents an integer of 0 or more. Furthermore, in equation (2), m
When 1 is 2 or more, the repeating unit can be a plurality of repeating units different from each other. ) [Chemical 4] (In formula (4), Z ^{4 to} Z ⁸ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, α 4 to α 8 each independently represent 0 or 1, and m 2 represents 0. Or represents an integer greater than that. Further, in the formula (4), when m2 is 2 or more, the repeating units can each be a plurality of different repeating units.) 3. The flame-retardant aromatic polycarbonate resin composition according to claim 1, wherein the component (B) is a silicone compound composed of MD units or MDT units (where M is a monofunctional compound). Siloxane units, D is 2
Functional siloxane units, T is a trifunctional siloxane unit). 4. The acid value of component (A) is from 0.0 to 3.
It is 0 (mg equivalent acid / 10kgPC), The flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 3. 5. The amount of Si—H in the component (B) is 0.
The flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 4, which is 2 to 1.0 mol / 100 g. 6. The amount of aromatic groups in the component (B) is 15
The flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 5, which is -60% by weight. 7. The flame-retardant aromatic polycarbonate resin composition according to any one of claims 1 to 6, wherein the component (B) has a volatilization amount of 10% or less as measured by the heating weight loss method at 105 ° C. for 3 hours. . 8. Aromatic polycarbonate resin (A) 10
0.001 to 0.3 part by weight of at least one compound (C) selected from a radical generator, an organic alkali metal salt, and an organic alkaline earth metal salt is further added to 0 part by weight. Item 5. A flame-retardant aromatic polycarbonate resin composition according to any one of items 1 to 7. 9. A molded article formed from the flame-retardant aromatic polycarbonate resin composition according to claim 1.