JP2003082219A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition having excellent mechanical characteristics and excellent thin flowability and having good flame retardance given by a method scarcely giving loads to environments. SOLUTION: This resin composition comprises (A) an aromatic polycarbonate, (B) a liquid crystal polyester, and (C) a sulfur-containing organic metal salt compound, wherein the weight ratio of the component A/the component B is 98/2 to 40/60, and the amount of the component C is 0.01 to 0.8 wt.% per 100 pts.wt. of the total composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition comprising an aromatic polycarbonate, a liquid crystal polyester and a sulfur-containing organometallic salt compound. More specifically, rigidity,
The present invention relates to a resin composition having excellent flame retardancy and molding processability, which is particularly suitable for thin-walled molded products.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are resins having excellent heat resistance, impact resistance, dimensional stability, etc., and are used in the fields of electric / electronic parts, mechanical parts, automobile parts, and O.
Widely used in the field of A equipment parts. In particular, it is widely used as an exterior material in OA equipment by taking advantage of its dimensional stability and impact resistance. In recent years, however, light and thin products have become smaller and smaller. There is a strong demand for high rigidity that can maintain strength even when designed, good fluidity that can maintain molding processability, and high flame retardancy that can maintain product safety.

Conventionally, in order to improve the rigidity, a method of mixing a fibrous inorganic reinforcing material such as glass fiber and an inorganic filler has been used, but in that case, there is a drawback that the fluidity of the resin is impaired. Was.

Many methods have been proposed for improving rigidity and fluidity at the same time by blending a liquid crystal polymer into a thermoplastic resin and forming the liquid crystal polymer into fibers in the composition. Many attempts have been made to incorporate a liquid crystalline polymer into an aromatic polycarbonate resin, and JP-A-07-258531 and the like describe examples in which a fibrous inorganic reinforcing material is incorporated to further increase the rigidity. . Further, as shown below, attempts have been made to add a bromine-based flame retardant or a phosphorus-based flame retardant to impart flame retardancy.

However, the above flame retardants require a relatively large amount to achieve flame retardancy, and may not be suitable due to the influence on other properties. In recent years, flame-retardant resin materials containing no bromine compound or phosphorus compound have been demanded in consideration of the influence on the environment.

Japanese Unexamined Patent Publication No. 03-95255 describes a resin composition comprising a liquid crystal polymer having a specific structure and heat resistance, a thermoplastic resin such as polycarbonate, and an organic bromine compound. However, this publication only discloses the flame retardancy of the bromine compound when the liquid crystal polymer is the main component, and does not disclose the effect of the organic metal salt in the liquid crystal polyester.

Japanese Unexamined Patent Publication No. 07-331051 describes a resin composition comprising a polycarbonate resin, a liquid crystal polymer, a flame retardant, and polytetrafluoroethylene. This publication describes a flame-retardant resin composition containing a polycarbonate resin as a main component. When the main component is a polycarbonate resin, even if polytetrafluoroethylene as a flame-retardant aid is blended, the flame-retardant property is still sufficient. It is disclosed that is not obtained. On the other hand, such a publication also improves the flame retardancy by blending a relatively large amount of the flame retardant, and the effect of improving the flame retardancy by a small proportion of components, especially the organometallic salt in a resin composition containing a liquid crystal polymer. It did not disclose the effect.

Japanese Unexamined Patent Publication No. 8-134343 discloses a resin composition for a disk drive chassis which comprises a polycarbonate resin, a liquid crystalline resin, an inorganic fiber and a flame retardant. However, even in this publication, flame retardancy is improved by adding a relatively large amount of flame retardant, and the effect of the organic metal salt in the resin composition containing the liquid crystal polymer is not disclosed.

On the other hand, a proposal has already been made that the flame retardancy of a resin composition comprising an aromatic polycarbonate and a polyester is controlled by a flame retardant containing no bromine or phosphorus.

JP-A-57-151643 discloses a resin composition comprising a polyarylate composed of a dihydric phenol and an aromatic dicarboxylic acid, and a flame retardant amount of an alkali (earth) metal salt of an aromatic sulfonic acid. And a resin composition in which an aromatic polycarbonate resin is blended in a small proportion is disclosed. JP-A-57-31950 discloses an aromatic polyester (carbonate) derived from diphenol and isophthalic acid and / or terephthalic acid.
And a resin composition comprising an alkali metal salt of an organic acid or the like. Further, JP-A No. 11-181265 discloses a resin composition comprising a polycarbonate resin, a perfluoroalkanesulfonic acid alkali (earth) metal salt, and a polyester resin. However, in each of the publications, there is no description about the liquid crystal polyester, and the effect of the organic metal salt in the resin composition containing the liquid crystal polymer is not disclosed.

[0011]

SUMMARY OF THE INVENTION In consideration of the above problems, an object of the present invention is to improve the rigidity and fluidity, to reduce the environmental load, and to make the flame retardant with a relatively small amount of flame retardant. Another object of the present invention is to provide the aromatic polycarbonate resin composition.

The inventors of the present invention have made earnest studies to achieve such an object, and as a result, the aromatic polycarbonate, the liquid crystal polyester, and the resin composition containing the specific metal salt compound in a specific amount meet the above-mentioned object. The present invention has been completed and the present invention has been completed.

[0013]

The present invention provides (A) an aromatic polycarbonate (component A), (B) a liquid crystalline polyester (component B), and (C) a sulfur-containing organometallic salt compound (C).
Component), and the weight ratio of A component and B component is (A)
/ (B) = 98/2 to 40/60, and the ratio of the C component is 0.001 to 0.8 per 100% by weight of the total composition.
It is related to the resin composition which is wt%.

The present invention more preferably relates to the above resin composition further containing (D) a fibrous inorganic reinforcing material (component D) in an amount of 1 to 50% by weight based on 100% by weight of the total composition, Further, the present invention is more preferably (E) phosphoric acid, phosphorous acid,
And at least one compound (component E) selected from their esters or metal salts, 100% by weight of the total composition
The present invention relates to the above resin composition containing 0.01 to 3% by weight.

Further, the present invention preferably relates to the above resin composition, wherein the component C is an alkali (earth) metal salt of perfluoroalkanesulfonic acid.

The details of the present invention will be described below.

The aromatic polycarbonate as the component A used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor, and the reaction method is an interfacial polycondensation method, a melt transesterification method, or a carbonate. The solid-state transesterification method of a prepolymer, the ring-opening polymerization method of a cyclic carbonate compound, etc. can be mentioned.

As a typical example of the dihydric phenol,
2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4
-Hydroxyphenyl) -3-methylbutane, 9,9-
Bis {(4-hydroxy-3-methyl) phenyl} fluorene, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene and the like can be mentioned. In particular, a homopolymer of bisphenol A can be mentioned. Such an aromatic polycarbonate resin is preferable because it has excellent impact resistance.

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.

In producing an aromatic polycarbonate by reacting the above dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method,
If necessary, a catalyst, a terminal stopper, an antioxidant for preventing the dihydric phenol from oxidizing and the like may be used. The aromatic polycarbonate may be a branched polycarbonate obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Examples of trifunctional or higher polyfunctional aromatic compounds include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane. Can be used.

When a polyfunctional compound which gives a branched polycarbonate is contained, such a proportion is 0.001 to 1 mol%, preferably 0.001 of the total amount of the aromatic polycarbonate.
It is 5 to 0.5 mol%, particularly preferably 0.01 to 0.3 mol%. Further, particularly 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 0.5 mol%, particularly preferably 0.01 to 0.3 mol%. The ratio can be calculated by ¹ H-NMR measurement.

Further, it may be a polyester carbonate obtained by copolymerizing an aromatic or aliphatic difunctional carboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include an aliphatic bifunctional carboxylic acid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. The aliphatic difunctional carboxylic acid may be linear, branched or cyclic. The aliphatic difunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Preferred examples of the aliphatic difunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid.

Further, it is also possible to use a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing a polyorganosiloxane unit.

The aromatic polycarbonate is a mixture of two or more of the above-mentioned polycarbonates having different dihydric phenols, polycarbonates containing a branching component, various polyester carbonates, and various aromatic polycarbonates such as polycarbonate-polyorganosiloxane copolymers. It may be one. Further, various kinds of polycarbonates having different production methods shown below, polycarbonates having different terminal stoppers, and the like can be used as a mixture of two or more kinds.

In the polymerization reaction of aromatic polycarbonate, 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. In order to accelerate the reaction, for example, tertiary amines such as triethylamine, tetra-n-butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds,
It is also possible to use a catalyst such as a quaternary phosphonium compound. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is 1
The pH during the reaction is preferably maintained at 9 or higher for about 0 minutes to 5 hours.

Further, in such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such an end terminator. Specific examples of monofunctional phenols include, for example, phenol and p-tert.
-Butylphenol, p-cumylphenol and isooctylphenol. 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, and among them, diphenyl carbonate is preferable.

A polymerization catalyst can 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. A catalyst such as an alkaline earth metal compound such as calcium oxide, barium hydroxide or magnesium hydroxide, or a nitrogen-containing basic compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine or triethylamine can be used. In addition, alkali (earth) metal alkoxides, alkali (earth)
It is possible to use a catalyst which is usually used for esterification reaction and transesterification reaction of organic acid salts of metals, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds and the like. 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 × 1 with ^respect to 1 mol of the dihydric phenol as a raw material.
It is selected in the range of 0 ^-3 equivalent, more preferably 1 x 10 ^{-7 to} 5 x 10 ^-4 equivalent.

In the reaction by the melt transesterification method, in order to reduce the phenolic terminal group, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenyl carbonate are obtained at the latter stage or after the completion of the polycondensation reaction. Compounds such as phenyl carbonate can be added.

Further, in the melt transesterification method, it is preferable to use a deactivator which neutralizes the activity of the catalyst. The amount of the deactivator is 0.5 to 1 mol of the remaining catalyst.
It is preferably used in a proportion of 50 mol. Further, it is used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and particularly preferably 0.01 to 100 ppm, relative to the polycarbonate after polymerization. Preferable examples of the quenching agent include phosphonium salts such as dodecylbenzenesulfonic acid tetrabutylphosphonium salt and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.

The viscosity average molecular weight of the aromatic polycarbonate is not specified, but if the viscosity average molecular weight is less than 10,000, the strength and the like decrease, and if it exceeds 50,000, the molding processability decreases. 1,000-5
Those of 10,000 are preferable, and 12,000 to 30,000
It is more preferable that it is 00, and even more preferable that it be 18,000.
It is 0-28,000. In this case, it is naturally possible to mix with a polycarbonate having a viscosity average molecular weight outside the above range.

The viscosity average molecular weight in the present invention is calculated by the following formula: 100 ml of methylene chloride at 20 ° C.
Was obtained from a solution in which 0.7 g of aromatic polycarbonate was dissolved using an Ostwald viscometer. Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of methylene chloride drop, and t is the sample Solution drop seconds] 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 viscosity average molecular weight of the aromatic polycarbonate resin composition of the present invention is measured in the following manner. That is, the composition was dissolved in 20 to 30 times its weight of methylene chloride, the soluble matter was collected by filtration through Celite, and the solution was removed and sufficiently dried to obtain a solid matter of methylene chloride-soluble matter. obtain. The specific viscosity at 20 ° C. calculated from the above equation from a solution of 0.7 g of the solid dissolved in 100 ml of methylene chloride is measured by using an Ostwald viscometer.

The component B liquid crystal polyester used in the present invention is a thermotropic liquid crystal polyester,
It has the property that polymer molecular chains are aligned in a certain direction in the molten state. The morphology of such an array state may be any of a nematic type, a smectic type, a cholesteric type, and a discotic type, and may be two or more types. Further, the structure of the liquid crystal polyester may be any structure such as a main chain type, a side chain type, and a rigid main chain bent side chain type, but the main chain type liquid crystal polyester is preferable.

The form of the above-mentioned array state, that is, the property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the confirmation of the anisotropic molten phase was performed by using a Leitz polarization microscope and Lei
It can be carried out by observing the molten sample placed on the tz hot stage under a nitrogen atmosphere at a magnification of 40 times. The polymers of the present invention, when examined between crossed polarisers, transmit polarized light and exhibit optical anisotropy, even in the melt stationary state.

The heat resistance of the liquid crystal polyester may be in any range, but it is suitable that the liquid crystal polyester forms a liquid crystal phase by melting at a portion close to the processing temperature of the polycarbonate resin. In this respect, the deflection temperature under load of liquid crystal polyester is 15
A temperature of 0 to 280 ° C, preferably 180 to 250 ° C is more suitable. Such liquid crystal polyester belongs to the so-called heat resistance category II type. When it has such heat resistance, it is excellent in moldability as compared with type I having higher heat resistance, and good flame retardancy as compared with type III having lower heat resistance.

The liquid crystal polyester used in the present invention is
Polyester and polyesteramide are included, and aromatic polyester and aromatic polyesteramide are preferable, and aromatic polyester and polyester partially containing aromatic polyesteramide in the same molecular chain are also preferable examples.

Particularly preferred are wholly aromatic polyesters and wholly aromatic polyesteramides having as a constituent component one or more compounds selected from the group of aromatic hydroxycarboxylic acids, aromatic hydroxyamines and aromatic diamines. Is. More specifically, 1) a polyester mainly composed of one or more aromatic hydroxycarboxylic acids and derivatives thereof, 2) mainly a) one or more aromatic hydroxycarboxylic acids and derivatives thereof, and b ) One or more aromatic dicarboxylic acids, alicyclic dicarboxylic acids and derivatives thereof and c) at least one or two or more aromatic diols, alicyclic diols, aliphatic diols and their derivatives Polyester, 3) mainly a) one or more aromatic hydroxycarboxylic acids and their derivatives, b) one or more aromatic hydroxyamines, aromatic diamines and their derivatives, and c) aromatics Polyester amide consisting of dicarboxylic acid, alicyclic dicarboxylic acid and one or more kinds of derivatives thereof, 4) Mainly a) aromatic hydr At least one of xyloxycarboxylic acid and its derivative, b) at least one of aromatic hydroxyamine, aromatic diamine and its derivative, and c) aromatic dicarboxylic acid, alicyclic dicarboxylic acid and its Examples thereof include: d) a polyesteramide composed of one or more derivatives, and d) an aromatic diol, an alicyclic diol, an aliphatic diol, and at least one or more of derivatives thereof. Polyesters comprising one or more of group hydroxycarboxylic acids and their derivatives are preferred.

If necessary, a molecular weight modifier may be used in combination with the above-mentioned constituents.

Preferred examples of specific compounds constituting the liquid crystal polyester of the present invention include 2,6-naphthalenedicarboxylic acid, 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene and 6-hydroxy-2-naphthoic acid. Naphthalene compound, 4,4'-diphenyldicarboxylic acid, biphenyl compound such as 4,4'-dihydroxybiphenyl, p-hydroxybenzoic acid, terephthalic acid,
Para-substituted benzene compounds such as hydroquinone, p-aminophenol and p-phenylenediamine, and their nucleus-substituted benzene compounds (substituents are selected from chlorine, bromine, methyl, phenyl and 1-phenylethyl), isophthalic acid, Meta-substituted benzene compounds such as resorcin and the following general formula (I), (II) or (III)
Is a compound represented by. Among them, p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are particularly preferable, and a liquid crystal polyester obtained by mixing both is preferable. The former is preferably in the range of 80 to 50 mol%, more preferably 75 to 60 mol%, and the latter is preferably 20 to 50 mol%, and preferably 25 to 40 mol%.
Is more preferable.

[0042]

[Chemical 1]

[0043]

[Chemical 2]

[0044]

[Chemical 3]

(However, X is C₁~ C_FourAlkylene groups and
And alkylidene group, -O-, -SO-, -SO₂-,-
It is a group selected from S- and -CO-, and Y is-.
(CH₂) _n-(N = 1 to 4), and -O (CH₂)_nO
It is a group selected from-(n = 1 to 4). ) The liquid crystal polyester used in the present invention has the above-mentioned structure.
In addition to the components, an anisotropic melt phase is partially present in the same molecular chain.
It may be polyalkylene terephthalate which is not used.
In this case, the alkyl group has 2 to 4 carbon atoms.

The basic method for producing the above-mentioned liquid crystal polyester used in the present invention is not particularly limited, and it can be produced according to a known polyester polycondensation method. The above liquid crystalline polyester also has a concentration of at least about 2.0 dl / g, such as about 2.0-10.0 dl / g when dissolved in pentafluorophenol at a concentration of 0.1% by weight at 60 ° C.
The logarithmic viscosity value (IV value) of is generally shown.

The blending ratio of the (A) aromatic polycarbonate used in the present invention and the (B) liquid crystal polyester is such that the weight ratio is (A) / (B) = 98/2 to 40/60, preferably 98 /. 2 to 60/40, more preferably 98/2
The range is from 80/20. When the blending ratio of the liquid crystal polyester is larger than this range, good flame retardancy cannot be achieved, and when the blending ratio is smaller than this range, the effect of improving the fluidity due to the blending of the liquid crystal polyester cannot be obtained.

The sulfur-containing organic metal salt compound used as the component C of the present invention is preferably a metal salt of an organic sulfonic acid, and the metal is preferably an alkali metal or an alkaline earth metal. As the alkali metal, lithium,
Examples thereof include sodium, potassium, rubidium, and cesium, and examples of the alkaline earth metal include beryllium, magnesium, calcium, strontium, and barium, with lithium, sodium, and potassium being particularly preferable. Further, these can be used not only alone but also as a mixture of two or more kinds.

The organic sulfonic acid metal salt of the present invention includes an aliphatic sulfonic acid alkali metal salt, an aliphatic sulfonic acid alkali earth metal salt, an aromatic sulfonic acid alkali metal salt, and an aromatic sulfonic acid alkali. Examples thereof include earth metal salts.

Preferable examples of the aliphatic sulfonic acid metal salt include alkali alkane sulfonate (earth) metal salt, and a part of the alkyl group of the alkane sulfonate alkali (earth) metal salt is substituted with a fluorine atom. Examples thereof include alkali (earth) metal salts of sulfonic acid and alkali (earth) metal salts of perfluoroalkane sulfonic acid, and these can be used alone or in combination of two or more kinds (here, The expression of an alkali (earth) metal salt is used to include both an alkali metal salt and an alkaline earth metal salt).

Preferred examples of the alkanesulfonic acid used in the alkali (earth) alkanesulfonic acid metal salt include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, methylbutanesulfonic acid, hexanesulfonic acid, Heptanesulfonic acid, octanesulfonic acid and the like can be mentioned, and these can be used alone or in combination of two or more. 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., and especially the number of carbon atoms 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 is used as the alkali (earth) perfluoroalkane sulfonate.
Preferred examples of the metal salt include potassium perfluorobutane sulfonate.

The aromatic sulfonic acid used in the alkali (earth) aromatic sulfonic acid metal salt may be a monomeric or polymeric sulfonic acid of aromatic sulfide, a sulfonic acid of aromatic carboxylic acid and 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 monomeric or polymeric aromatic sulfide alkali (earth) metal salt of aromatic sulfide is described in JP-A-50-98539,
For example, diphenyl sulfide-4,4'-disodium disulfonate, diphenyl sulfide-4,4 '
And dipotassium disulfonate.

Alkali (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 No. 50-98544, and examples thereof include potassium sulfonate of benzene sulfonate.

As the monomeric or polymeric alkali (earth) aromatic sulfonic acid metal salt, there is disclosed 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.

Monomeric or polymeric alkali (earth) aromatic sulfone sulfonic acid metal salts are 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 alkali (earth) metal sulfonate 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.

The C component may also include alkali (earth) metal salts of sulfuric acid esters, particularly alkali (earth) metal salts of sulfuric acid esters of monohydric and / or polyhydric alcohols. it can. As the sulfuric acid ester of such monohydric and / or polyhydric alcohols,
Methyl sulfate ester, ethyl sulfate ester, lauryl sulfate ester, hexadecyl sulfate ester, polyoxyethylene alkylphenyl ether sulfate ester, pentaerythritol mono-, di-, tri-, tetra-sulfate ester, lauric acid monoglyceride sulfate ester, palmitic acid monoglyceride ester Examples thereof include sulfuric acid ester and sulfuric acid ester of stearic acid monoglyceride. Preferable examples of the alkali (earth) metal salt of these sulfates include alkali (earth) metal salts of lauryl sulfate.

Of the above-listed metal salt compounds of sulfonic acid or sulfuric acid ester, alkali (earth) metal salts of aromatic sulfonic acid and alkali (earth) metal salts of perfluoroalkane sulfonic acid are more preferable components. The alkali (earth) metal salts of perfluoroalkane sulfonic acids are particularly preferred.

The amount of the above-mentioned component C used in the present invention is 0.001 to 0.8% by weight based on 100% by weight of the total resin composition. Preferably 0.005-0.15% by weight,
It is more preferably 0.005 to 0.1% by weight, still more preferably 0.01 to 0.08% by weight. If the amount added is larger than this range, problems such as acceleration of decomposition of the aromatic polycarbonate occur, and if it is smaller than this range, the flame retardancy-improving effect cannot be obtained.

In the present invention, in order to further improve the rigidity and flame retardancy of the resin composition, it is more preferable to add a fibrous inorganic reinforcing material as the D component.

Examples of the D component fibrous inorganic reinforcing material include glass fiber, carbon fiber, metal fiber, asbestos, rock wool, ceramic fiber, slag fiber, potassium titanate whiskers, boron whiskers, aluminum borate whiskers, calcium carbonate whiskers, Examples thereof include titanium oxide whiskers, and fibers obtained by surface-coating these reinforcing agents with a different material such as a metal, and it is also possible to use a combination of two or more of these.

Among these fibrous inorganic reinforcing materials, glass fibers and carbon fibers are preferable, and carbon fibers (including metal-coated fibers) are particularly preferable. Since carbon fiber has good thermal conductivity, it is relatively difficult to make it flame-retardant in a thin wall. The present invention achieves good flame retardancy even in a composition containing such a carbon fiber with a small amount of an organic metal salt. Further, by containing a fibrous inorganic reinforcing agent such as carbon fiber, the effect of further improving flame retardancy is also exhibited.

The glass fiber and the carbon fiber can be selected and used from long fiber type (roving), short fiber chopped strand, milled fiber, and the like. The number average aspect ratio of the milled fiber is preferably 5 or more.

The component D fibrous inorganic reinforcing material includes a sizing agent (eg, polyvinyl acetate, urethane, acryl, polyester sizing agent, etc.), a coupling agent (eg, silane compound,
It may be treated with a boron compound, a titanium compound, etc.) or another surface treatment agent.

The blending amount of the fibrous inorganic reinforcing material of the component D is preferably 1 to 50% by weight in the total resin composition,
It is more preferably 5 to 30% by weight. If the blending amount exceeds 50% by weight, the moldability of the composition will be poor. Further, the ratio of the D component is preferably the following ratio in relation to the liquid crystal polyester of the B component. That is, the weight ratio of the B component and the D component is (B) / (D) = 30 / 70-
80/20 is preferable, and (B) / (D) = 3
More preferably 5/65 to 70/30,
It is more preferable that (B) / (D) = 40/60 to 65/35. In such a range, the moldability and mechanical properties such as weld properties are excellent. Further, the total weight ratio of the B component and the D component is 100% by weight of the total composition,
35% by weight or less, preferably 25% by weight,
This is a more preferable aspect in that both moldability and mechanical properties such as impact strength can be achieved at the same time.

In the case of the present invention, in order to more effectively exert the effect of improving the mechanical properties by fiberizing the liquid crystal polyester of the component B during injection molding, it is efficient if the liquid crystalline polyester is microdispersed in the matrix phase in advance. Target.
Therefore, it is preferable to mix at least one compound selected from phosphoric acid, phosphorous acid, and their esters or metal salts as the E component as a dispersion aid for microdispersing the liquid crystalline polyester in the matrix phase. .

Examples of the phosphoric acid or phosphorous acid ester of the present invention include trimethyl phosphate and tetrakis (2,4
Di-t-butylphenyl) -4,4'-biphenylene phosphonite, bis (2,6-di-t-butyl-4-)
Methylphenyl) pentaerythritol-diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-diphosphite, tris (2,4-)
Examples thereof include di-t-butylphenyl) phosphite, and phosphite ester is preferable, and pentaerythritol type phosphite ester is particularly preferable.

Further, examples of the metal salt of phosphoric acid or phosphorous acid of the present invention include metaphosphate, orthophosphate, hydrogen orthophosphate, and the like. Examples of the metal constituting the metal salt include Ia or IIa of the periodic table. Group elements are preferable from the viewpoint of blending effect, and examples thereof include sodium metaphosphate, sodium phosphite, monosodium phosphate, disodium phosphate,
Examples include trisodium phosphate, monobasic calcium phosphate, dibasic calcium phosphate, tribasic calcium phosphate, monopotassium phosphate, dipotassium phosphate, and tripotassium phosphate.

The compounding amount of at least one compound selected from phosphoric acid, phosphorous acid and the ester or metal salt thereof as the component E is preferably 0.01 to 3% by weight in the whole composition. , 0.01 to 0.8% by weight is more preferable. If the blending amount exceeds 3% by weight, the composition may have poor heat resistance and mechanical properties. Further, when it is 0.01% by weight or more, an effective fiberization promoting effect is exhibited.

In the resin composition of the present invention, other thermoplastic resins (for example, polyester, polyamide, polyacetal, modified polyphenylene ether, styrene resins such as ABS, acrylic resins, acrylic resins, etc. may be used as long as the object of the present invention is not impaired. Resin, polyolefin resin, polyphenylene sulfide, etc.), other flame retardants (eg brominated epoxy,
Brominated polystyrene, brominated polycarbonate, brominated polyacrylate, triphenyl phosphate, phosphate oligomer, phosphonic acid amide, silicone flame retardants, etc.), flame retardant aids (eg sodium antimonate, antimony trioxide, etc.), dripping prevention Agents (such as polytetrafluoroethylene capable of forming fibrils), nucleating agents (such as sodium stearate, ethylene-sodium acrylate), antioxidants (such as hindered phenol compounds), impact modifiers , UV absorber,
A light stabilizer, a release agent, a lubricant, a coloring agent and the like can be added. Further, in the present invention, various commonly known fillers such as glass flakes, wollastonite, kaolin clay, mica, and talc other than the fibrous inorganic reinforcing material can be used in combination according to the purpose of use.

Any method may be adopted for producing the resin composition of the present invention. For example, a method of pre-mixing each component, and optionally other components, then melt-kneading and pelletizing can be mentioned. As means for premixing,
A Nauter mixer, a V type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, etc. can be mentioned. In the pre-mixing, granulation may be carried out by an extrusion granulator or a briquetting machine, depending on the case. After premixing, the mixture is melt-kneaded by a melt-kneader typified by a vented twin-screw extruder, and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring container, but a vented twin-screw extruder is preferable. other,
It is also possible to adopt a method in which each component, and optionally other components, are independently pre-mixed and fed to a melt-kneader typified by a twin-screw extruder.

[0080]

EXAMPLES The present invention will be described in detail below with reference to examples. However, the present invention is not limited to these. In addition,
Various properties in the examples were measured by the following methods. The following raw materials were used as raw materials. (1) Mechanical properties: The bending test complies with ASTM D790, and the test piece shape has a length of 127 mm and a width of 12.7 mm.
× It carried out using the thing of thickness 3.2mm. The impact strength is in accordance with ASTM D256, and the test piece thickness is 3.2 m.
It was evaluated by measuring notched Izod impact strength at m. (2) Flammability: Evaluated by a method (UL94 standard) determined by Underwriters Laboratories, USA. When the thickness of the test piece was 0.8 mm, the case of passing the V-2 rank was marked with ◯, and the case of failing was marked with x. (3) Flowability: An Archimedes type spiral flow length with a flow path thickness of 1 mm and a flow path width of 8 mm was used with an injection molding machine (SG-150U, Sumitomo Heavy Industries, Ltd.) to obtain a cylinder temperature of 310.
C., mold temperature 80.degree. C., injection pressure 118 MPa. (4) Raw materials The following raw materials were used. (A) Polycarbonate resin: Panlite L-125
0WQ (Teijin Kasei Co., Ltd., viscosity average molecular weight 24,90
0) (B) Liquid crystalline polyester: Vectra A-950 (manufactured by Polyplastics Co., Ltd.) (C) Perfluoroalkanesulfonic acid potassium salt: Megafac F-114P (Dainippon Ink and Chemicals, Inc.)
(D-1) Glass fiber: ECS-03T-511, 13
μm diameter, 3 mm chopped strand (manufactured by Nippon Electric Glass Co., Ltd.) (D-2) Carbon fiber: Bethfight HTA-C6-
U, 7.5 μm diameter, 6 mm chopped strand (manufactured by Toho Tenax Co., Ltd.) (E) Distearyl pentaerythritol diphosphite: ADEKA STAB PEP-8 (manufactured by Asahi Denka Kogyo KK)

[Examples 1 to 6 and Comparative Examples 1 to 5] The components shown in Table 1 were dry blended in the proportions shown in Table 1, and then the diameter was 30 mmφ, L / D = 33.2, and the kneading zone was used. Using a vented twin-screw extruder (KTX30 manufactured by Kobe Steel, Ltd.) equipped with two screws, the mixture was melt-kneaded at a cylinder temperature of 300 ° C., extruded, and strand-cut to obtain pellets. The pellets were dried at 100 ° C. for 5 hours by a hot air circulation dryer. After drying, the injection molding machine (manufactured by Toshiba Machine Co., Ltd .: IS-150EN) uses a cylinder temperature of 300 ° C., a mold temperature of 80 ° C., and a molding cycle of 40.
A molded product for each characteristic molding was molded in seconds. Each characteristic was measured using these molded articles. The spiral flow length was measured by the above method. The results are shown in Table 1.

[0082]

[Table 1]

As is clear from the results shown in Table 1, blending the aromatic polycarbonate with the liquid crystal polyester improves mechanical properties and fluidity, but its flame retardancy is insufficient (Comparative Examples 1 to 1). 4) Furthermore, by adding a small amount of a sulfonic acid metal salt compound, flame retardancy can be imparted without impairing its properties (Examples 1 to 1).
6). In the impact strength evaluation, liquid crystal polyester is blended when the fibrous inorganic reinforcing material is contained as compared with the case where the fibrous inorganic reinforcing material is not contained (Example 1, Comparative Examples 1 and 2). As a result, it can be seen that the composition is less deteriorated and has more balanced characteristics (Examples 2 to 6 and Comparative Examples 3 to 5).

[0084]

EFFECTS OF THE INVENTION The aromatic polycarbonate resin composition of the present invention has high rigidity, good moldability, and is flame-retarded by a method having a small environmental load. It is useful for a wide range of applications, such as the field of OA equipment parts such as mechanical parts, and the field of automobile parts, and the industrial effect produced by it is exceptional.

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Claims (7)

[Claims] 1. An aromatic polycarbonate (A component), a (B) liquid crystal polyester (B component), and (C).
It is composed of a sulfur-containing organic metal salt compound (C component), and the weight ratio of the A component and the B component is (A) / (B) = 98/2 to 4
A resin composition in which the proportion of C component is 0/60 and 0.001 to 0.8% by weight based on 100% by weight of the total composition. 2. Further, (D) fibrous inorganic reinforcing material (component D)
The resin composition according to claim 1, which comprises 1 to 50% by weight based on 100% by weight of the total composition. 3. Further, at least one compound (E component) selected from (E) phosphoric acid, phosphorous acid, and their esters or metal salts is added to 0.0 per 100% by weight of the total composition.
The resin composition according to claim 1, which contains 1 to 3% by weight. 4. The resin composition according to claim 1, wherein the component B is an aromatic polyester composed of one or more of aromatic hydroxycarboxylic acid and derivatives thereof. 5. The resin composition according to claim 1, wherein the C component is an alkali (earth) metal salt of perfluoroalkanesulfonic acid. 6. The D-component is glass fiber.
The resin composition according to any one of 5 above. 7. The D-component is a carbon fiber, wherein the D-component is a carbon fiber.
The resin composition according to any one of 1.