JP3281076B2 - Aromatic polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition containing an aromatic polycarbonate, an aromatic polyester, and a flame retardant, and more particularly, to the above resin composition having good heat stability during melting.

[0002]

2. Description of the Related Art Aromatic polycarbonates are usually produced by the phosgene method and are used in a wide range of applications because of their excellent properties such as impact resistance and heat resistance. On the other hand, polyesters are used in a wide range of fields such as household electric appliances and electronic equipment parts because of their excellent properties. Polyesters are often modified by incorporating the aforementioned polycarbonate resins due to their low impact resistance and low heat distortion temperature. For the above-mentioned applications, a high flame retardancy of V-0 is often required in UL94, and a flame retardant represented by an organic halogen compound and a flame retardant aid represented by antimony oxide are added. Has been carried out, such a resin composition is for example European Patent Application A
No. 0229957.

[0003]

However, if the above-described flame retardant and flame retardant are blended with the resin composition comprising the above-mentioned aromatic polycarbonate and polyester, the thermal stability during melting is impaired. It is. In order to improve the thermal stability during melting, attempts have been made to incorporate diantimony tetroxide as a flame retardant aid in addition to the organic halogen compound. However, even with this resin composition, when a higher molding temperature is required, or when the residence time in the molding machine is long, sufficient melting stability is not maintained.

Accordingly, the present invention provides a flame-retardant resin composition based on an aromatic polycarbonate and an aromatic polyester, which solves the above-mentioned drawbacks, improves the thermal stability during melting, and as a result has excellent mechanical properties. The purpose is to provide things.

[0005]

The present invention relates to a resin composition comprising A) 30 to 86 parts by weight of a polycarbonate, B) 10 to 50 parts by weight of an aromatic polyester, and C) 4 to 20 parts by weight of an organic halogen compound. Wherein the polycarbonate is a melt polymerization product of an aromatic dihydroxy compound and a carbonic acid diester, and D) an acidic sulfur-containing compound having a pKa ≦ 3, or a derivative formed therefrom with respect to the polycarbonate.
It is a resin composition containing 0.1 to 10 ppm.

[0006] The present resin composition has extremely good thermal stability when melted. As shown in the following Examples and Comparative Examples, the thermal stability of the present invention is remarkably improved as compared with a system using an aromatic polycarbonate produced by a conventional phosgene method and containing no sulfur-containing compound. .

Here, the melt polymerization product of the aromatic dihydroxy compound and the carbonic acid diester is a polycarbonate obtained by a melting method using the aromatic dihydroxy compound and the carbonic acid diester as raw materials. The melting method itself is known, and is a method for synthesizing a polycarbonate by a transesterification reaction of a dihydroxy compound and a carbonic acid diester in a molten state.

[0008] The aromatic dihydroxy compound is not particularly limited, and various known compounds can be used. As an example, the following expression

[0009]

Embedded image (Where ^Ra and ^Rb are each independently a halogen or a monovalent hydrocarbon group, and X is -C ( ^Rc ) ( ^Rd )
—, —C (＝ R ^e ) —, —O—, —S—, —SO— or —SO ₂ —, and R ^c and R ^d are each independently a hydrogen atom or a monovalent hydrocarbon group. R ^e is a divalent hydrocarbon group, and p and q each independently represent an integer of 0 to 4), for example, bis (4-hydroxyphenyl) methane, 1,1- Bis (4-hydroxyphenyl)
Ethane, 2,2-bis (4-hydroxyphenyl) propane,
2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy
Bis (hydroxyaryl) alkanes such as -1-methylphenyl) propane, 1,1-bis (4-hydroxy-t-butylphenyl) propane, and 2,2-bis (4-hydroxy-3-bromophenyl) propane Bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane; 4,4′-dihydroxydiphenyl ether, 4,4 ′ -Dihydroxyaryl ethers such as dihydroxy-3,3'-dimethylphenyl ether; 4,
Dihydroxydiaryl sulfides such as 4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide; 4,4'-dihydroxydiphenyl sulphoxide, 4,4'-dihydroxy-3,3'- Dihydroxydiarylsulfoxides such as dimethyldiphenylsulfoxide; dihydroxydiarylsulfones such as 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone; and the like. Not limited. Of these, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. In addition to the above, as the aromatic dihydroxy compound, the following general formula

[0010]

Embedded image (Where R ^f is independently a hydrocarbon group having 1 to 10 carbon atoms or a halide or a halogen atom, and m is an integer of 0 to 4), for example, Resorcinol, and 3-methylresorcinol, 3-ethylresorcinol, 3-propylresorcinol, 3-butylresorcinol, 3-t-butylresorcinol, 3-phenylresorcinol, 3-phenylresorcinol
Substituted resorcinols such as cumyl resorcin, 2,3,4,6-tetrafluororesorcin, 2,3,4,6-tetrabromoresorcin; catechol; hydroquinone, and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propyl Hydroquinone, 3-butylhydroquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,
Substituted hydroquinones such as 3,5,6-tetra-t-butylhydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromohydroquinone, and the following formula

[0011]

Embedded image 2,2,2 ', 2'-tetrahydro-3,3,3', 3'-tetramethyl-1,1'-spirobi- [1H-indene] -7,7'-diol represented by You can also.

These aromatic dihydroxy compounds may be used alone or in combination of two or more.

There are no particular restrictions on the carbonic diester. For example, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, diethyl carbonate, dimethyl carbonate, dibutyl Examples include, but are not limited to, carbonate, dicyclohexyl carbonate, and the like. Preferably, diphenyl carbonate is used.

These carbonates may be used alone or in combination of two or more.

The carbonic acid diester may contain a dicarboxylic acid or a dicarboxylic acid ester. Examples of dicarboxylic acids and dicarboxylic acid esters include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl terephthalate and diphenyl isophthalate; succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacin Acid, decandioic acid, dodecandioic acid, diphenyl sebacate, diphenyl decandioate,
Aliphatic dicarboxylic acids such as diphenyl dodecane diacid;
Cyclopropane dicarboxylic acid, 1,2-cyclobutane dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3 -Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diphenylcyclopropanedicarboxylate, diphenyl 1,2-cyclobutanedicarboxylate, diphenyl 1,3-cyclobutanedicarboxylate, diphenyl 1,2-cyclopentanedicarboxylate, 1,3 -Diphenyl cyclopentanedicarboxylate, diphenyl 1,2-cyclohexanedicarboxylate,
Alicyclic dicarboxylic acids such as diphenyl 3-cyclohexanedicarboxylate and diphenyl 1,4-cyclohexanedicarboxylate can be mentioned. These dicarboxylic acids or dicarboxylic acid esters may be used alone,
Further, two or more kinds may be used in combination. The dicarboxylic acid or dicarboxylic acid ester is added to the above-mentioned carbonic acid diester preferably in an amount of 50 mol% or less, more preferably 30 mol% or less.
It is contained in an amount of not more than mol%.

In producing the polycarbonate, a polyfunctional compound having three or more functional groups in one molecule can be used together with the aromatic dihydroxy compound and the carbonic acid diester. As these polyfunctional compounds, compounds having a phenolic hydroxyl group or a carboxyl group are preferable, and compounds having three phenolic hydroxyl groups are particularly preferable. Specific examples of preferred compounds include 1,1,1-tris (4-hydroxyphenyl) ethane, 2,2 ′, 2 ″ -tris (4-hydroxyphenyl) diisopropylbenzene,
α-methyl-α, α ′, α′-tris (4-hydroxyphenyl) -1,4-diethylbenzene, α, α ′, α ″ -tris (4-
(Hydroxyphenyl) -1,3,5-triisopropylbenzene, phloroglysin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane-2,1,3,5-tri (4 -Hydroxyphenyl) benzene, 2,2-bis- [4,4- (4,4'-dihydroxyphenyl) -cyclohexyl] -propane, trimellitic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, etc. Is mentioned. Particularly preferably, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″-
Use tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene or the like. The polyfunctional compound is preferably used in an amount of 0.03 to 1 mole of the aromatic dihydroxy compound.
It is used in an amount of at most mol, more preferably from 0.001 to 0.02 mol, particularly preferably from 0.001 to 0.01 mol.

Further, when producing polycarbonate,
The resulting polycarbonate has the following formula

[0018]

Embedded image (Here, the aromatic ring or the chromanyl group may be substituted with a halogen or an alkyl group having 1 to 9 carbon atoms.) A compound into which one or more terminal groups can be introduced can be further used. Examples of the compound capable of introducing a hydroxyl group represented by (1) include diol compounds such as bisphenol A. Further, phenol, diphenyl carbonate and the like as compounds capable of introducing a phenoxy group represented by (2); pt-butylphenol, pt-butylphenyl as compounds capable of introducing a pt-butylphenoxy group represented by (3) P-cumylphenol, p-cumylphenylphenyl as compounds capable of introducing a p-cumylphenoxy group (p-phenylisopropylphenoxy group) represented by (4), such as phenyl carbonate and pt-butylphenyl carbonate; Carbonate, p-cumylphenyl carbonate and the like can each be mentioned. As the chromanylphenoxy group represented by (5) in the above formula, the following formula:

[0019]

Embedded image And a chromanylphenoxy group. As a compound into which the group represented by (5-1) can be introduced, 2,2,
4-trimethyl-4- (4-hydroxyphenyl) chroman, 2,
2,4,6-tetramethyl-4- (3,5-dimethyl-4-hydroxyphenyl) chroman, 2,3,4-trimethyl-2-ethyl-4- (3-
Nonyl-4-hydroxyphenyl) -7-nonyl-chroman,
2,2,4-trimethyl-4- (3,5-diethyl-4-hydroxyphenyl) -6-ethylchroman, 2,2,4,6,8-pentamethyl-4-
(3,5-dimethyl-4-hydroxyphenyl) chroman, 2,
2,4-triethyl-3-methyl-4- (4-hydroxyphenyl)
Chroman, 2,2,4-trimethyl-4- (3-bromo-4-hydroxyphenyl) chroman, 2,2,4-trimethyl-4- (3-bromo
-4-hydroxyphenyl) -6-bromochroman, 2,2,4-trimethyl-4- (3,5-dibromo-4-hydroxyphenyl) -6-
Bromochroman, 2,2,4-trimethyl-4- (3,5-dibromo-4
-Hydroxyphenyl) -6,8-dibromochroman, among which 2,2,4-trimethyl-4-
(4-hydroxyphenyl) chroman is preferred; (5-2)
2,2,3-Trimethyl-3- (4-hydroxyphenyl) chroman and 2,2,3,6-tetramethyl-3- (3,5-dimethyl-4) as compounds into which the group represented by -Hydroxyphenyl) chroman, 2,3,4-trimethyl-2-ethyl-3- (3-nonyl-4
-Hydroxyphenyl) -7-nonyl-chroman, 2,2,3-trimethyl-3- (3,5-diethyl-4-hydroxyphenyl)-
6-ethyl-chroman, 2,2,3,6,8-pentamethyl-3- (3,
5-dimethyl-4-hydroxyphenyl) chroman, 2,2,3-
Triethyl-3-methyl-3- (4-hydroxyphenyl) chroman, 2,2,3-trimethyl-3- (3-bromo-4-hydroxyphenyl) -6-bromochroman, 2,2,3-trimethyl-3 -
(3,5-dibromo-4-hydroxyphenyl) -6-bromochroman, 2,2,3-trimethyl-3- (3,5-dibromo-4-hydroxyphenyl) -6,8-dibromochroman and the like. Among them, 2,2,3-trimethyl-3- (4-hydroxyphenyl) chroman is particularly preferred; 2,4,4-trimethyl is a compound into which the group represented by (5-3) can be introduced. -2- (2-hydroxyphenyl) chroman, 2,4,4,6-tetramethyl-2-
(3,5-dimethyl-2-hydroxyphenyl) chroman, 2,
3,4-trimethyl-4-ethyl-2- (3,5-dimethyl-2-hydroxyphenyl) -7-nonyl-chroman, 2,4,4-trimethyl-2- (3,5-dimethyl-2- (Hydroxyphenyl) -6-ethylchroman, 2,4,4,6,8-pentamethyl-2- (3,5-dimethyl
2-hydroxyphenyl) -6-ethylchroman, 2,4,4-trimethyl-2- (3-bromo-2-hydroxyphenyl) chroman, 2,4,4-trimethyl-2- (3-bromo-2 -Hydroxyphenyl) -6-bromochroman, 2,4,4-trimethyl-2- (3,5
-Dibromo-2-hydroxyphenyl) -6-bromochroman, 2,4,4-trimethyl-2- (3,5-dibromo-2-hydroxyphenyl) -6,8-dibromochroman, and the like. Among them, 2,2,4-trimethyl-2- (2-hydroxyphenyl) chroman is particularly preferable; as a compound into which the group represented by (5-4) can be introduced, 2,4,4-trimethyl-2- ( 4-Hydroxyphenyl) chroman, 2,4,4,6-tetramethyl-2-
(3,5-dimethyl-4-hydroxyphenyl) chroman, 2,
4,4-triethyl-2- (4-hydroxyphenyl) chroman,
2,3,4-trimethyl-4-ethyl-2- (3,5-dimethyl-4-hydroxyphenyl) -7-nonyl-chroman, 2,4,4-trimethyl-2- (3,5-diethyl- 4-hydroxyphenyl) -6-ethyl-chroman, 2,4,4,6,8-pentamethyl-2- (3,5-dimethyl
-4-hydroxyphenyl) -6-ethylchroman, 2,4,4-trimethyl-2- (3-bromo-4-hydroxyphenyl) chroman, 2,4,4-trimethyl-2- (3-bromo-4 -Hydroxyphenyl) -6-bromochroman, 2,4,4-trimethyl-2- (3,5-dibromo-4-hydroxyphenyl) -6-bromochroman, 2,
4,4-trimethyl-2- (3,5-dibromo-4-hydroxyphenyl) -6,8-dibromochroman and the like, among which 2,4,4-trimethyl-2- (4 -Hydroxyphenyl) chroman is preferred. In the above, the aromatic ring or the aliphatic ring may be further substituted with a halogen or an alkyl group having 1 to 9 carbon atoms. These compounds may be used alone or in combination of two or more. In the present invention, the proportion of the dihydroxy compound residue in the terminal group is preferably 50% or less, particularly preferably 30% or less.

Preferably, the aromatic dihydroxy compound 1
The diester carbonate is used in an amount of from 1.00 to 1.30 mol, in particular from 1.01 to 1.20 mol, per mol and the two are reacted in the presence of a catalyst.

[0021] As the catalyst, for example, the present applicant JP
The compounds proposed in 4-175368 can be used. For example, it is preferable to use (a) organic acid salts, inorganic acid salts, oxides, hydroxides, hydrides or alcoholates of metals such as alkali metals and alkaline earth metals. Specific examples of these compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium carbonate, sodium acetate, potassium acetate, lithium acetate, and stearin. Sodium, potassium stearate, lithium stearate,
Sodium borohydride, lithium borohydride, sodium borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium bisphenol A Salts, dipotassium salts, dilithium salts, phenol sodium salts, potassium salts, lithium salts and the like; calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, Strontium hydrogen carbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, stearic acid Magnesium, it can be mentioned strontium stearate, and the like. These compounds may be used alone,
Two or more kinds may be used in combination. These alkali metal compounds and / or alkaline earth metal compounds are preferably used in an amount of 1 mole per mole of the aromatic dihydroxy compound.
It is used in an amount of 0 ^-8 to 10 ^-3 mol, more preferably 10 ^-7 to 10 ^-6 mol, particularly preferably 10 ^-7 to 8 × 10 ^-7 mol.

As the catalyst, a basic compound (b) may be used together with the alkali metal compound and / or the alkaline earth metal compound. Examples of basic compounds include
For example, nitrogen compounds, specifically, ammonium hydroxides having an alkyl, aryl or araryl group, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide; trimethylamine, triethylamine ,
Tertiary amines such as dimethylbenzylamine and triphenylamine; secondary or primary amines having an alkyl group such as a methyl group and an ethyl group; and aryl groups such as a phenyl group and a toluyl group; ammonia; Examples include, but are not limited to, basic salts such as hydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, and tetramethylammonium tetraphenylborate. Of these, ammonium hydroxides are particularly preferred. These basic compounds may be used alone or in combination of two or more.

In the present invention, as the catalyst, (a) the above-mentioned alkali metal compound and / or alkaline earth metal compound,
And (b) a high molecular weight polycarbonate can be obtained with high polymerization activity by using a combination comprising a nitrogen-containing basic compound.

Alternatively, a combination of (a) an alkali metal compound and / or an alkaline earth metal compound, (b) a nitrogen-containing basic compound, and (c) boric acid or a boric acid ester as a catalyst, etc. Can be used. When a catalyst comprising such a combination is used, (a) an alkali metal compound and / or an alkaline earth metal compound are used in the amounts described above, and (b) a nitrogen-containing basic compound is added to 1 mole of an aromatic dihydroxy compound. It is preferably used in an amount of from 10 ^-6 to 10 ^-1 mol, especially from 10 ^-5 to 10 ^-2 mol, based on the total amount. (c) As the boric acid or borate ester, the following general formula B (OR ^g ) _r (OH) _3-r (where R ^g is a hydrogen atom, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group) Or r is an aromatic hydrocarbon group;
Are preferable, and examples thereof include: boric acid, trimethyl borate, triethyl borate, tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and boric acid. Trinaphthyl and the like can be mentioned. Of these, triphenyl borate is particularly preferred. These (c) boric acid or boric acid ester of the above (a), when used as a catalyst with (b), the amount 10 ^-6 10 ^-1 mole relative to 1 mole of the aromatic dihydroxy compound, particularly 10 ^{- It} is preferably from ⁵ to 10 ^-2 mol.

The conditions such as temperature and pressure during the melt polymerization reaction are arbitrary, and known conditions can be used.
Specifically, the first-stage reaction is preferably performed at 80 to 250 ° C.
More preferably 100-230 ° C, particularly preferably 120-19
The reaction is carried out at a temperature of 0 ° C., preferably for 0 to 5 hours, more preferably 0 to 4 hours, particularly preferably 0.25 to 3 hours at normal pressure. Next, the reaction temperature is raised while reducing the pressure of the reaction system to carry out the reaction between the aromatic dihydroxy compound and the carbonic acid diester, and finally 240 to 320 ° C. under a reduced pressure of 0.05 to 5 mmHg.
The reaction between the aromatic dihydroxy compound and the carbonic acid diester is preferably carried out at a temperature of

The reaction between the aromatic dihydroxy compound and the carbonic acid diester as described above may be carried out in a continuous manner or in a batch manner. Further, the reaction apparatus used for performing the above reaction may be a tank type, a tube type, or a tower type.

The aromatic polyester used in the present invention is also known per se, and is a polymer or a polymer obtained by a condensation reaction containing an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof as main components. It is a copolymer. As the aromatic dicarboxylic acid component, for example, dicarboxylic acid having a benzene nucleus such as terephthalic acid and isophthalic acid, naphthalene-1,5-dicarboxylic acid, and dicarboxylic acid having a naphthalene nucleus such as naphthalene-2,7-dicarboxylic acid or the like Ester-forming derivatives and the like. In addition, a small amount of a dicarboxylic acid other than the aromatic dicarboxylic acid, for example, adipic acid, sebacic acid or an ester-forming derivative thereof may be used. As the diol component, the formula HO (CH ₂ ) _n OH (n is 2 to
Glycols such as ethylene glycol, tetramethylene glycol, hexamethylene glycol and diethylene glycol, cyclohexanediol, neopentyl glycol, cyclohexanedimethanol, and 1,4-bisoxyethoxybenzene;
Examples thereof include diols having an aromatic ring such as bisphenol A, and ester-forming derivatives thereof. Preferred aromatic polyesters are poly (1,4-butylene) terephthalate, polyethylene terephthalate, 1,4-cyclohexylene dimethylene terephthalate / isophthalate copolymer, especially poly (1,4-butylene) terephthalate and polyethylene terephthalate . Its molecular weight is preferably 1: 1 between phenol and tetrachloroethane.
Intrinsic viscosity measured at 30 ° C using 1 weight ratio mixture as solvent
Those having a range of 0.50 or more, particularly preferably 0.55 or more, are used.

The organic halogen compounds used in the resin composition of the present invention include tetrachlorobisphenol A, tetrabromobisphenol A, tetrabromobutane, hexabromobutane, hexabromobenzene, decabromodiphenyl oxide, hexabromocyclododecane,
Chlorinated paraffin, perchlorocyclodecane, pentabromophenol, pentachlorophenol, tetrabromophthalic anhydride, tris (halopropyl) phosphate, tris (haloethyl) phosphate, pentabromotoluene, pentachlorotoluene, hexabromobiphenyl, perchlorocyclo Dodecane, chlorinated polyethylene, chlorinated polycarbonate, brominated polycarbonate, brominated epoxy, polychlorostyrene, polyvinyl chloride, ethylene bistetrabromophthalimide, polydibromophenylene oxide and the like can be mentioned. These organic halogen compounds may be used alone or in the form of a mixture of two or more.

When the resin composition according to the present invention contains less than 30 parts by weight of the polycarbonate obtained by the melting method, the mixture becomes brittle, and when it contains more than 86 parts by weight, the flame retardancy becomes insufficient. If less than 10 parts by weight of polyester is used, the heat distortion temperature will be too high for many applications, and if more than 50 parts by weight of polyester will be used, the mechanical properties will be insufficient. If the amount of the flame retardant is less than 4 parts by weight, sufficient flame retardancy cannot be achieved, and the resin composition having more than 20 parts by weight of the flame retardant exhibits corrosive behavior.

Further, the resin composition of the present invention has a pKa ≦ 3
Is contained in an amount of 0.1 to 10 ppm based on the polycarbonate obtained by the melting method. This improves the thermal stability of the resin composition of the present invention, and suppresses a decrease in molecular weight particularly during molding. Preferably, the sulfur-containing compound is contained in an amount of 0.5 to 5 ppm based on the polycarbonate. The sulfur-containing compound may be of any type as long as it is acidic or a derivative thereof having a pKa of 3 or less.

[0031]

Embedded image (Where R ^h is an alkyl group having 1 to 50 carbon atoms or a group in which a hydrogen atom in the group is substituted by a halogen atom, and R ⁱ is a hydrogen atom or an alkyl group having 1 to 50 carbon atoms or A group in which a hydrogen atom in the group is substituted by a halogen atom, and m 'is an integer of 0 to 3). Specific examples of these compounds include sulfonic acids such as benzene sulfonic acid and p-toluene sulfonic acid; methyl benzene sulfonate, ethyl benzene sulfonate, butyl benzene sulfonate, octyl benzene sulfonate, phenyl benzene sulfonate, p-toluene sulfone Sulfonates such as methyl acrylate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, phenyl p-toluenesulfonate; and trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated polystyrene And compounds such as methyl acrylate-sulfonated styrene copolymer, but are not limited thereto. Two or more of these compounds can be used in combination. Particularly preferably, butyl paratoluenesulfonate is used.

In the present invention, antimony oxide and / or fluorinated polyolefin can be mixed in order to further improve the flame retardancy and the dripping prevention. Here, antimony oxide includes antimony trioxide, antimony tetroxide, antimony pentoxide, antimony pentoxide, and the like. The fluorinated polyolefin includes polytrifluoroethylene, polytetrafluoroethylene, polyhexafluoropropylene, polychlorotrifluoroethylene, and the like.

The resin composition of the present invention may contain, in addition to the above-mentioned components, any conventional additives such as pigments, dyes, reinforcing agents, fillers, impact modifiers, heat-resistant agents, oxidation inhibitors, weathering agents,
It may contain a lubricant, a release agent, a crystal nucleating agent, a plasticizer, a flame retardant, a flow improver, an antistatic agent and the like.

The resin composition of the present invention can be obtained by mixing the above-mentioned components in an arbitrary order. In general, a melt mixing method is desirable. There is no particular limitation on the temperature and time required for melt mixing, and they can be appropriately determined depending on the composition of the material. Mixing equipment, especially extruders, Banbury mixers,
Radar, kneaders and the like are mentioned as examples.

The resin composition of the present invention is particularly suitable for molding by injection molding and extrusion molding, and the present invention also includes such molded articles.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited to the following Examples.

[0037]

【Example】

[0038]

Reference Example 1 Synthesis of Polycarbonate (PC1) by Melting Method Bisphenol A (Nihon GE Plastics Co., Ltd.)
0.44 mmol) and 0.44 mmol of diphenyl carbonate (manufactured by Any) were charged into a 250-liter stirred tank, purged with nitrogen, and then melted at 140 ° C.

Then, the temperature was raised to a temperature of 180 ° C., 0.011 mol of triphenyl borate was added, and the mixture was stirred for 30 minutes.

Next, as a catalyst, sodium hydroxide 0.000
44 mol and tetramethylammonium hydroxide 0.11
Mole was added and stirred for 30 minutes. Next, the temperature was raised to 210 ° C. and the pressure was gradually lowered to 200 mmHg. After 30 minutes, the temperature was raised to 240 ° C. and the pressure was gradually reduced to 15 mmHg. Thereafter, the temperature and pressure were kept constant, and the amount of phenol distilled out was measured. When the amount of phenol distilled out disappeared, the pressure was returned to atmospheric pressure with nitrogen. The time required for the reaction was 1 hour.

The intrinsic viscosity (η) of the obtained reaction product is 0.15 dl.
/ G.

Next, the pressure of the reaction product was increased by a gear pump, and the reaction product was inserted into a centrifugal thin film evaporator to proceed the reaction. The temperature and pressure of the thin film evaporator were controlled at 270 ° C. and 2 mmHg, respectively. 290 ° C, 0.2 mmHg from bottom of evaporator by gear pump
Biaxial horizontal stirring polymerization tank (L / D =
3, 40kg in the stirring blade rotation diameter 220mm, inner volume 80 liters)
/ Hour and polymerized at a residence time of 30 minutes.

Next, in a molten state, the polymer was supplied to a twin-screw extruder (L / D = 17.5, barrel temperature
285 ° C.), kneaded with 2 ppm of butyl p-toluenesulfonate with the resin, formed into a strand through a die, and cut with a cutter into pellets.

The intrinsic viscosity (IV) of the obtained polymer is 0.
It was 49 dl / g.

[0045]

Examples 1 to 7 and Comparative Examples 1 to 7 The following components were blended in the ratios (parts by weight) shown in Tables 1 and 2, and were heated at 270 ° C. in a 65 mm single screw extruder (L / D = 17.5). Extruded to make pellets. PC1: polycarbonate obtained by Reference Example 1 (containing 2 ppm of a sulfur compound) PC2: polycarbonate obtained by a phosgene method from bisphenol A (intrinsic viscosity: 0.50 dl / g) PBT: polybutylene terephthalate (trade name: Barox)
PET: polyethylene terephthalate (50/50 phenol / tetrachloroethane mixture, measured at 30 ° C., 0.3
FR-1: Brominated polystyrene [softening point of about 220 ° C and 6
Commercial polystyrene having a bromine content of 8.5% by weight,
Trademark Pyrocheck 68PBC, manufactured by Ferro] FR-2: Tetrabromobisphenol A (trademark Flay
Mukat 120G, manufactured by Tosoh Corporation FR-3: Tetrabromobisphenol A (TBBP
A) -A copolymer of bisphenol A (BPA) and phosgene, copolymer ratio: TBBPA / BPA / phosgene = 13
/ 20/67, bromine content 31% by weight The FR-3 was produced as follows. 2
m ³ of tank-type agitation tank bisphenol A (Japan Jiipu
74.6 mol, tetrabromo
Bisphenol A (trademark frame cut 120G, Tosoh
48.5 mol, 200 l dichloromethane
And 200 liters of ion-exchanged water.
A suspension was formed while blowing. Next, add
60 g of sodium drosulfite and sodium hydroxide
110 liters of an aqueous solution containing 540 moles of aluminum
Then, the above dihydroxy compound was dissolved at 15 ° C. This
250 mol of phosgene to the solution at a rate of 4.2 mol / min
Supplied. The reaction temperature rose to 36 ° C. Phosgene
After the blowing is completed, 32 g of triethylamine is added,
The reaction solution was further stirred for 60 minutes to carry out a polymerization reaction. That
After that, the reaction solution is allowed to stand, the organic layer is separated, and neutralized with hydrochloric acid.
Then, the substrate was washed with ion-exchanged water until the electrolyte disappeared. Profit
To dichloromethane solution of polycarbonate
100 liters and 250 liters of ion-exchanged water
And heated to 98 ° C to
Ruene is distilled off, and the brominated polycarbonate (F
A powder of R-3) was obtained. Sb ₂ O ₃ : Antimony trioxide T: Commercially available fluorinated polyolefin (trade name, Teflon, manufactured by DuPont) IM: Methyl methacrylate-butadiene-styrene copolymer (trade name, Kaneace B-56, manufactured by Kanegafuchi Kogyo Co., Ltd.)

Using the obtained pellets, each test piece was injection molded at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. using a 150 t molding machine.

The following points were evaluated for the above test pieces and pellets. * 1/8 "Izod impact strength (with notch): Impact strength of test specimen was measured according to ASTM D256. * Tensile strength: Tensile strength of test specimen was measured according to ASTM D638. * Initial MI (initial melt index): M of pellet
I was measured at a temperature of 250 ° C. and a load of 5 kg according to the method of JIS k7210. * 260 ° C./10 min MI: The same operation as the initial MI was performed on a 3 mm-thick molded plate injection-molded after staying at 260 ° C. for 10 minutes. * Silver streak: 3 mm thick molded plate obtained by injection molding from pellets without holding at 260 ° C, and 2
The occurrence of silver streaks was visually evaluated for the 3 mm-thick molded plate injection-molded after being retained at 60 ° C. for 10 minutes as follows: ：: no silver streaks were observed Δ: slight silver streaks were observed ×: Silver streak was observed in the entire molded product. In the table below, the silver streak of the molded plate obtained without holding at 260 ° C. was defined as “initial” and the molding obtained after holding was performed. The silver streak on the plate is indicated as "stagnant".

The results of the evaluation are shown in Tables 1 and 2.

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[Table 1]

[0050]

[Table 2]

[0051]

As is clear from the examples, the resin composition according to the present invention has better thermal stability at the time of melting than a resin composition containing a polycarbonate resin obtained by the phosgene method, and And the appearance of the molded article is very unlikely to deteriorate due to silver streaks (generated as a result of thermal decomposition).

Claims (3)

(57) [Claims] 1. A resin composition comprising: A) 30 to 86 parts by weight of a polycarbonate; B) 10 to 50 parts by weight of an aromatic polyester; and C) 4 to 20 parts by weight of an organic halogen compound, wherein the polycarbonate is an aromatic dihydroxy compound. D) an acidic sulfur-containing compound having a pKa ≦ 3 or a derivative formed therefrom, which is a melt polymerization product of the compound and a carbonic acid diester,
A resin composition containing 0.1 to 10 ppm. 2. The resin composition according to claim 1, wherein the sulfur-containing compound is butyl paratoluenesulfonate. 3. The resin composition according to claim 1, further comprising antimony oxide and / or fluorinated polyolefin.