JPH083397A - Flame retardant thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a flame-retardant, polycarbonate/ABS blend-type thermoplastic resin composition exhibiting an excellent flame retardancy in addition to high impact resistant properties, high fluidity and substantially satisfactory heat resistance. CONSTITUTION:This flame retardant thermoplastic resin composition contains (A) 90 to 50 pts.wt. polycarbonate, (B) 3 to 50 pts.wt. copolymer containing (a) an aromatic vinyl monomer unit and (b) vinyl cyanide monomer unit, (C) 50 to 1 pts.wt. copolymer containing (a) an aromatic vinyl monomer unit, (b) a vinyl cyanide monomer unit and (c) a rubbery polymer unit, (D) 1 to 30 pts.wt. composite rubber-based graft copolymer and (E) 1 to 30 pts.wt. flame retardant.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is a polymer alloy of polycarbonate (hereinafter abbreviated as PC) and acrylonitrile / styrene / butadiene copolymer (hereinafter also abbreviated as ABS), which has high HDT and excellent The present invention relates to a flame-retardant thermoplastic resin composition having impact strength and exhibiting good fluidity as compared with conventional PC / ABS polymer alloys.

[0002]

2. Description of the Related Art Aromatic PC resins have excellent mechanical strength,
Demand is increasing in a wide range of fields as a high-performance resin, that is, an engineering plastic that exhibits impact resistance, heat resistance, and electrical characteristics. However, the processing temperature of polycarbonate is relatively high, and therefore, the fluidity thereof is not sufficiently satisfactory.

Such an aromatic polycarbonate (P
C) by blending ABS resin with P
Techniques for improving the fluidity of C have been used for some time. (For example, JP-B-38-15225, JP-A-48-12170, JP-A-57-21530, and JP-A-5-21530.
No. 8-46269 and the like. )

Thus, ABS in polycarbonate
Although it has been disclosed that excellent fluidity and high impact resistance strength can be obtained by filling the composition with, it is pointed out that the flame retardancy of the polycarbonate resin is also lowered at the same time.

In order to solve the drawback that the flame retardant properties of PC / ABS blends are deteriorated, for example, JP-A-4-3581 is used.
As disclosed in Japanese Laid-Open Patent Publication No. 52-52, it is known to add a resorcinol tetraphenyl diphosphate flame retardant (hereinafter referred to as RDP). However, R
The use of DP reduces the heat resistance of the PC / ABS composition and thus places significant restrictions on the material's application.

[0006]

DISCLOSURE OF THE INVENTION According to the present invention, by incorporating a specific flame retardant, in addition to high impact resistance and high fluidity, a practically sufficient level of heat resistance and excellent flame retardancy are provided. An object of the present invention is to provide a flame-retardant PC / ABS resin composition that exhibits characteristics.

[0007]

Means for Solving the Problems An object of the present invention is to provide A) 90 to 50 parts by weight of an aromatic polycarbonate, B) (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer. A copolymer containing 3 to 50 parts by weight of a copolymer containing 50 to 1 parts of C) (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component and (c) a rubbery polymer. Parts by weight, D) 1 to 30 parts by weight of composite rubber-based graft copolymer, and E) 1 to 30 parts by weight of flame retardant.

The aromatic polycarbonate as the component (A) in the present invention may contain PC which is obtained by the conventionally known interfacial method or PC which is obtained by the melting method and which has a low end cap. This low end-capped PC is a PC / A
Good weld line strength of BS polymer blends is achieved (see US Pat. No. 5,055,523).

The low-end-capped PC in this case is obtained by melt polymerization of an aromatic dihydroxy compound and a carbonic acid diester, and its PC is a phenolic end group (I) and a non-phenolic end group (II). ) Equivalence ratio (I)
/ (II) is 1/19 or more, preferably 1/10 or more, and particularly preferably 1/5 or more. The ratio is 1
If it is less than / 19, the compatibility with the thermotropic liquid crystal polyester is not improved and layer peeling occurs, resulting in a decrease in mechanical strength, which is not preferable.

Preferably, the above-mentioned phenolic terminal group (I) has the following formula:

[0011]

Embedded image And the non-phenolic terminal group (II)

[0012]

Embedded image Indicated by. In the above formula, R ¹ and R ² are each independently substituted with a hydrogen atom, a straight chain or branched, unsubstituted or halogen atom having 20 or less carbon atoms, preferably a fluorine, chlorine or bromine atom. Represents an alkyl group.

The adjustment of the equivalent ratio of the terminal groups of the above-mentioned polycarbonate can be easily carried out by changing the molar ratio of the aromatic dihydroxy compound and the carbonic acid diester as the raw materials when the polycarbonate is produced by the melt polymerization.

For example, when bisphenol A is used as the aromatic dihydroxy compound and diphenyl carbonate is used as the carbonic acid diester, the terminal group of the polycarbonate is a phenolic residue derived from bisphenol A and a phenyl group derived from diphenyl carbonate.
When the molar ratio of bisphenol A is increased, the equivalent ratio (I) / (II) of the phenolic terminal group (I) and the non-phenolic terminal group (II) in the produced polycarbonate becomes large.

Further, the polycarbonate of the present invention may be branched. Such branched polycarbonates are obtained as branched thermoplastic random branched carbonates by reacting polyfunctional aromatic compounds with diphenols and / or carbonate precursors.

Conventionally used polycarbonates, particularly polycarbonates obtained by a method of reacting an aromatic dihydroxy compound such as bisphenol A with phosgene (in particular, an interfacial method), have a phenolic terminal group (I) and a non-phenolic group. The equivalent ratio (I) / (II) of the sex terminal group (II) is less than 1/19, which is not preferable.

The method itself for producing the polycarbonate of the present invention is known, and is a method for synthesizing a polycarbonate by transesterification reaction of an aromatic dihydroxy compound and a carbonic acid diester in a molten state.

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

[0019]

Embedded image (Wherein R ^a and R ^b are each independently a halogen or a monovalent hydrocarbon group, and X is —C (R ^c ) (R ^d ).
-, -C (= R ^e )-, -O-, -S-, -SO- or -SO _2- , 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-1-methylphenyl) propane, 1,1- Bis (hydroxyaryl) alkanes such as bis (4-hydroxy-t-butylphenyl) propane and 2,2-bis (4-hydroxy-3-bromophenyl) propane; 1,1-bis (4-hydroxyphenyl) Bis (hydroxyaryl) cycloalkanes such as cyclopentane and 1,1- (4-hydroxyphenyl) cyclohexane; 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, etc. Dihydroxy aryl ethers; 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,
Dihydroxydiaryl sulfides such as 3'-dimethylphenyl sulfide; 4,4'-dihydroxydiphenyl sulfoxide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide; 4,4'-dihydroxy Diphenyl sulfone,
Examples thereof include, but are not limited to, dihydroxydiarylsulfones such as 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone. 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

[0020]

[Chemical 4] (Wherein R ^f is each independently a hydrocarbon group having 1 to 10 carbon atoms or a halogen compound thereof or a halogen atom, and m is an integer of 0 to 4), for example, resorcin. , And 3-methylresorcin, 3-
Ethylresorcin, 3-propylresorcin, 3-butylresorcin, 3-t-butylresorcin, 3-phenylresorcin, 3-cumylresorcin, 2,3,4,6-tetrafluororesorcin, 2,3,4,6 -Substituted resorcins such as tetrabromoresorcin; catechol; hydroquinone, and 3-methylhydroquinone, 3-ethylhydroquinone, 3-propylhydroquinone, 3-butylhydroquinone, 3-t-butylhydroquinone, 3-phenylhydroquinone, 3-cumyl Hydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butylhydroquinone, 2,3,
Substituted hydroquinone such as 5,6-tetrafluorohydroquinone and 2,3,5,6-tetrabromohydroquinone, and the following formula

[0021]

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

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

The carbonic acid diester is not particularly limited, and examples thereof include 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, carbonates, dicyclohexyl carbonates, and the like. Diphenyl carbonate is preferably used.

These carbonate esters 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 the dicarboxylic acid and dicarboxylic acid ester 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, sebacine. Acids, decanedioic acid, dodecanedioic acid, diphenyl sebacate, diphenyl decanedioate, diphenyl dodecanedioate, and other aliphatic dicarboxylic acids; cyclopropanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid , 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclopropanedicarboxylic acid diphenyl, 1 , 2-Cyclobutanedicarboxylic acid diph Alkenyl, 1,3-cyclobutane dicarboxylic acid, diphenyl 1,2-cyclopentane dicarboxylic acid, diphenyl 1,3-cyclopentane dicarboxylic acid, diphenyl 1,2-cyclohexane dicarboxylic acid diphenyl, 1,
Examples thereof include alicyclic dicarboxylic acids such as diphenyl 3-cyclohexanedicarboxylic acid and diphenyl 1,4-cyclohexanedicarboxylic acid.

These dicarboxylic acids or dicarboxylic acid esters may be used alone or in combination of two or more. The dicarboxylic acid or dicarboxylic acid ester is contained in the carbonic acid diester in an amount of preferably 50 mol% or less, more preferably 30 mol% or less.

In producing a polycarbonate, it is also possible to use a polyfunctional compound having three or more functional groups in one molecule together with an aromatic dihydroxy compound and a carbonic acid diester. As these polyfunctional compounds, compounds having a phenolic hydroxyl group or a carboxyl group are preferable, and a compound containing three phenolic hydroxyl groups is 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-fodoxyphenyl) -1,4-diethylbenzene, α, α', α "-tris (4-hydroxyphenyl) -1,3,5-tri Isopropylbenzene, 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 and the like can be mentioned.

Particularly preferably, 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ', α "-tris (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like are used. The polyfunctional compound is preferably 0.03 mol or less, more preferably 0.001 to 0.02 mol, particularly preferably 0.001 to 0.01 mol, per mol of the aromatic dihydroxy compound. Used in quantity.

When producing polycarbonate,
The resulting polycarbonate has the following formula

[0031]

[Chemical 6] (Here, the aromatic ring or the chromanyl group may be substituted with halogen or an alkyl group having 1 to 9 carbon atoms.)
Further, a compound capable of introducing one or more of the terminal groups can be used. Examples of the compound capable of introducing the hydroxyl group represented by (1) include diol compounds such as bisphenol A. Further, as the compound capable of introducing the phenoxy group represented by (2), phenol, diphenyl carbonate and the like; as the compound capable of introducing the pt-butylphenoxy group represented by (3), pt-butylphenol, p -T-
Butylphenylphenylcarbonate, pt-butylphenylcarbonate, etc .; p-cumylphenol as a compound capable of introducing the p-cumylphenoxy group (p-phenylisopropylphenoxy group) represented by (4),
Examples thereof include p-cumylphenyl phenyl carbonate and p-cumyl phenyl carbonate. As the chromanylphenoxy group represented by (5) in the above formula,

[0032]

[Chemical 7] And a chromanylphenoxy group such as As a compound capable of introducing the group represented by (5-1)
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 -Four-
(3,5-dibromo-4-hydroxyphenyl) -6,8-dibromochroman and the like can be mentioned. Among them, 2,5
2,4-trimethyl-4- (4-hydroxyphenyl) chroman is preferred; 2,2,3-trimethyl-3- (4-hydroxyphenyl) as the compound capable of introducing the group represented by (5-2) Chroman, 2,2,3,6-tetramethyl-3- (3,5-dimethyl-4-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 can be mentioned, and of these, 2,2,3-trimethyl-3- (4-hydroxyphenyl) chroman is particularly preferable; (5- 3,4,4-trimethyl-2- (2-hydroxyphenyl) chroman, 2,4,4,6-tetramethyl-2- (3,5-dimethyl) as a compound capable of introducing the group represented by 3) 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 can be mentioned. Of these, especially 2,
4,4-trimethyl-2-2- (hydroxyphenyl) chroman is preferred; as a compound capable of introducing the group represented by (5-4), 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 can be mentioned, and of these, 2,4,4-trimethyl-2- (4-hydroxyphenyl) chroman is particularly preferable.

In the above, the aromatic ring or the aliphatic ring is
It may be further substituted with halogen or an alkyl group having 1 to 9 carbon atoms. These compounds may be used alone or in combination of two or more.

Aromatic dihydroxy compound 1 is preferred.
1.00 to 1.30 mol, especially 1.01 to mol
Both are reacted in the presence of a catalyst using a carbonic acid diester in an amount of 1.20 mol.

As the catalyst, for example, the applicant of the present invention can
The compounds proposed in 4-175368 can be used. As examples, (a) organic acid salts, inorganic acid salts, oxides of metals such as alkali metals and alkaline earth metals,
Preference is given to using hydroxides, hydrides or alcoholates. 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, stearin. Sodium acid, potassium stearate, lithium stearate, sodium borohydride, lithium borohydride,
Sodium phenyl borohydride, sodium benzoate, potassium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium salt of bisphenol A, dipotassium salt, dilithium salt, Sodium, potassium salt, lithium salt, etc. of phenol; calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium hydrogen carbonate, barium hydrogen carbonate, magnesium hydrogen carbonate, strontium hydrogen carbonate, calcium carbonate, barium carbonate, Examples thereof include magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, and strontium stearate, but are not limited thereto. These compounds may be used alone or in combination of two or more. These alkali metal compounds and / or alkaline earth metal compounds are preferably 10 ^-8 to 10 ^-3 mol, more preferably 10 ^-7 to 10 ^-6 mol, particularly preferably 1 mol of the aromatic dihydroxy compound. 10 ^-7 ~ 8
Used in an amount of × 10 ^-7 mol.

Further, as a catalyst, together with the above-mentioned alkali metal compound and / or alkaline earth metal compound, (b)
You may use a basic compound. As an example of the basic compound, for example, a nitrogen compound, specifically, an ammonium having an alkyl, aryl or araryl group such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide or trimethylbenzylammonium hydroxide. Hydroxides; tertiary amines such as trimethyleneamine, triethylamine, dimethylbenzylamine, triphenylamine; secondary or primary having alkyl groups such as methyl group, ethyl group, etc., aryl groups such as phenyl group, toluyl group, etc. Amines; ammonia; tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutylammonium tetraphenylborate, tetramethylammonium And the like can be mentioned basic salts such as tiger tetraphenylborate, but are not limited to. Of these, ammonium hydroxides are particularly preferable. These basic compounds may be used alone or in combination of two or more.

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

Alternatively, as a catalyst, (a) an alkali metal compound and / or an alkaline earth metal compound, (b)
A combination of a nitrogen-containing basic compound and at least one of (c) boric acid and boric acid ester can be used. When a catalyst composed of such a combination is used, (a) an alkali metal compound and / or an alkaline earth metal compound is used in an amount as described above, and (b) a nitrogen-containing basic compound is used in an amount of 1 mol of an aromatic dihydroxy compound. With respect to 10 ^-6 to 10 ^-1 mol, especially 10 ^-5
It is preferably used in an amount of 10 ⁻² mol. Examples of the boric acid or boric acid ester (c) include the following general formula B (OR ³ ) _n ′ (OH) _{3−n ′} (wherein R ³ is a hydrogen atom, an aliphatic hydrocarbon group, or an alicyclic carbon atom). A hydrogen group or an aromatic hydrocarbon group, and n'is 1 to
It is an integer of 3. ) Are preferred, and examples thereof include boric acid, trimethyl borate, triethyl borate,
Examples thereof include tributyl borate, trihexyl borate, triheptyl borate, triphenyl borate, tritolyl borate, and trinaphthyl borate. Of these, triphenyl borate is particularly preferable. 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 ^{- 5} to 1
It is preferably 0 ^-2 mol.

Conditions such as temperature and pressure at the time of the melt polymerization reaction are arbitrary, and known conventional conditions can be used. Specifically, the reaction in the first step is preferably 80 to 250.
C., more preferably 100 to 230.degree. C., particularly preferably 120 to 190.degree. C., preferably 0 to 5 hours, more preferably 0 to 4 hours, particularly preferably 0.25 to 3 hours.
Perform at normal pressure for time. Then, the reaction temperature is raised while the reaction system is under reduced pressure to cause the reaction between the aromatic dihydroxy compound and the carbonic acid diester, and finally, under the reduced pressure of 0.05 to 5 mmHg, the aromatic dihydroxy compound is heated at a temperature of 240 to 320 ° C. It is preferred to carry out the reaction of with a carbonic acid diester.

The reaction between the aromatic dihydroxy compound and the carbonic acid diester as described above may be carried out continuously or batchwise. Further, the reaction apparatus used when carrying out the above reaction may be of a tank type, a tube type, or a column type.

Next, the component (B) is a copolymer containing the aromatic vinyl monomer component (a) and the vinyl cyanide monomer (b). Examples of the aromatic vinyl monomer component (a) include styrene, α-methylstyrene, 0-, m-, or p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluoro. Examples thereof include styrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene and the like, and these are used alone or in combination of two or more.
Preferred are styrene and α-methylstyrene.

Examples of the vinyl cyanide monomer component (b) include acrylonitrile and methacrylonitrile, and one or more of these may be used. The composition ratio of these is not particularly limited and is selected according to the application.

The composition ratio of (a) / (b) is not particularly limited, but in the component (B), (a) is preferably 95-.
50% by weight, (b) is 5 to 50% by weight, more preferably (a) is 92 to 65% by weight, (b) ga8 to 3
It is 5% by weight.

Preferred examples of the component (B) include SAN
A resin (styrene-acrylonitrile copolymer) may be used.

There are no particular restrictions on the production of the copolymer of component (B), and generally known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization and emulsion polymerization can be used. It can also be obtained by blending separately copolymerized resins.

The blending ratio of the above components (A) and (B) is from 99 to 1 parts by weight of (B), preferably from 10 to 99 parts by weight of (A), relative to 1 to 99 parts by weight of (A). On the other hand, it is 90 to 1 part by weight of (B).

Next, the component (C) will be described. (C)
Is a copolymer containing (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer. (A) Aromatic vinyl monomer component and (b)
Examples of the vinyl cyanide monomer component include those shown in the above-mentioned component (b). Examples of the rubbery polymer (c) include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers. Diene rubbers such as polymers, random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butene,
Copolymers of ethylene and α-olefins, copolymers of ethylene-unsaturated carboxylic acid esters such as ethylene-methacrylate and ethylene-butyl acrylate, acrylic acid ester-butadiene copolymers, such as butyl acrylate-butadiene copolymer Acrylic elastic polymers such as polymer, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene non-conjugated diene terpolymer such as ethylene-propylene-hexadiene copolymer, butylene-isoprene copolymer, chlorinated polyethylene And these are used alone or in combination of two or more. Preferable rubbery polymers are ethylene-propylene non-conjugated diene terpolymer, diene rubber and acrylic elastic polymer, and styrene-butadiene copolymer in styrene-butadiene copolymer in this styrene-butadiene copolymer. It is a polymer, and the styrene content in this styrene-butadiene copolymer is preferably 50% by weight or less.

The component (C) includes the above-mentioned components (a),
In addition to (b) and (c), the monomer (d) copolymerizable with these components can be used within a range that does not impair the object of the present invention. Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth). ) Α, β such as acrylate, 2-ethyl (meth) acrylate, and 2-ethylhexyl methacrylate
-Unsaturated carboxylic acid esters; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-O-chlorophenyl Examples thereof include imide compounds of α, β-unsaturated dicarboxylic acid such as maleimide; and the like, and one or more of these monomers are used.

The copolymer of the component (C) is preferably a graft copolymer obtained by graft-copolymerizing the other component in the presence of the rubbery polymer (c), more preferably A.
BS resin (acrylonitrile-butadiene-styrene copolymer), AES (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer, AA)
S resin (acrylonitrile-acrylic elastic polymer-styrene copolymer).

In the component (C), each component (a),
The composition ratio of (b) and (c) is not particularly limited, and each component is blended depending on the application. Further, as the method for producing the copolymer of the component (C), the same method as the above-mentioned component (B) can be adopted.

Next, the component (D) used in the present invention is a polyorganosiloxane rubber component and a polyalkyl (meth).
It is a composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl-based monomers to a composite rubber having a structure in which an acrylate rubber component is alternately intertwined with each other to form a composite integral.

The production of such a composite rubber graft copolymer can be carried out, for example, by the method disclosed in JP-A-64-79257.

Such a composite rubber can be preferably produced by an emulsion polymerization method. First, a latex of polyorganosiloxane rubber is prepared, and then rubber particles of the polyorganosiloxane rubber latex are impregnated with a monomer for synthesis of an alkyl (meth) acrylate rubber,
It is preferred to polymerize the alkyl (meth) acrylate rubber synthesis monomer.

The organosiloxane rubber component can be prepared by emulsion polymerization using, for example, the following organosiloxane and cross-linking agent (I), in which case a graft crossing agent (I) can also be used in combination.

Examples of the organosiloxane include chain organosiloxanes such as dimethylsiloxane. Further, various cyclic organosiloxanes having a 3-membered ring or more, preferably a 3 to 6-membered ring can also be used. Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. . These organosiloxanes may be used alone or in admixture of two or more. The amount of these used is preferably 50% by weight or more, and more preferably 70% by weight or more in the polyorganosiloxane rubber component.

The crosslinking agent (I) may be trifunctional or tetrafunctional.
Functional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxylan, and tetrabutoxysilane can be used. In particular, a tetrafunctional crosslinking agent is preferable, and among these, tetraethoxysilane is particularly preferable. The crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used is 0.1 to 3 in the polyorganosiloxane rubber component.
0% by weight is preferred.

The graft crossing agent (I) has the following formula: CH ₂ ═C (R ² ) —COO— (CH ₂ ) _p —SiR ¹ _n O _{(3-N) / 2} (I-1) CH _{2 ^{= CH-SiR 1 n O (}} 3-n) / 2 (I-2) or ^{_{HS- (CH 2) p -SiR 1}} n O (3-n) / 2 (I-3) ( in the above formulas, R ¹ is a lower alkyl group, for example, a methyl group,
Represents an ethyl group, a propyl group or the like or a phenyl group, R
² represents a hydrogen atom or a methyl group, n represents 0, 1 or 2 and p represents an integer of 1 to 6. The compound which can form the unit shown by these is used. The above formula (I-1)
The (meth) acryloyloxysiloxane capable of forming the unit (1) has a high grafting efficiency, so that it can form an effective graft chain, and is advantageous in that it exhibits high impact resistance. Incidentally, methacryloyloxysiloxane is particularly preferable as the one capable of forming the unit of the formula (I-1). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltridimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxy. Examples thereof include propylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutoxybutyldioxymethylsilane and the like. These may be used alone or in combination of two or more. The amount of the graft crossing agent used is preferably 0 to 10% by weight in the polyorganosiloxane rubber component.
Is.

For the production of the latex of the polyorganosiloxane rubber component, the methods described in, for example, US Pat. Nos. 2,891,920 and 3,294,725 can be used. In the practice of the present invention, for example, an organosiloxane, a cross-linking agent (I), and optionally a mixture of a graft crossing agent (I) are added in the presence of a sulfonic acid-based emulsifier such as alkylbenzene sulfonic acid or alkyl sulfonic acid, for example, a homogenizer. It is desirable to produce it by a method of shear-mixing with water using the above. Alkylbenzene sulfonic acid is particularly preferable because it acts as an emulsifier of organosiloxane and at the same time serves as a polymerization initiator. At this time, a metal salt of alkylbenzene sulfonic acid,
It is preferable to use a metal salt of alkyl sulfonic acid in combination, because it has the effect of keeping the polymer constant during the graft polymerization.

Next, the polyalkyl (meth) acrylate rubber component constituting the above composite rubber may be synthesized by using the following alkyl (meth) acrylate, crosslinking agent (II) and graft crossing agent (II). it can.

As the alkyl (meth) acrylate,
For example, methyl acrylate, ethyl acrylate, n
-Propyl acrylate, n-butyl acrylate, 2
-Alkyl acrylates such as -ethylhexyl acrylate and hexyl methacrylates, 2-ethylhexyl methacrylate, alkyl methacrylates such as alkyl methacrylates such as n-lauryl methacrylate, and the like, and the use of n-butyl acrylate is particularly preferable.

Examples of the crosslinking agent (II) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate.

Examples of the graft crossing agent (II) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent. These crosslinking agents and graft crossing agents may be used alone or in combination of two or more. The total amount of these crosslinking agents and graft crossing agents used is preferably 0.1 to 20% by weight in the polyalkyl (meth) acrylate rubber component.

The polymerization of the polyalkyl (meth) acrylate rubber component is carried out by adding the above alkyl (meth) acrylate into the latex of the polyorganosiloxane rubber component neutralized by the addition of an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate. ) An acrylate, a cross-linking agent and a graft crossing agent are added and impregnated into the polyorganosiloxane rubber particles, and then a normal radical polymerization initiator is allowed to act. As the polymerization progresses, a crosslinked network of polyalkyl (meth) acrylate rubbers entwined with each other in the crosslinked network of polyorganosiloxane rubber is formed, and the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are substantially inseparable. A composite rubber latex of is obtained. In carrying out the present invention, as the composite rubber, the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the main skeleton of the polyalkyl (meth) acrylate rubber component is a repeating unit of n-butyl acrylate. A composite rubber having is preferably used.

The composite rubber thus prepared by emulsion polymerization can be graft-copolymerized with a vinyl monomer. The gel content measured by extracting this composite rubber with toluene at 90 ° C. for 12 hours is preferably 80% by weight or more.

In order to satisfy the balance of the flame retardant, impact resistance agent, appearance, etc., the ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component in the above composite rubber is 3 to The latter is preferably 97 to 10% by weight with respect to 90% by weight, and the average particle diameter of the composite rubber is preferably 0.08 to 0.6 μm.

As the vinyl-based monomer to be graft-polymerized on the above composite rubber, styrene, α-methylstyrene,
Aromatic alkenyl compounds such as vinyltoluene; methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate; various vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. Vinyl-based monomers are mentioned, and a particularly preferable vinyl-based monomer that can be used alone or in combination of two or more is methyl methacrylate. The vinyl-based monomer is the above-mentioned composite rubber 30.
It is preferably contained in a proportion of 5 to 70% by weight with respect to 95% by weight.

The composite rubber-based graft copolymer (D) is a composite rubber-based graft copolymer obtained by adding the above vinyl-based monomer to the above-mentioned composite rubber latex and polymerizing it in a single stage or multiple stages by a radical polymerization technique. The combined latex can be separated and recovered by introducing it into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salting out and coagulating.

Such a composite rubber graft copolymer (D) is commercially available, for example, from Mitsubishi Rayon Co., Ltd. as METABLEN S-2001.

The flame retardant of component (E) used in the flame retardant thermoplastic resin composition of the present invention is represented by the following formula

[0070]

Embedded image (Here, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, and R ¹ = R ² = R ³
Except when = R ⁴ = H. X'represents a divalent or higher valent organic group, P is 0 or 1, Q is an integer of 1 or more, for example, an integer of 30 or less, R is an integer of 0 or more) Is mentioned. However, it is not limited to these.

In the above formula (Formula 8), examples of the organic group include an alkyl group which may be substituted or not, a cycloalkyl group and an aryl group. When substituted, examples of the substituent include an alkyl group,
Examples thereof include an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, and a halogenated aryl group, and a group in which these substituents are combined (for example, an arylalkoxyalkyl group) or a substitution thereof. A group in which the groups are combined by an oxygen atom, a sulfur atom, a nitrogen atom or the like and combined (for example, an arylsulfonylaryl group) may be used as a substituent. The divalent or higher valent organic group is formed by removing one or more hydrogen atoms bonded to carbon atoms from the above-mentioned organic groups.
It means a group having a valency or higher. Examples include alkylene groups, and preferably (substituted) phenylene groups, polynuclear phenols such as those derived from bisphenols,
The relative position of two or more free valences is arbitrary. Particularly preferred are hydroquinone, resorcinol, diphenylol methane, diphenylol dimethyl methane,
Examples thereof include dihydroxydiphenyl, p, p'-dihydroxydiphenyl sulfone, bisphenol A, bisphenol S, dihydroxynaphthalene and the like.

Specific examples of the phosphate compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl. Diphenyl phosphate, diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, bis (2,3-dibromopropyl) -2,3-dichloropropylphosphate, tris (2,3 -Dibromopropyl) phosphate, and bis (chloropropyl) monooctyl phosphate, bisphenol A tetraphenyl diphosphate Bisphenol A tetra cresyl diphosphate, bisphenol A tetra xylylene diphosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetra cresyl diphosphate, hydroquinone tetra xylylene diphosphate,
Bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene, wherein R ¹ , to R ⁴ are alkoxy such as methoxy, ethoxy and propoxy, or preferably (substituted) phenoxy such as phenoxy, methyl (substituted) phenoxy. Triphosphates, preferably triphenyl phosphate and various bisphosphates.

The above component (E) is the component (A) to (D).
1 to 30 parts by weight, preferably 3 to 20 parts by weight, and preferably 5 to 15 parts by weight with respect to 100 parts by weight in total. If the amount of component (E) is less than the above range, the effect of the present invention is not sufficiently exhibited, and if it is more than the above range, heat resistance is impaired.

The composition of the present invention may further contain an anti-dripping agent. The fluorinated polyolefin that can be used as such an anti-dripping agent is commercially available or can be produced by a known method. It is, for example, 100-100 in an aqueous medium using a free-radical catalyst (eg sodium, potassium or ammonium peroxydisulfate).
1000 psi pressure and 0-200 ° C, preferably 2
It is a white solid obtained by polymerizing tetrafluoroethylene at a temperature of 0 to 100 ° C. See, for example, Brubaker US Pat. No. 23939.
See 67.

Although not essential, relatively large particles such as an average particle size of 0.3 to 0.7 mm (mainly 0.5 m)
It is preferable to use a resin in the state of particles of m). This is better than regular polytetrafluoroethylene powder with a particle size of 0.05-0.5 mm. The reason why such a relatively large particle size material is particularly preferred is that it readily disperses in the polymer and exhibits a tendency to bind the polymers together to form a fibrous material. Such a suitable polytetrafluoroethylene is called Type 3 according to ASTM and is actually DuPont (EI D
From upont de Nemoursand Company), Teflon 6 (Tef
lon 6) is commercially available. Alternatively, it can be obtained commercially as Teflon 30J manufactured by Mitsui DuPont Fluorochemicals. The fluorinated polyolefin is preferably 0.1% by weight based on 100 parts by weight of the component (A).
01 to 2 parts by weight, more preferably 0.05 to 1.0 parts by weight are used.

The flame-retardant thermoplastic resin composition according to the present invention may be used, in addition to the above-mentioned components, as long as the physical properties of the composition are not impaired, the resin may be mixed, molded or the like depending on its purpose. Other conventional additives such as pigments, dyes, reinforcing agents (glass fiber, carbon fiber, etc.), fillers (carbon black, silica, titanium oxide, etc.), heat-resistant agents, antioxidants, weathering agents, lubricants, Well-known additives such as a release agent, a crystal nucleating agent, a plasticizer, a fluidity improver, and an antistatic agent can be added.

There is no particular limitation on the method for producing the resin composition of the present invention, and ordinary methods can be satisfactorily used. However, melt blending is generally preferred. The use of small amounts of solvent is possible, but generally not required. As an apparatus, an extruder, a Banbury mixer, a roller, a kneader and the like can be mentioned as an example. These devices can be operated batchwise or continuously. The order of mixing the components is not particularly limited.

[0078]

The present invention will be further disclosed below with reference to Examples. In addition, "part" in an Example shows a weight part.

The materials used for carrying out the thermoplastic resin composition according to the present invention are as follows.

The component (A) polycarbonate is PC
(60) used LX polycarbonate (trade name; manufactured by Nippon GE Plastics Co., Ltd.), which has 60% of phenolic terminal groups and has low terminal sealing. Also, PC
For (1), a commonly available polycarbonate having a phenolic terminal group of 1% or less was used.

The following components were used for the other components. Ingredient (B) SAN resin: SR30B (trademark; manufactured by Ube Saikon Co., Ltd.) Component (C) ABS resin: UX050 (trademark; manufactured by Ube Saikon Co., Ltd.) Component (D) Metabrene S-2001 (trademark) (methyl methacrylate) -Butyl acrylate-dimethyl siloxane copolymer, Mitsubishi Rayon Co., Ltd. Component (E) (1) BPA tetraphenyl diphosphate: CR741 (trademark; manufactured by Daihachi Chemical Co., Ltd.) (2) BPA tetracresyl diphosphate: CR74
1C (trademark; manufactured by Daihachi Chemical Co., Ltd.) (3) Resorcinol diphosphate: CR733S
(Trademark; optional component manufactured by Daihachi Chemical Co., Ltd. Polytetrafluoroethylene: Teflon 3
0J (trademark; manufactured by Mitsui DuPont Fluorochemicals Co., Ltd.)

Using the above materials, a twin-screw extruder manufactured by Toshiba Machine Co., Ltd. was used.
Extrusion was performed at 00 rpm and a barrel temperature of 270 to 280 ° C., and the pellets were produced by cutting into a predetermined length.

Using the pellets thus produced, a test piece for flame retardancy test was molded by an 80t injection molding machine manufactured by Toyo Kikai Metal Co., Ltd. Molding conditions are barrel temperature 26
The mold temperature was set to 0 ° C and the mold temperature to 50 ° C.

The flame retardancy test is UL94 / V0, VI, VII.
The test based on the above was performed. Five test pieces were tested at a thickness of 1/16 inch according to the test method shown in Bulletin 94 "Combustion Test for Material Classification" (hereinafter referred to as UL-94) of Underwriters Laboratory Inc. According to this test method, the test material was rated to any one of UL-94 V-0, VI and V-II based on the results of the five data sources. The criteria for each V grade for UL-94 are outlined below.

V-0: The average flame holding time after removing the ignition flame is 5 seconds or less, and all the samples do not drop the fine flame igniting the absorbent cotton. VI: Average flame holding time after removing the ignition flame is 2
It is 5 seconds or less, and all the samples do not drop the fine flame that ignites the absorbent cotton. V-II: Average flame holding time after removing the ignition flame is 2
It is less than 5 seconds, and these samples fall through a fine flame igniting absorbent cotton.

Further, the tensile strength test was conducted using the standard AS.
It was carried out according to the TM method. In the examples, 70 parts by weight of PC (60) was used, and a test piece was prepared from a composition in which the amount ratio of other components was changed, and the flame retardancy and physical properties were measured. The component ratios of the composition and the test results are as shown in Tables 1 to 3.

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

[Table 3]

[0090]

[Effect] The physical properties of the molded product obtained from the flame-retardant thermoplastic resin composition according to the present invention are superior to those of the conventional product in flame retardant properties, and further excellent in impact resistance and tensile properties. Becomes

As described above, since it has excellent flame retardancy and good physical properties, especially high toughness, it can be expected to be applied to a wide range of applications.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location C08L 51/00 LKR LKS 51/08 LLS LLT 55/02 LMC LME LMF 69/00 LPP (72) Invention Hideyuki Itoi, 2-2 Kinugaoka, Moka City, Tochigi Prefecture, Japan Japan Plastics Co., Ltd.

Claims (2)

[Claims] 1. A) 90 to 50 parts by weight of a polycarbonate, B) 3 to 50 parts by weight of a copolymer containing (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer, and C ) (A) Aromatic vinyl monomer component, (b) Vinyl cyanide monomer component, and (c) Copolymer containing 50 to 1 part by weight of a rubber-like polymer, and D) Composite rubber-based graft copolymer A flame-retardant thermoplastic resin composition comprising: 1 to 30 parts by weight of a coalesce; and E) a flame retardant of 1 to 30 parts by weight. 2. The flame retardant according to claim 1, which is one or a combination of two or more selected from the group consisting of a) a phosphate compound, b) a brominated epoxy, and c) a brominated polycarbonate. Flame-retardant thermoplastic resin composition.