JP2855486B2 - Flame retardant 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 flame-retarded resin composition containing a polycarbonate resin.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins are frequently used as engineering plastics because of their excellent physical properties. Various attempts have been made. Among them, a composition in which a phosphate compound is blended with an aromatic polycarbonate resin and an ABS resin has high flame retardancy. That is, excellent results are obtained in the UL94 combustion tests V0, V1, and V2. This flame retardancy evaluation test is performed using a bar-shaped sample having a length of 127 mm and a width of 12.7 mm. However, in such a resin composition, in the square plate test of the UL94 5V test, if the thickness of the square plate (152 × 152 mm) is less than 2.8 mm, a hole is formed and the test cannot be performed at 5 VA. Pass. Similarly, CSA standard C22.2 No.0.6 using square plate (100 × 150 mm)
In the test A of -M1982, if the thickness of the sample is less than 2.8 mm, the sample is rejected due to a hole or the like.

[0003] Aromatic polycarbonate resin and ABS
The resin composition containing the base resin has excellent physical properties such as impact resistance and dimensional accuracy, including interior and exterior of automobiles,
Widely used for housings of OA equipment. However, in particular, in housing applications of various devices, in order to respond to recent demands for cost reduction and weight reduction of devices, the trend toward thinning is increasing. Therefore, in thin housings, UL94 5V testing and C
Aromatic polycarbonate resin compositions that pass the SA test are desired.

[0004] Therefore, the present invention, even if molded to a thickness of less than 2.8 mm, passed 5VA in the UL94 5V test,
It is another object of the present invention to provide a polycarbonate-based resin composition having excellent flame retardancy that passes a CSA test.

[0005]

Means for Solving the Problems The flame-retardant resin composition of the present invention comprises (A) polycarbonate and / or the following formula (3):

[0006]

Embedded image And the following formula (Formula 4):

[0007]

Embedded image In the above formula, R and R 'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbonoxy group, and W is a divalent hydrocarbon group, -S-, -SS-, -O
-, -S (= O)-,-(O =) S (= O)-, or -C (= O)-, and n and n 'are each independently an integer of 0 to 4, X is a divalent aliphatic group having 6 to 18 carbon atoms, b is 0 or 1, and has a structural unit represented by the formula: ) And 2 to 30 of the total amount of the structural units of
Copolyestercarbonate which accounts for mol%
1 to 99 parts by weight, and (B) (b-1) a rubbery polymer, (b) an aromatic vinyl monomer component, and (c) a vinyl cyanide monomer component, A copolymer containing as a component, and / or a copolymer containing (b-2) an aromatic vinyl monomer component (b) and a vinyl cyanide monomer component (c) as a component of the copolymer And (C) 1 to 20 parts by weight of a phosphoric acid ester compound and (D) 0.1 to 10 parts by weight, based on 100 parts by weight of the total of (A) and (B). It is characterized by including.

The present invention is characterized in that the resins (A) and (B) are combined with the components (C), (D) and (E), and the resins (C), (D) and (E) )), If any one is missing, UL94 5V test with a thin square plate,
Test, CSA test, and test cannot be passed.

In the present invention, component (A) is a polycarbonate and / or copolyestercarbonate. The polycarbonate used in the present invention is an aromatic polycarbonate prepared by a known phosgene method or a melt method (see, for example, JP-A-63-215763 and JP-A-2-124934).

The copolyester carbonate used in the present invention must have the structural units represented by the above formulas (Chem. 3) and (Chem. 4). First, (Chemical 3)
The structural unit represented by is composed of a diphenol component and a carbonate component. The following formula (Formula 5) shows a diphenol that can be used to introduce a diphenol component.

[0011]

Embedded image In the above formula, R, R ', W, n, n' and b have the same meanings as described above. Regarding R and R ', examples of the halogen atom include a chlorine atom and a bromine atom. As a monovalent hydrocarbon group, a carbon number of 1 to 1
Alkyl group having 2 such as methyl group, ethyl group, propyl group, decyl group; cycloalkyl group having 4 to 8 carbon atoms such as cyclopentyl group and cyclohexyl group; aryl group having 6 to 12 carbon atoms such as Phenyl group, naphthyl group, biphenyl group and the like; aralkyl group having 7 to 14 carbon atoms such as benzyl group and cinnamyl group; or alkaryl group having 7 to 14 carbon atoms such as tolyl group and cumenyl group. And preferably an alkyl group. Examples of the hydrocarbon group of the hydrocarbon oxy group include the aforementioned hydrocarbon groups. Such a hydrocarbon oxy group is an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group or an alkaryloxy group, and an alkoxy group and an aryloxy group are preferred.

When W is a divalent hydrocarbon group,
Alkylene groups having 2 to 30 carbon atoms, such as alkylene groups having 1 to 30 carbon atoms, for example, methylene group, ethylene group, trimethylene group, octamethylene group, etc., or ethylidene group, propylidene group, etc .;
And a cycloalkylene group having 6 such as a cyclohexylene group, a cyclododecylene group or the like, or a cycloalkylidene group such as a cyclohexylidene group.

The diphenols useful in the present invention include, for example, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A); 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane ; 2,2-bis (3,5-
Dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-bis (4-hydroxy 1,4-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane 4,4-
Dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether, and the like.
The diphenols described in 2,999,835, 3,028,365, 3,334,154 and 4,131,575 can be used.

[0014] Examples of the precursor for introducing the carbonate component include phosgene and diphenyl carbonate.

Next, the structural unit represented by the chemical formula (4) comprises a diphenol component and a diacid component. For the introduction of the diphenol component, the same diphenol as described above can be used. The monomer used to introduce the diacid component is a diacid or an equivalent thereof. The divalent acid is, for example, an aliphatic diacid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. The divalent acid or its equivalent may be linear, branched, or cyclic. The aliphatic diacid is preferably α, ω-dicarboxylic acid. As such a divalent acid, for example, straight-chain saturated aliphatic dicarboxylic acids such as sebacic acid (decandioic acid), dodecandioic acid, tetradecandioic acid, icodecandioic acid, and the like are preferable, and sebacic acid and dodecane acid are preferable. Diacids are particularly preferred. Examples of the equivalent substance include the above-mentioned divalent acids, for example, acid halides such as acid chloride, and diaromatic esters such as diphenyl ester. However, the carbon number of the ester portion of the ester is not included in the carbon number of the acid described above. The above divalent acid or its equivalent may be used alone or in combination of two or more.

The copolyester carbonate used in the component (A) has the following two structural units represented by the following formulas (Chemical Formula 3) and (Chemical Formula 4) in the following proportions. That is, the amount of the structural unit represented by (Chem. 4) is 2 to 30 mol%, preferably 5 to 25 mol%, more preferably 7 to 20 mol% of the total amount of (Chem. 3) and (Chem. 4). It is. If the amount of the compound (Chem. 4) is less than 2 mol%, the transition temperature (Tg) is insufficiently lowered, so that the fluidity is lowered. If it is more than 30 mol%, excellent physical properties equivalent to polycarbonate, for example, mechanical strength, heat resistance and the like cannot be obtained.

The weight average molecular weight of the copolyester carbonate is usually from 10,000 to 100,000, preferably from 18,000 to 4
It is 0,000. Here, the weight average molecular weight is defined as GP weight using polystyrene corrected for polycarbonate.
C (gel permeation chromatography). Further, those having an intrinsic viscosity of 0.35 to 0.65 dl / g measured at 25 ° C. in methylene chloride are preferred.

The above-mentioned copolyester carbonate can be produced by a known polycarbonate production method, for example, an interfacial polymerization method using phosgene, a melt polymerization method, or the like. For example, it can be prepared by the methods described in US Pat. No. 4,238,596 to Quinn and US Pat. No. 4,238,597 to Quinn and Markezich. Specifically, first, an acid halide is formed prior to the reaction between the ester-forming group and the diphenol, and then reacted with phosgene. Goldberg (Goldb
erg) basic solution method (US Pat. No. 3,169,121)
In this, a pyridine solvent can be used, and a dicarboxylic acid is used. α, ω-dicarboxylic acid (eg sebacic acid)
A melt polymerization method using a diester of (for example, diphenyl ester) can also be used. A preferred production method is
U.S. Pat.No. 4,286,083 discloses Kochanowski.
nowski). In this method, a lower diacid such as adipic acid is converted into a salt form (preferably an alkali metal salt such as a sodium salt) in advance, and is added to a reaction vessel in which diphenol is present. During the reaction with phosgene, the aqueous phase is brought to an alkaline pH, preferably between about pH 8 and
9 and then a minimum of about 5 for the remaining reaction with phosgene.
At%, raise the pH to 10-11.

In the case of the interfacial polymerization method, for example, the bischloroformate method, it is preferable to use a general catalyst system well known in the synthesis of polycarbonate and copolyestercarbonate. Primary catalyst systems include amines such as tertiary amines, amidines or guanidines. Tertiary amines are commonly used, of which trialkylamines such as triethylamine are particularly preferred.

The copolyester carbonate of the component (A) has a sufficient impact strength even if the terminal is phenol, but pt-butylphenol, isononylphenol, isooctylphenol, m- or p-cumylphenol. By introducing a bulkier terminal group such as (preferably p-cumylphenol), a chromanyl compound, for example, chroman, a copolyester carbonate having better low-temperature impact properties can be obtained.

When component (A) contains both polycarbonate and copolyestercarbonate, the mixing ratio of both is arbitrary.

Next, the component (B) will be described. The component (B) is (b-1) and / or (b-2). First, (b-1) is a copolymer containing (a) a rubbery polymer, (b) an aromatic vinyl monomer component, and (c) a vinyl cyanide monomer component.

The rubbery polymer (a) used in the present invention includes a random copolymer and a block copolymer of polybutadiene, polyisoprene, and styrene-butadiene;
A hydrogenated product of the block copolymer, acrylonitrile
Diene rubbers such as butadiene copolymer, butadiene-isoprene copolymer, random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butene, ethylene and α-olefin Copolymer with ethylene, methacrylate, ethylene-unsaturated carboxylic acid ester such as butyl acrylate, acrylate-butadiene copolymer such as butyl acrylate-butadiene copolymer Ethylene-propylene non-conjugated diene terpolymers such as elastic polymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer, and butylene Isoprene copolymer, and chlorinated polyethylene and the like, to use them in one or more. Preferred rubbery polymers are ethylene-propylene rubber, ethylene-propylene non-conjugated diene terpolymer, diene rubber and acrylic elastic polymer, particularly preferably polybutadiene and styrene-
It is a butadiene copolymer, and the styrene content in the styrene-butadiene copolymer is preferably 50% by weight or less.

The vinyl cyanide monomer component (b) used in the present invention includes, for example, acrylonitrile, methacrylonitrile, etc., and one or more of these are used.

The aromatic vinyl monomer component (c) used in the present invention includes, for example, styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, Monobromostyrene, dibromostyrene, fluorostyrene, p-
Examples thereof include tert-butylstyrene, ethylstyrene, and vinylnaphthalene, and one or more of these are used. Preferred are styrene and α-methylstyrene.

In the present invention, (b-1) of component (B) includes, in addition to the above components (a), (b) and (c), (d) a monomer which can be copolymerized with these components. The body can be used as long as the object of the present invention is not impaired. Examples of such copolymerizable monomers include α, such as acrylic acid and methacrylic acid.
β-unsaturated carboxylic acid, methyl (meth) acrylate,
Α, β-unsaturated carboxylic esters such as ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl (meth) acrylate and 2-ethylhexyl methacrylate; maleic anhydride, itaconic anhydride Α, β-unsaturated dicarboxylic anhydrides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, No-chlorophenylmaleimide and the like, imide compounds of α, β-unsaturated dicarboxylic acid; These monomers are used alone or in combination of two or more.

In component (b-1), each component (a), (b)
The composition ratio of (c) and (c) is not particularly limited, and each component is blended according to the use.

The copolymer of the component (b-1) includes (a)
A graft copolymer in which other components are graft-copolymerized in the presence of a rubbery polymer is preferable, and more preferably an ABS resin (acrylonitrile-butadiene-styrene copolymer) and an AES resin (acrylonitrile-ethylene-propylene-styrene) Copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer), and AAS resin (acrylonitrile-acrylic elastic polymer-styrene copolymer).

There are no particular restrictions on the method for producing the copolymer of component (b-1), and generally known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization are used. It is also possible to obtain the component (b-1) by blending separately copolymerized resins.

The component (B) (b-2) is a copolymer containing (b) an aromatic vinyl monomer component and (c) a vinyl cyanide monomer component. Specific examples of these include:
The above (b-1) includes those shown as (b) and (c), and the composition ratio thereof is not particularly limited and is selected according to the application. Preferred (b-2) is
SAN resin (styrene-acrylonitrile copolymer). In addition, the method for producing the copolymer of the component (b-2) can be the same as that of the above (b-1).

The preferred component (B) is a blend of (a) a graft copolymer obtained by graft copolymerizing other components in the presence of a rubbery polymer and a copolymer of (b-2). .

The mixing ratio of the above components (A) and (B) is such that (B) is 99 to 1 part by weight based on 1 to 99 parts by weight of (A).
(B) is 90 to 5 parts by weight with respect to 10 parts to 95 parts by weight of (A).

The component (C) phosphate compound used in the present invention is represented by the following formula (Formula 6):

[0034]

Embedded image [Here, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, but R ¹ = R ² =
X 'represents a divalent or higher valent organic group, p is 0 or 1, q is an integer of 1 to 30, R ³ = R ⁴ = H is excluded.
r represents an integer of 0 or more; provided that when r = 0, the following cases are excluded: (i) R ¹ = R ³ = φ, and R ⁴ = φ− (R ⁵ −
_φ) 2; _(ii) in ^{R 1} = ^φ, and ^{R 3 = R 4 = φ-} R 5 -φ; (iii) in ^R 1 = R ³ = φ, and ^{R 4} = ^{φ-R 5} -
φ; or (iv) R ¹ = R ³ = R ⁴ = φ-R ⁵ -φ; wherein φ represents a phenyl group substituted or unsubstituted with an alkyl group, and R ⁵ represents a direct bond; -C
H ₂ —, —CH (CH ₃ ) — or — (CH ₃ ) C (C
H ₃ ) —represents a group].

In the above formula, examples of the organic group include an alkyl group which may or may not be substituted, a cycloalkyl group and an aryl group. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, and a halogenated aryl group. Combined groups (eg, arylalkoxyalkyl groups, etc.) or groups obtained by combining these substituents with an oxygen atom, sulfur atom, nitrogen atom, etc. (eg, arylsulfonylaryl groups, etc.) may be used as a substituent. Good. The divalent or higher valent organic group means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above-described organic group. For example, an alkylene group, and preferably (substituted)
Examples include phenylene groups and those derived from polynuclear phenols such as bisphenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred are:
Hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p'-dihydroxydiphenylsulfone, dihydroxynaphthalene and the like can be mentioned.

Specific examples of the phosphoric ester 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-dichloropropyl phosphate, tris (2,3-dibromopropyl) phosphate and bis (chloropropyl) monooctyl phosphate, wherein R ^{1 to} R ⁴ are alkoxy such as methoxy, ethoxy and Propoxy, or preferably (substituted) phenoxy, such as bisphenol A bisphosphate, which is phenoxy, methyl (substituted) phenoxy, hydroquinone bisphosphate, resorcinol bisphosphate, trioxybenzene triphosphate, and the like, preferably triphenyl phosphate and Various bisphosphates.

The above component (C) is added in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight, based on a total of 100 parts by weight of the components (A) and (B). If the amount of the component (C) is less than the above range, the effects of the present invention will not be sufficiently exhibited, and if it is more than the above range, heat resistance will be impaired.

The component (D) polyorganosiloxane used in the present invention is known per se and can be represented by, for example, the following general formula (Formula 7).

[0039]

Embedded image (In the above formula, R _x is each independently a hydrogen atom, an aromatic group, an aliphatic group or an alicyclic group, and m is 0 or 1
Specific examples of R _x include, in the case of an aromatic group, an aryl group such as a phenyl group, a xylyl group, and a tolyl group; a halogenated aryl group such as a chlorophenyl group; a phenylethyl group;
An aralkyl group such as a benzyl group; in the case of an aliphatic group, an alkyl group such as a methyl, ethyl, or propyl group;
Examples thereof include alkenyl groups such as vinyl group, propenyl group and butenyl group; cyanoalkyl groups such as cyanoethyl group and cyanobutyl group; haloalkyl groups such as chlorobutyl group; and cycloaliphatic groups such as cyclohexyl group. R _x may be the same or different. R _x is preferably selected from methyl, phenyl and vinyl. A product obtained by adding a reactive functional group, for example, an epoxy group, an amino group, a carboxylic acid group, a carboxylic acid ester group, a mercapto group, a hydroxyl group, etc. to a part of the polyorganosiloxane represented by the above formula (Formula 7), or A kneaded product obtained by kneading the polyorganosiloxane represented by the above formula (Formula 7) with a polyolefin resin or the like can also be used as the component (D). Such kneaded materials are disclosed in, for example, JP-A-3-21611, JP-A-3-21612, and JP-A-3-21613. The component (D) in the present invention also includes polysiloxane in which a siloxane bond has a three-dimensional network structure and an organic group is bonded to a silicon atom, for example, Tospearl (trade name, manufactured by Toshiba Silicone Co., Ltd.).

Component (D) is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total of components (A) and (B).
Use 5 to 5 parts by weight. If the amount is less than the above range, the effect of the invention is not sufficiently exhibited.

The resin composition of the present invention further contains (E) a fluorinated polyolefin as an anti-dripping agent. The fluorinated polyolefin can be obtained commercially or can be produced by a known method. that is,
For example, tetrafluoroethylene is polymerized in an aqueous medium at a pressure of 100 to 1000 psi and a temperature of 0 to 200 ° C, preferably 20 to 100 ° C, using a free radical catalyst (eg, sodium, potassium or ammonium peroxydisulfate). Is obtained as a white solid. For more information, see Bruker
Baker, U.S. Pat. No. 2,393,967. Although not essential, relatively large particles, e.g.
mm) is preferably used. This is better than regular polytetrafluoroethylene powders having a particle size of 0.05-0.5 mm. The reason that such relatively large particle size materials are particularly preferred is that they readily disperse in the polymer and tend to combine the polymers to form a fibrous material. Such a suitable polytetrafluoroethylene is what is referred to as type 3 according to ASTM and is in fact DuPont (EID).
upon de Nemours and Compa
ny) as Teflon 6 (Teflon 6). Alternatively, it can be commercially obtained as Teflon 30J from Mitsui DuPont Fluorochemicals. The fluorinated polyolefin is used in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 1.0 part by weight, per 100 parts by weight of the component (A).
Use parts by weight.

The resin composition of the present invention may contain, in addition to the above components, other additives, such as pigments, which are commonly used according to the purpose at the time of mixing and molding the resin, as long as the physical properties are not impaired. Dyes, reinforcing agents (glass fiber, carbon fiber, etc.),
Adding fillers (carbon black, silica, titanium oxide, etc.), heat-resistant agents, antioxidant inhibitors, weathering agents, lubricants, release agents, crystal nucleating agents, plasticizers, flow improvers, antistatic agents, etc. Can be.

The method for producing the resin composition of the present invention is not particularly limited, and ordinary methods can be used satisfactorily. However, the melt mixing method is generally preferred. The use of small amounts of solvents is possible but generally not necessary. Examples of the apparatus include, in particular, an extruder, a Banbury mixer, a roller, a kneader, etc., which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

[0044]

The present invention will be described in more detail with reference to the following examples.
explain. In the examples, the following components were used.
Was.Component (A)  PC: polycarbonate of bisphenol A (trademark;
Kisane, Nippon GE Plastics Co., Ltd.), salt
0.50 dl / g intrinsic viscosity measured at 25 ° C. in methylene chloride CPEC: copolyester ka produced as follows
-Carbonate: 7.2 g of dodecane diacid (DDDA) (31
Mmol) and 2.7 g of NaOH tablets (68 mmol)
Is dissolved in 180 ml of water, and disodium
A salt was produced. Next, a sample outlet is provided at the bottom, and
Into a 2000ml Molton flask with 5 ports
Stirrer blade, pH measuring end, injection tube and dry ice condenser
A claisen adapter with a denser was attached. this
In a polymerization flask, add 71 g (311 mm) of bisphenol A.
Mol), 0.9 ml of triethylamine, p-cumylfe
2.0 g (9 mmol) of phenol, methylene chloride 22
0 ml and the previously prepared disodium salt of DDDA
I charged. Subsequently, the flask was charged with 2 phosgene.
Injected at a rate of g / min. At this time, 50% NaOH aqueous solution
The solution was brought to pH 8 for 10 minutes while adding the solution through the injection tube.
Maintained. After that, continue to inject more phosgene
Add a 50% NaOH aqueous solution from the injection tube to
H was adjusted to 10.5 and maintained at this pH for 10 minutes. use
The total amount of phosgene that was added was 40 g (400 mmol)
there were. After the reaction, adjust the pH of the solution to 11 to 11.5.
And the organic solvent phase was separated from the aqueous phase. Organic solvent phase
Three times with 300 ml of 2% hydrochloric acid, and then with 30 parts of ion-exchanged water.
After washing 5 times with 0 ml, dry with anhydrous magnesium sulfate
And filtered. Put this in 1500 ml of methanol
To precipitate the polymer. Filter the resulting polymer by filtration
Separate, once with 500 ml of methanol and then ion exchange.
After washing four times with 500 ml of water replacement, at 110 ° C for 15 hours
Dried. Thus, the structures of the following formulas (Formula 8) and (Formula 9)
Copolyester having units in a 90:10 molar ratio
-Carbonate was obtained. This intrinsic viscosity (in methylene chloride
(Measured at 25 ° C.) was 0.50 dl / g. Below
This is abbreviated as CPEC.

[0045]

Embedded image

[0046]

Embedded image Component (B) b-1: ABS resin, trademark UX 050 (manufactured by Ube Saikon Corporation) b-2: SAN resin, trademark SR 30B (manufactured by Ube Saikon Co., Ltd.) Component (C) CR733S: trademark, phenylresorcinol polyphosphate, large Hachi Chemical Co., Ltd. TPP: Triphenyl phosphate component (D) TSF-437: Trademark, manufactured by Toshiba Silicone Co., Ltd., polymethylphenylsiloxane siligraft-210:
Trademark, manufactured by Nippon Unicar Co., Ltd., low density polyethylene-modified polysiloxane, silicone content 60% component (E) Teflon 30J: trademark, polytetrafluoroethylene,
The components of Examples 1 to 4 and Comparative Examples 1 to 3 manufactured by Mitsui Dupont Fluorochemical Co., Ltd. were mixed at the ratio (weight ratio) shown in Table 1 and 280
Single screw extruder (65mm) set at 100 ° C and 100 ° C
And extruded to produce pellets. Next, the pellets were injection molded at a set temperature of 280 ° C. and a mold temperature of 80 ° C. The Izod impact strength of the obtained molded product was measured, and the flame retardancy was evaluated. Table 1 shows the results.

The evaluation test of the resin composition is as follows.
I went there. (1) Izod impact strength (Kg-cm / cm) Measured according to ASTM D 256 with 1/8 inch thickness and notch.
Specified. (2) Flame retardancy testUL94 / V0, VI, VII test  Underwriters Laboratories In 5 Test Bars
Corporation's Bulletin 94 "for fuel classification
Test method shown in "Bake test" (hereinafter referred to as UL-94)
Tested at 1/16 inch thickness according to the method. This test
By the method, the test material was determined based on the results of five samples.
Any of UL-94 V-0, VI and V-II
Was rated. Of each V grade for UL-94
The criteria are as follows. V-0: Average flame holding time after removing the ignition flame is 5
Sub-second, and all samples ignite cotton wool
Do not fall. VI: average flame holding time after removing the ignition flame is 25
Sub-second, and all samples ignite cotton wool
Do not fall. V-II: Average flame holding time after removing the ignition flame
Less than 25 seconds and these samples ignite cotton wool
Fall the fine flame.

In addition, all test rods of UL-94 have specific V
If you do not pass the grade, you must not be classified into that grade
Has been stipulated. If this condition is not met,
Five test bars give the rating of one worst test bar
available. For example, one test rod was classified as V-II
In all cases, the grade for all five test bars is V-II.
You.UL94 / 5V test (5 inch flam test)  First, test A (bar test) was performed. If you fail Test A
In this case, it was judged as 5V rejection. If you pass Test A,
Then, a test B (square plate test) was performed. If you pass Test B
Is determined to be 5 VA, and if it fails Test B, it is determined to be 5 VB
Specified. If you pass Test B but do not pass Test A
In this case, it is determined as 5V rejection. Note that any of the tests
Even so, the thickness was 2.5 mm.CAS test  Thickness according to CSA standard C22.2 No.0.6 -M1982
Test A (127 mm frame test)
Test was carried out.

[0049]

[Table 1]

In the CSA test, ○ indicates pass, and X indicates rejection.

[0051]

According to the present invention, it is possible to provide a polycarbonate resin composition having excellent flame retardancy even when it is formed thin. Therefore, the resin composition of the present invention is industrially very useful.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 25/12 69:00 83:04 27:18) (56) References JP-A-2-69557 (JP, A JP-A-55-151057 (JP, A) JP-A-50-78643 (JP, A) JP-A-2-115262 (JP, A) JP-A-3-190958 (JP, A) JP-A-4- 226150 (JP, A) JP-A-64-2746 (JP, A) JP-A-62-277464 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 25/12 C08L 51 / 00-51/10 C08L 55/02 C08L 69/00 C08L 83/00-83/16 C08G 63/64

Claims (1)

(57) [Claims] (A) Polycarbonate and / or the following formula (Formula 1): And the following formula (Formula 2): In the above formula, R and R 'are each independently a halogen atom, a monovalent hydrocarbon group or a hydrocarbonoxy group, and W is a divalent hydrocarbon group, -S-, -SS-, -O
-, -S (= O)-,-(O =) S (= O)-, or -C (= O)-, and n and n 'are each independently an integer of 0 to 4, X is a divalent aliphatic group having 6 to 18 carbon atoms, b is 0 or 1, and has a structural unit represented by the following formula. (B) (b-1) (a) a rubbery polymer; (b) 1 to 99 parts by weight of a copolyestercarbonate occupying 2 to 30 mol% of the total amount of the structural units of A) a copolymer containing an aromatic vinyl monomer component and (c) a vinyl cyanide monomer component as constituent components of the copolymer;
Or (b-2) (b) an aromatic vinyl monomer component and (c)
The copolymer containing 99 to 1 parts by weight of a copolymer containing a vinyl cyanide monomer component as a component of the copolymer, and (C) the following formula: (Formula 10): [Here, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, but R ¹ = R ² =
X 'represents a divalent or higher valent organic group, p is 0 or 1, q is an integer of 1 to 30, R ³ = R ⁴ = H is excluded.
r represents an integer of 0 or more; provided that when r = 0, the following cases are excluded: (i) R ¹ = R ³ = φ and R ⁴ = φ− (R ⁵ −
_φ) 2; _(ii) in ^{R 1} = ^φ, and ^{R 3 = R 4 = φ-} R 5 -φ; (iii) in ^R 1 = R ³ = φ, and ^{R 4} = ^{φ-R 5} -
φ; or (iv) R ¹ = R ³ = R ⁴ = φ-R ⁵ -φ; wherein φ represents a phenyl group substituted or unsubstituted with an alkyl group, and R ⁵ represents a direct bond; -C
H ₂ —, —CH (CH ₃ ) — or — (CH ₃ ) C (C
H ₃₎ - phosphoric acid ester compound 1-20 parts by weight represented by a group], and (D) comprises a polyorganosiloxane 0.1-10 parts by weight, and (E) Fluorinated polyolefin, component ( A) A flame-retardant resin composition containing 0.01 to 2 parts by weight per 100 parts by weight.