JPH04300937A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To provide a polycarbonate resin composition having remarkably excellent flame-retardancy even in a state to have thin wall thickness. CONSTITUTION:The objective flame-retardant resin composition contains (A) 1-99 pts.wt. of a polycarbonate and/or a copolyester carbonate having aliphatic segment, (B) 99-1 pts.wt. of an ABS resin and/or SAN resin, (C) 1-20 pts.wt. (based on 100 pts.wt. of A+B) of a phosphoric acid ester compound and (D) 0.1-20 pts.wt. of a siloxane polyether imide.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition containing a polycarbonate resin.

0002

[Prior Art and Problems to be Solved by the Invention] Aromatic polycarbonate resins are widely used as engineering plastics due to their excellent physical properties, but since they lack flame retardancy, Various attempts have been made. Among these, a composition in which a phosphoric acid ester compound is blended with an aromatic polycarbonate resin and an ABS resin has high flame retardancy. That is, it achieved excellent results in UL94 combustion tests V0, V1, and V2. This flame retardant evaluation test was performed using a 127 mm long and 12 mm wide test piece.
The test is carried out using a 7 mm bar-shaped sample. However, in the square plate test of the UL94 5V test, such a resin composition failed to form a square plate (152 x 152 mm).
If the thickness is less than 2.8 mm, perforation will occur and
Failed the VA exam. Similarly, a square plate (100 x 15
0 mm) using CSA standard C22.2 No. 0
．． In test A of 6-M1982, the sample thickness was 2
．． If it is less than 8 mm, it will be rejected due to holes etc.

[0003] Also, aromatic polycarbonate resin and ABS
Resin compositions containing these resins have excellent physical properties such as impact resistance and dimensional accuracy, and are suitable for use in automobile interiors and exteriors, etc.
Widely used for housings of OA equipment, etc. However, especially in housing applications for various types of equipment, there has been an increasing trend toward thinner housings in order to meet the recent demands for lower costs and lighter weight of equipment. Therefore, in a thin housing, the UL94 5V test and CS
An aromatic polycarbonate-based resin composition that passes the A test is desired.

[0004] Therefore, the present invention has developed a polycarbonate-based resin that has excellent flame retardancy such that even when molded to a thickness thinner than 2.8 mm, it passes 5VA in the UL94 5V test and also passes the CSA test. The purpose is to provide a composition.

[0005]

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

[0006]

[Chemical formula 3] and the following formula (Chemical formula 4):

[0007]

[Image Omitted] In the above formula, R and R' each independently represent a halogen atom, a monovalent hydrocarbon group, or a hydrocarbon oxy group, and W represents a divalent hydrocarbon group, -S-, -S -S-, -O-
, -S(=O)-, -(O=)S(=O)-, or -
C(=O)-, n and n' are each independently an integer of 0 to 4, X is a divalent aliphatic group having 6 to 18 carbon atoms, and b is 0 or 1; It has a structural unit represented by, and the amount of the structural unit of (Chemical formula 4) is (
A copolyester carbonate that accounts for 2 to 30 mol% of the total amount of structural units of chemical formula 3) and (chemical formula 4)
1 to 99 parts by weight, and (B) (b-1) (a) rubbery polymer, (b) aromatic vinyl monomer component, and (c
) A copolymer containing a vinyl cyanide monomer component as a constituent component of the copolymer, and/or (b-2) (b)
Contains 99 to 1 part by weight of a copolymer containing an aromatic vinyl monomer component and (c) a vinyl cyanide monomer component as constituent components of the copolymer, and a total of 100 parts by weight of (A) and (B). It is characterized by containing 1 to 20 parts by weight of (C) a phosphoric acid ester compound and 0.1 to 20 parts by weight of (D) siloxane polyetherimide based on the weight part.

The present invention is characterized in that the resins (A) and (B) are combined with the components (C) and (D), and any one of (C) and (D) is missing. Therefore, a thin square plate cannot pass both the UL94 5V test and the CSA test.

In the present invention, component (A) is a polycarbonate and/or a copolyestercarbonate. The polycarbonate used in the present invention is an aromatic polycarbonate made by the known phosgene method or melting method (for example, JP-A-63-2157
63 and JP-A-2-124934).

[0010] Furthermore, the copolyester carbonate used in the present invention must have structural units represented by the above formulas (Formula 3) and (Formula 4). First, (chemical formula 3)
The structural unit represented by consists of a diphenol component and a carbonate component. The diphenol that can be used to introduce the diphenol component is shown in the following formula (Chemical formula 5).

[0011]

embedded image In the above formula, R, R′, W, n, n′ and b have the same meanings as shown above. Regarding R and R', examples of the halogen atom include, for example, a chlorine atom or a bromine atom. The monovalent hydrocarbon group has 1 to 1 carbon atoms.
Alkyl groups having 2 carbon atoms, such as methyl, ethyl, propyl, decyl, etc.; cycloalkyl groups having 4 to 8 carbon atoms, such as cyclopentyl, cyclohexyl; aryl groups having 6 to 12 carbon atoms, such as phenyl group, naphthyl group, biphenyl group, etc.; aralkyl group having 7 to 14 carbon atoms, such as benzyl group, cinnamyl group; or alkaryl group having 7 to 14 carbon atoms, such as tolyl group, cumenyl group, etc. and is preferably an alkyl group. Further, examples of the hydrocarbon group of the hydrocarbon oxy group include the above-mentioned hydrocarbon groups. Such hydrocarbonoxy groups include alkoxy groups, cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, and alkaryloxy groups, with alkoxy groups and aryloxy groups being preferred.

Furthermore, when W is a divalent hydrocarbon group,
Alkylene groups having 1 to 30 carbon atoms, such as methylene group, ethylene group, trimethylene group, octamethylene group, alkylidene groups having 2 to 30 carbon atoms, such as ethylidene groups, propylidene groups, or 6 to 16 carbon atoms.
cycloalkylene groups, such as cyclohexylene groups, cyclododecylene groups, etc., or cycloalkylidene groups, such as cyclohexylidene groups.

Examples of diphenols useful in the present invention include 2,2-bis(4-hydroxyphenyl)propane (so-called bisphenol A);
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-hydroxyphenyl)decane; 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, etc., and others include U.S. Patent Specifications Nos. 2,999,835 and 3,028,365.
No. 3,334,154 and No. 4,131,5
Diphenols described in No. 75 can be used.

[0014] Precursors for introducing the carbonate component include, for example, phosgene and diphenyl carbonate.

Next, the structural unit represented by (Formula 4) consists of a diphenol component and a diacid component. Regarding the introduction of the diphenol component, the same diphenols as those mentioned above can be used. The monomer used to introduce the dihydric acid component is a dihydric acid or its equivalent. The dihydric acid is, for example, an aliphatic diacid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. This divalent acid or its equivalent substance may be linear, branched, or cyclic. The aliphatic diacid is preferably α,ω-dicarboxylic acid. As such divalent acids, for example, linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid are preferable, and sebacic acid and dodecanedioic acid are preferred. Particularly preferred are diacids. In addition, examples of equivalent substances include acid halides such as acid chlorides, diaromatic esters such as diphenyl esters, etc. of the divalent acids mentioned above. However, the number of carbon atoms in the ester portion of the ester is not included in the number of carbon atoms in the acid mentioned above. The above divalent acids or their equivalents may be used alone or in combination of two or more.

The copolyester carbonate used in component (A) has the above-mentioned two types of structural units represented by (Chemical Formula 3) and (Chemical Formula 4) in the following proportions. That is, (C4
) is the amount of the structural unit shown in (Chem.3) and (Chem.4)
2 to 30 mol%, preferably 5 to 25 mol% of the total amount of
, more preferably 7 to 20 mol%. If the amount of (Formula 4) is less than 2 mol %, the transition temperature (Tg) will not be lowered sufficiently, resulting in a decrease in fluidity. Also, 30
If the amount exceeds mol%, excellent physical properties equivalent to those of polycarbonate, such as mechanical strength and heat resistance, cannot be obtained.

The weight average molecular weight of the copolyester carbonate is usually 10,000 to 100,000, preferably 18,000 to 40,000. The weight average molecular weight here is measured by GPC (gel permeation chromatography) using polystyrene corrected for polycarbonate. In addition, the intrinsic viscosity measured at 25°C in methylene chloride is 0.35~
0.65 dl/g is preferred.

The above copolyester carbonate can be produced by known polycarbonate production methods, such as interfacial polymerization using phosgene and melt polymerization. For example, Quinn U.S. Pat. No. 4,238,
No. 596 and Quinn and Markesig (
Markezich) U.S. Patent No. 4,238,597
It can be manufactured by the method described in the specification. Specifically, first, an acid halide is formed prior to the reaction of the ester-forming group with the diphenol, and then the acid halide is reacted with phosgene. Furthermore, Goldberg
In the basic solution method (U.S. Pat. No. 3,169,121), a pyridine solvent can be used and dicarboxylic acids are used. Melt polymerization methods using diesters of α,ω-dicarboxylic acids (such as sebacic acid), such as diphenyl esters, can also be used. A preferred method of manufacture is the Kochanowski modification of US Pat. No. 4,286,083. In this method, a lower diacid such as adipic acid is previously formed into a salt form (preferably an alkali metal salt such as a sodium salt) and added to a reaction vessel in which diphenol is present. During the reaction with phosgene, the aqueous phase is maintained at an alkaline pH, preferably about pH 8-9, and then with a minimum of about 5% remaining of the reaction with phosgene, the aqueous phase is adjusted to pH 1.
Raise it to 0-11.

In the case of interfacial polymerization methods, such as the bischloroformate method, it is preferred to use common catalyst systems well known for the synthesis of polycarbonates and copolyestercarbonates. The main catalyst systems include amines such as tertiary amines, amidine or guanidine. Tertiary amines are commonly used, with trialkylamines such as triethylamine being particularly preferred.

[0020] The copolyester carbonate of component (A) has sufficient impact strength even if its terminal end is phenol; Introducing bulkier end groups such as milphenol (preferably p-cumylphenol), chromanyl compounds, such as chroman, can yield copolyester carbonates with better low temperature impact properties.

[0021] When component (A) contains both polycarbonate and copolyester carbonate, the blending ratio of both may be arbitrary.

Next, component (B) will be described. 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 polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, acrylonitrile- Diene rubbers such as butadiene copolymers and butadiene-isoprene copolymers, ethylene-propylene random and block copolymers, ethylene-butene random and block copolymers, ethylene and α-olefins Copolymers with ethylene-unsaturated carboxylic acid esters such as ethylene-methacrylate and ethylene-butyl acrylate; acrylic ester-butadiene copolymers such as butyl acrylate-butadiene copolymers; Elastic polymers, copolymers of ethylene and vinyl fatty acids such as ethylene-vinyl acetate, ethylene-propylene non-conjugated diene terpolymers such as ethylene-propylene-ethylidenenorbornene copolymers, ethylene-propylene-hexadiene copolymers, butylene - Isoprene copolymers, chlorinated polyethylene, etc., and these may be used alone or in combination of two or more. Preferred rubbery polymers include ethylene-propylene rubber, ethylene-propylene non-conjugated diene terpolymers, diene rubbers and acrylic elastomeric polymers, and particularly preferred are polybutadiene and styrene-butadiene copolymers; The styrene content in the butadiene copolymer is preferably 50% by weight or less.

Examples of the vinyl cyanide monomer component (b) used in the present invention include acrylonitrile, methacrylonitrile, etc., and one or more of these may be 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,
Examples include monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, and vinylnaphthalene, and one or more of these may be used. Preferably styrene, α
-Methylstyrene.

In the present invention, component (B) (b-1) includes, in addition to the above components (a), (b) and (c),
(d) Monomers copolymerizable with these components can be used within a range that does not impair the object of the present invention. 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)acrylate,
α,β-unsaturated carboxylic acid esters such as 2-ethyl (meth)acrylate and 2-ethylhexyl methacrylate; α,β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; maleimide, N- Examples include imide compounds of α,β-unsaturated dicarboxylic acids such as methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-o-chlorophenylmaleimide; these monomers may be used alone or in combination. Used in two or more types.

In component (b-1), each component (a),
There is no particular restriction on the composition ratio of (b) and (c), and each component is blended according to the intended use.

As the copolymer of component (b-1), (a
) Preferred are graft copolymers in which other components are graft copolymerized in the presence of a rubbery polymer, and more preferred are ABS resins (acrylonitrile-butadiene-styrene copolymers) and AES resins (acrylonitrile-ethylene-propylene-copolymers). styrene copolymer), ACS resin (
Acrylonitrile-chlorinated polyethylene-styrene copolymer) and AAS resin (acrylonitrile-acrylic elastic polymer-styrene copolymer).

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

Next, (b-2) of component (B) is (b)
It is a copolymer containing an aromatic vinyl monomer component and (c) a cyanide vinyl monomer component. Specific examples of these include (b) and (c) in (b-1) above.
), and their composition ratios are not particularly limited and are selected depending on the application. Preferable (b-
2) is SAN resin (styrene-acrylonitrile copolymer). Furthermore, as for the method for producing the copolymer of component (b-2), the same method as in (b-1) above can be used.

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

The blending ratio of the above-mentioned components (A) and (B) is 1 to 99 parts by weight of (A) and 99 to 1 part by weight of (B).
parts by weight, preferably from 10 to 95 parts by weight of (A) (
B) in an amount of 90 to 5 parts by weight.

The component (C) phosphoric ester compound used in the present invention has the following formula (Chemical formula 6):

[0034]

(Here, R1, R2, R3 and R4 each independently represent a hydrogen atom or an organic group, but R1
=R2 =R3 =R4 Except for the case of =H. X' represents an organic group having a valence of 2 or more, p is 0 or 1, q is an integer of 1 or more and, for example, 30 or less, and r is an integer of 0 or more. ) Examples include phosphoric acid ester compounds represented by: However, it is not limited to these.

In the above formula, the organic group includes, for example, an alkyl group, which may or may not be substituted, a cycloalkyl group, an aryl group, and the like. In addition, 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. A combined group (e.g., arylalkoxyalkyl group, etc.) or a group (e.g., arylsulfonylaryl group, etc.) in which these substituents are bonded through an oxygen atom, sulfur atom, nitrogen atom, etc. may be used as a substituent. good. Furthermore, the term "divalent or higher valence organic group" means a divalent or higher valence group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above-mentioned organic group. Examples include alkylene groups, and preferably (substituted) phenylene groups, those derived from polynuclear phenols such as bisphenols, the relative positions of the two or more free valences being arbitrary. Particularly preferred are hydroquinone, resorcinol, diphenylolmethane,
diphenyloldimethylmethane, dihydroxydiphenyl, p,p'-dihydroxydiphenylsulfone,
Examples include dihydroxynaphthalene.

Specific examples of phosphoric acid ester compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, and octyldiphenyl. 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, R1 to R4 are alkoxy such as methoxy, ethoxy and propoxy, or preferably (substituted) phenoxy, such as phenoxy, methyl (substituted) phenoxy, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcinol bisphosphate, trioxybenzene triphosphate, etc., preferably triphenyl phosphate and various bisphenol It is phosphate.

The above component (C) is composed of component (A) and (
It is added in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight, per 100 parts by weight of B). If the amount of component (C) is less than the above range, the effects of the present invention will not be fully exhibited,
If the amount exceeds the above range, heat resistance will be impaired.

Next, the component (D) siloxane polyetherimide used in the present invention is known per se, and has the formula (Chemical formula 7)
:

[0039]

[C7] repeating unit and the following formula (Chemical formula 8):

[0040]

A repeating unit represented by the formula (wherein T is -O- or -O-
is a group of Z-O-, and the group -O- or -O-Z-O-
The divalent bond of is at the 3,3', 3,4', 4,3' or 4,4' position: Z is (A)

[0041]

[Chemical formula 9] ,

[0042]

[Chemical formula 10] ,

[0043]

[Chemical formula 11] ,

[0044]

[Chemical formula 12] ,

[0045]

[Chemical formula 13] ,

[0046]

[Chemical formula 14] and

[0047]

[Chemical formula 15] and (B) general formula

[0048]

embedded image (wherein, X is -Cy H2y- (where y is an integer from 1 to about 5), -C(=O)-, -(O=)S(=O)
-, -O-, and -S-); and R is a member of the group consisting of (a) 6 to about 20 divalent organic groups; Aromatic hydrocarbon groups having carbon atoms and halogenated derivatives thereof, (b) 2-
an alkylene group having about 20 carbon atoms, a cycloalkylene group having 3 to about 20 carbon atoms, and (c) general formula

[0049]

[Chemical formula 17] (wherein, Q is -S-, -O-, -C(=O)-, -(O
=)S(=O)-, and -Cx H2x- (x is 1 to
is a member selected from the group consisting of (an integer of approximately 5)
is a divalent organic group selected from the group consisting of divalent groups,
R1 are monovalent hydrocarbon groups that are the same or different from each other, n and m are each an integer from 1 to about 10, and g is an integer from 1 to about 40), or consist essentially of the formula

[0050]

[Chemical formula 18] [In the formula, M is

[0051]

[Chemical formula 19] ,

[0052]

[C20] and

[0053]

[Image Omitted] (where B is -S- or -C(=O)-, and R' is of the formula

[0054]

embedded image (wherein R1 are the same or different monovalent hydrocarbon groups, n and m are each an integer of 1 to about 10, and g is an integer of 1 to about 40) consisting essentially of repeating units represented by

Preferably, n and m are each 3, and g has an average value ranging from about 9 to about 20.

The diamine component of the siloxane polyetherimide generally contains about 20-50 mole percent amine-terminated organosiloxane and about 50-80 mole percent other organic diamines. Preferably, the diamine component contains about 25 to about 40 mole percent, most preferably about 30 mole percent, amine-terminated organosiloxane.

The siloxane polyetherimide used in the present invention may be produced by any method commonly used for the production of polyetherimides. One currently preferred method of manufacture is described in US Pat. No. 4,417,044.

Component (D) is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on a total of 100 parts by weight of components (A) and (B). If the amount is less than the above range, the effects of the invention will not be sufficiently exhibited.

The resin composition of the present invention may further contain an anti-dripping agent. Fluorinated polyolefins that can be used as such anti-dripping agents are commercially available or can be produced by known methods. 100 in an aqueous medium using a free radical catalyst (e.g. sodium, potassium or ammonium peroxydisulfate).
It is a white solid obtained by polymerizing tetrafluoroethylene under a pressure of ~1000 psi and a temperature of 0-200°C, preferably 20-100°C. For more information, see Brubaker, US Pat. No. 2,393,967. Although not essential, it is preferred to use resins in the form of relatively large particles, for example particles with an average particle size of 0.3 to 0.7 mm (mainly 0.5 mm). This is 0
．． It is better than normal polytetrafluoroethylene powder with particle size of 0.05-0.5 mm. Such relatively large particle size materials are particularly preferred because they tend to disperse easily in polymers and bond together to form fibrous materials. Such preferred polytetrafluoroethylene is referred to as Type 3 according to ASTM and is actually manufactured by E.I.
t de Nemours and Company)
It is commercially available as Teflon 6 from Teflon 6. Alternatively, Mitsui DuPont Fluorochemical Company's Teflon 3
Commercially available as 0J. The fluorinated polyolefin is preferably 0.01 to 2 parts by weight, more preferably 0.05 to 1.0 parts by weight, per 100 parts by weight of component (A).
Use parts by weight.

In addition to the above-mentioned components, the resin composition of the present invention may contain other commonly used additives such as pigments, pigments, etc., depending on the purpose, when mixing the resin or molding. dyes, reinforcing agents (glass fiber, carbon fiber, etc.),
Fillers (carbon black, silica, titanium oxide, etc.)
, a heat resistant agent, an oxidative deterioration inhibitor, a weathering agent, a lubricant, a mold release agent, a crystal nucleating agent, a plasticizer, a fluidity improver, an antistatic agent, etc. can be added.

There are no particular limitations on the method for producing the resin composition of the present invention, and conventional methods can be used satisfactorily. However, melt mixing methods are generally preferred. The use of small amounts of solvent is possible, but generally not necessary. Examples of equipment include extruders, Banbury mixers, rollers, kneaders, etc., which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

[0062]

EXAMPLES The present invention will be explained in more detail with the following examples. In addition, the following components were used in the examples. Component (A) PC: Bisphenol A polycarbonate (trademark: Lexan, manufactured by Japan GE Plastics Co., Ltd.)
, intrinsic viscosity 0.50, measured at 25°C in methylene chloride.
dl/gCPEC: Copolyester carbonate produced as follows; Dodecanedioic acid (DDDA) 7.2
g (31 mmol) and 2.7 g (68 mmol) of NaOH tablets.
mmol) was dissolved in 180 ml of water to produce the disodium salt of DDDA. Next, a 2000 ml Molton flask with a sample outlet at the bottom and five ports at the top was equipped with a stirring blade, a pH measuring end, an injection tube, and a Claisen adapter with a dry ice condenser. 71 g of bisphenol A (31 g) was added to this polymerization flask.
1 mmol), 0.9 ml of triethylamine, 2.0 g (9 mmol) of p-cumylphenol, 220 ml of methylene chloride, and the previously prepared disodium salt of DDDA were charged. Subsequently, phosgene was injected into the flask at a rate of 2 g/min. At this time, 50%N
While adding aOH aqueous solution from the injection tube, adjust the solution to pH 8.
was maintained for 10 minutes. Thereafter, while continuing to inject phosgene, 50% NaOH aqueous solution was added through the injection tube to bring the pH of the solution to 10.5, and this pH was maintained for 10 minutes. The total amount of phosgene used was 40 g (400 mmol). After the reaction is completed, the pH of the solution is adjusted to 11-1.
1.5 and the organic solvent phase was separated from the aqueous phase. The organic solvent phase was washed three times with 300 ml of 2% hydrochloric acid and then five times with 300 ml of ion-exchanged water, dried over anhydrous magnesium sulfate, and filtered. Add this to 1500 m of methanol
1 to precipitate the polymer. The obtained polymer was separated by filtration, washed once with 500 ml of methanol and then four times with 500 ml of ion-exchanged water, and then heated at 110°C.
It was dried for 15 hours. Thus, the following formulas (Chemical formula 23) and (
A copolyester carbonate having the structural unit of formula 24) in a molar ratio of 90:10 was obtained. Its intrinsic viscosity (measured in methylene chloride at 25°C) is 0.50 dl/g
Met. This will be abbreviated as CPEC below.

[0063]

[C23]

[0064]

[Chemical formula 24] Component (B) b-1: ABS resin, trademark UX 050 (manufactured by Ube Saikon Co., Ltd.) b-2: SAN resin, trademark SR 30B (manufactured by Ube Saicon Co., Ltd.) Component (C) CR733S: Trademark, phenylresorcin Polyphosphate, Daihachi Chemical Co., Ltd. TPP: Triphenylphosphate component (D) Siloxane polyetherimide: 2,2-bis[4
-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride with 60 mol% m-phenylenediamine and 40 mol% amine-terminated dimethylpolysiloxane (
Random copolymer optional component obtained from an amine component consisting of the formula (where n and m are 3 and g is 9 on average) Teflon 30J: Trademark, polytetrafluoroethylene, manufactured by DuPont Mitsui Fluorochemical Co., Ltd. Example 1 to 3 and Comparative Examples 1 to 3 Each component was mixed in the ratio (weight ratio) shown in Table 1, and 28
A single screw extruder (65 mm) set at 0 °C and 100 rpm
mm) to create pellets. This pellet was then 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 to evaluate flame retardancy. The results are shown in Table 1.

[0065] The evaluation test for the resin composition was conducted as follows. (1) Izod impact strength (Kg-cm/cm) AS
Measured according to TM D 256, 1/8 inch thick, notched. (2) Flame retardancy test UL94/V0, VI, VII test Five test bars were tested according to Underwriters Laboratories Inc.'s Bulletin 94 "Flammability Test for Material Classification" (hereinafter referred to as UL-94). The test was performed at a thickness of 1/16 inch according to the test method. This test method evaluates the test material to UL-94 V-0, VI and V-II based on the results of five samples.
It was evaluated as one of the following grades. The criteria for each V rating for UL-94 are roughly as follows. V-0: Average flame retention time after removing ignition flame is 5
It takes less than a second, and all samples do not drop the fine flame that ignites the absorbent cotton. VI: Average flame retention time after removing ignition flame is 2
The time is 5 seconds or less, and all samples do not drop the fine flame that ignites the absorbent cotton. V-II: The average flame retention time after removing the ignition flame is 25 seconds or less, and these samples drop a fine flame that ignites the absorbent cotton.

[0066] UL-94 also stipulates that all test bars must pass a particular V class before being classified into that class. If this condition is not met, the five test bars are given the grade of the single worst performing test bar. For example, if one test bar is classified as V-II, the rating for all five test bars is V-II. UL94/5V test (5-inch flam test) First, test A (bar test) was conducted. If test A failed, it was determined that 5V failed. If you pass exam A, then
Test B (square plate test) was conducted. 5 if you pass exam B
It was determined to be VA, and if it failed test B, it was determined to be 5VB. In addition, if test B is passed but test A is not passed, it is determined that 5V is not passed. In addition, in any test, the thickness was 2.5 mm. CAS Test CSA Standard C22.2 No. 0.6-M198
Test A (127 mm frame test) was conducted on a test piece with a thickness of 2.5 mm in accordance with 2.

[0067]

[Table 1]

[0068]

Effects of the Invention According to the present invention, it is possible to provide a polycarbonate resin composition which exhibits extremely excellent flame retardancy even when molded thinly. Therefore, the resin composition of the present invention is industrially very useful.

Claims (1)

[Claims] Claim 1: (A) Polycarbonate and/or the following formula (Chemical formula 1): [Chemical formula 1] and the following formula (Chemical formula 2): [Chemical formula 2] In the above formula, R and R' each independently represent a halogen an atom, a monovalent hydrocarbon group, or a hydrocarbon oxy group, W is a divalent hydrocarbon group, -S-, -S-S-, -O-
, -S(=O)-, -(O=)S(=O)-, or -
C(=O)-, n and n' are each independently an integer of 0 to 4, X is a divalent aliphatic group having 6 to 18 carbon atoms, and b is 0 or 1; It has a structural unit represented by, and the amount of the structural unit of (Chemical formula 2) is (
A copolyester carbonate that accounts for 2 to 30 mol% of the total amount of structural units of Chemical Formula 1) and (Chemical Formula 2)
1 to 99 parts by weight, and (B) (b-1) (a) rubbery polymer, (b) aromatic vinyl monomer component, and (c
) A copolymer containing a vinyl cyanide monomer component as a constituent component of the copolymer, and/or (b-2) (b)
Contains 99 to 1 part by weight of a copolymer containing an aromatic vinyl monomer component and (c) a vinyl cyanide monomer component as constituent components of the copolymer, and a total of 100 parts by weight of (A) and (B). A flame-retardant resin composition containing 1 to 20 parts by weight of (C) a phosphoric acid ester compound and 0.1 to 20 parts by weight of (D) siloxane polyetherimide.