JP2000119502A - Flame retardant thermoplastic resin composition - Google Patents

Abstract

(57) [Abstract] (Modified) [PROBLEMS] Thermoplastic resin composition excellent in solvent resistance, thermal stability, impact resistance and weather resistance, flame-retarded with compounds other than compounds containing chlorine and bromine Get things. SOLUTION: From the group consisting of (A) a polycarbonate resin and (B) an aromatic vinyl, a vinyl cyanide, an alkyl (meth) acrylate, an N-substituted maleimide and a vinyl monomer copolymerizable therewith. 100% by weight of a resin mixture comprising a copolymer of 90 to 99.9% by weight of one or more selected monomers and 0.1 to 10% by weight of an unsaturated carboxylic acid and / or an acid anhydride thereof Parts by weight of (C) phosphate ester flame retardant 0.1 to 3
0 to 15 parts by weight of a copolymer comprising (D) an olefin unit, an alkyl (meth) acrylate unit and a glycidyl (meth) acrylate unit,
And the other are blended to produce a thermoplastic resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a thermoplastic resin composition flame-retarded with a compound other than a compound containing chlorine or bromine. More specifically, compared to a conventionally known composition, a thermoplastic resin flame-retardant with a compound other than a compound containing chlorine or bromine, which has excellent solvent resistance, thermal stability, impact resistance and weather resistance, Composition.

[0002]

2. Description of the Related Art Polycarbonate resin / aromatic vinyl resin alloy is widely used as a resin having excellent impact resistance, moldability and heat resistance for various uses.

In recent years, especially in the use of electric and electronic parts, in order to ensure fire safety, the resin used must conform to UL-94 V-0 or 5VA (US Underwriters Laboratory Standard). In many cases, a high degree of flame retardancy is required, and in order to cope with these, it is necessary to make the composition flame-retardant. On the other hand, with increasing interest in environmental issues mainly in Europe, there is a demand for a composition capable of exhibiting such high flame retardancy without using a compound containing chlorine or bromine.

As a technique for imparting such high flame retardancy to a polycarbonate resin / aromatic vinyl resin alloy without using a compound containing chlorine or bromine, various studies have been made on the use of phosphorus-based flame retardants. Have been.

For example, Japanese Patent Application Laid-Open No. 61-55145 discloses a technique of adding a monophosphate flame retardant and a fluorinated polyolefin to a resin composition comprising a polycarbonate resin and an ABS resin.
Japanese Patent Application Laid-Open No. 7-304943 discloses a technique of adding an oligomeric phosphate-based flame retardant and a fluorinated polyolefin to a resin composition comprising a polycarbonate resin and an ABS resin. For adding a phosphate-based flame retardant and a fluorinated polyolefin to a resin composition consisting of

However, all such compositions use butadiene rubber as a rubber component. For this reason, when a large molded article is injection-molded at a high speed, or when the composition is retained at a high temperature, there is a problem that discoloration occurs due to deterioration of the butadiene rubber. Also,
Butadiene rubber does not have good weather resistance, and the phosphate compound added as a flame retardant causes decomposition or modification reaction by light, so that these compositions generally tend to have poor weather resistance.

Further, as a technique for making an alloy of a polycarbonate resin and a styrene-maleic anhydride copolymer flame-retardant, Japanese Patent Application Laid-Open No. 61-127760 discloses a polycarbonate resin and a styrene-maleic anhydride copolymer. Of adding a monophosphate flame retardant and a fluorinated polyolefin to a resin composition comprising

However, since such a composition does not contain a rubber component, there is a problem that the impact strength is extremely low, and the use is very limited.

Further, since both the polycarbonate resin and the aromatic vinyl resin are amorphous resins and are easily dissolved in a solvent, an alloy made of these resins is also resistant to solvents, and is used in a place where it comes into contact with the solvent. There is also a problem that can not be used.

An object of the present invention is to improve the heat stability, solvent resistance, and weather resistance of a flame retarded polycarbonate resin / aromatic vinyl resin alloy without using a compound containing bromine or chlorine, and An object of the present invention is to obtain a resin composition having excellent impact resistance.

[0011]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a resin mixture comprising a vinyl-based copolymer containing a carboxylic acid or an acid anhydride thereof and a polycarbonate-based resin contains phosphorus. By adding an acid ester-based flame retardant, a specific (meth) acrylate-based copolymer containing a glycidyl group and a compound having a specific anti-dripping property, a compound containing bromine and chlorine is not added. High heat resistance, solvent resistance, and weather resistance are improved over the conventionally known compositions, and a composition excellent in impact resistance is obtained. And found that the present invention was completed.

That is, the present invention relates to (A) a polycarbonate resin and (B) an aromatic vinyl, vinyl cyanide, an alkyl (meth) acrylate, an N-substituted maleimide, and a vinyl monomer copolymerizable therewith. One or more monomers 90 to 99.9 selected from the group consisting of
% (Hereinafter referred to as "%") and a copolymer comprising unsaturated carboxylic acid and / or an acid anhydride thereof at 0.1 to 10%, and the weight ratio (A) / (B) of both is 95. / 5
(C) Phosphate ester-based flame retardant is added to 100 parts by weight (hereinafter referred to as "parts") of the resin mixture, which is 50 to 50/50.
1 to 30 parts, (D) an olefin unit, 0.1 to 15 parts of a copolymer comprising a (meth) acrylic acid alkyl ester unit and a (meth) acrylic acid glycidyl ester unit having 1 to 10 carbon atoms in an alkyl group, As the component (E), (E
1) 0.1 to 50 parts of silicone, 0.1 to 100 parts of (E2) silicate compound, and 0.0 of (E3) fluorinated resin
The present invention relates to a flame-retardant thermoplastic resin composition comprising at least one selected from the group consisting of 05 to 5 parts.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate resin (A) used in the present invention is specifically obtained by reacting a phenol compound having a valency of 2 or more with a carbonic diester such as phosgene or diphenyl carbonate. Things.

As the dihydric phenol, there are various ones. In particular, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A) is preferable. Examples of the dihydric phenol other than bisphenol A include bis (4-hydroxyphenyl) methane,
Bis- (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) naphthylmethane, bis (4-hydroxyphenyl)-(4-isopropylphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) Methane, 1,1-bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) ethane, 1-phenyl-1,1-bis (4-hydroxyphenyl) ethane, 1 , 2-bis (4-hydroxyphenyl) ethane, 2-methyl-1,
1-bis (4-hydroxyphenyl) propane, 2,2
-Bis (3,5-dimethyl-4-hydroxyphenyl)
Propane, 1-ethyl-1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-
(Hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) butane, 2,2-bis ( 4-hydroxyphenyl) pentane, 4-methyl-2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, Dihydroxydiarylalkanes such as 2,2-bis (4-hydroxyphenyl) nonane and 1,10-bis (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) -3,
3,5-trimethylcyclohexane, 1,1-bis (4
-Hydroxyphenyl) cyclohexane, dihydroxydiarylcycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclodecane, bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4)
Dihydroxydiaryl sulfones such as -hydroxyphenyl) sulfone, bis (4-hydroxyphenyl)
Dihydroxydiaryl ethers such as ether and bis (3,5-dimethyl-4-hydroxyphenyl) ether; 4,4′-dihydroxybenzophenone;
Dihydroxydiaryl ketones such as 3 ′, 5,5′-tetramethyl-4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide,
Dihydroxydiaryl sulfides such as bis (3,5-dimethyl-4-hydroxyphenyl) sulfide;
Dihydroxydiarylsulfoxides such as bis (4-hydroxyphenyl) sulfoxide, dihydroxydiphenyls such as 4,4′-dihydroxydiphenyl,
And dihydroxyarylfluorenes such as 9,9-bis (4-hydroxyphenyl) fluorene. In addition to dihydric phenols, dihydroxybenzenes such as hydroquinone, resorcinol, and methylhydroquinone; 1,5-dihydroxynaphthalene;
And dihydroxynaphthalenes such as dihydroxynaphthalene. These dihydric phenols and the like may be used alone or in combination of two or more.

Examples of the carbonic acid diester compound include diaryl carbonates such as diphenyl carbonate and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

In the present invention, the polycarbonate resin as the component (A) may contain a branched polycarbonate if necessary.

Examples of the branching agent used for obtaining the branched polycarbonate include phloroglucin, melitic acid, trimellitic acid, trimellitic acid chloride, trimellitic anhydride, gallic acid, n-propyl gallate, protocatechuic acid, pyromellitic acid, pyromellitic acid. Acid dianhydride, α-
Resorcinic acid, β-resorcinic acid, resorcinaldehyde, isatin bis (o-cresol), benzophenonetetracarboxylic acid, 2,4,4′-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2, 4,4′-trihydroxyphenyl ether, 2,2 ′, 4,4′-tetrahydroxyphenyl ether, 2,4,4′-trihydroxydiphenyl-2-propane, 2,2′-bis (2,4 -Dihydroxyphenyl) propane, 2,2 ', 4,4'-tetrahydroxydiphenylmethane, 2,4,4'-trihydroxydiphenylmethane, 1- [α-methyl-α-
(4'-dihydroxyphenyl) ethyl] -3-
[Α ′, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (4′-dihydroxyphenyl) ethyl] -4- [α ′, α′-bis (4 "-Hydroxyphenyl) ethyl] benzene, α,
α ′, α ″ -tris (4-hydroxyphenyl) -1,
3,5-triisopropylbenzene, 2,6-bis (2
-Hydroxy-5'-methylbenzyl) -4-methylphenol, 4,6-dimethyl-2,4,6-tris (4'-hydroxyphenyl) -2-heptene, 4,6
-Dimethyl-2,4,6-tris (4'-hydroxyphenyl) -heptane, 1,3,5-tris (4'-hydroxyphenyl) benzene, 1,1,1-tris (4-
Hydroxyphenyl) ethane, 2,2-bis [4,4-
Bis (4'-hydroxyphenyl) cyclohexyl] propane, 2,6-bis (2'-hydroxy-5'-isopropylbenzyl) -4-isopropylphenol, bis [2-hydroxy-3- (2'-hydroxy-5) '-
Methylbenzyl) -5-methylphenyl] methane, bis [2-hydroxy-3- (2′-hydroxy-5′-isopropylbenzyl) -5-methylphenyl] methane,
Tetrakis (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) phenylmethane, 2 ′,
4 ′, 7-trihydroxyflavan, 2,4,4-trimethyl-2 ′, 4 ′, 7-trihydroxyflavan,
Examples thereof include 1,3-bis (2 ′, 4′-dihydroxyphenylisopropyl) benzene and tris (4′-hydroxyphenyl) -amyl-s-triazine.

In some cases, the polycarbonate resin as the component (A) may be a polycarbonate resin comprising a polycarbonate part and a polyorganosiloxane part.
A polyorganosiloxane copolymer may be used. At this time, the degree of polymerization of the polyorganosiloxane portion is preferably 5 or more.

In addition, as the polycarbonate resin as the component (A), for example, a linear aliphatic divalent carboxylic acid such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid or the like may be used as a copolymer monomer. May be used.

As the terminal terminator at the time of polymerization of the polycarbonate resin, various known terminators can be used. Specifically, examples of the monohydric phenol include phenol, p-cresol, pt-butylphenol, pt-octylphenol, p-cumylphenol, and nonylphenol.

Further, in order to increase the flame retardancy, a copolymer with a phosphorus compound or a polymer whose terminal is blocked with a phosphorus compound may be used. Further, in order to enhance the weather resistance, a copolymer with a dihydric phenol having a benzotriazole group can be used.

The viscosity average molecular weight of the polycarbonate resin (A) used in the present invention is preferably 10,000 to 10,000.
60000, more preferably 15,000 to 45
000, particularly preferably 18,000 to 35,000. When the viscosity average molecular weight is less than 10,000, the strength and heat resistance of the obtained resin composition are often insufficient.
When the viscosity average molecular weight exceeds 60,000, molding processability is often insufficient.

Specific examples of the polycarbonate resin (A) include, for example, those used in Examples described later. These are used alone or in combination of two or more. There is no limitation on how to combine two or more kinds. For example, those having different monomer units, different copolymerization molar ratios, and / or different molecular weights are arbitrarily combined.

The component (B) used in the present invention is selected from aromatic vinyl, vinyl cyanide, alkyl (meth) acrylate, N-substituted maleimide and vinyl monomers copolymerizable therewith. 90 to 99.9% of at least one kind of monomer (hereinafter, also referred to as monomer (b)) and 0.1 to 1 of unsaturated carboxylic acid and / or acid anhydride thereof
The copolymer consisting of 0% (hereinafter, also referred to as copolymer (B)) is a component mainly used for the purpose of improving the moldability and impact resistance of the polycarbonate resin.

Among the monomers (b) used in the production of the copolymer (B), the aromatic vinyl compounds include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, α-methylstyrene and α-methylstyrene. Methylstyrene, vinyltoluene and divinylbenzene, etc., as vinyl cyanide compounds, acrylonitrile and methacrylonitrile, etc., as (meth) acrylic acid alkyl esters,
Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, I-butyl acrylate,
For example, alkyl (meth) acrylates having 1 to 20 carbon atoms in the alkyl group, such as t-butyl acrylate, 2-ethylhexyl acrylate and stearyl acrylate, are exemplified by maleimide, N-substituted maleimide,
-Methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and derivatives thereof, respectively. Examples of the vinyl monomer copolymerizable with the aromatic vinyl, vinyl cyanide, alkyl (meth) acrylate and N-substituted maleimide include vinyl alkyl ether, unsaturated amino compound, dialkyl maleate, and the like. Examples include allyl alkyl ethers, diene compounds, and vinyl acetate.

The vinyl alkyl ether includes vinyl methyl ether, vinyl ethyl ether, vinyl i
-Propyl ether, vinyl n-propyl ether, vinyl i-butyl ether, vinyl n-amyl ether,
Vinyl i-amyl ether, vinyl 2-ethylhexyl ether and vinyl octadecyl ether; the unsaturated amino compounds include acrylamide and methacrylamide; and the maleic acid dialkyl esters include maleic acid di-n-amyl ester and maleic acid. Acid di-butyl ester, maleic acid dimethyl ester, maleic acid di-n-propyl ester, maleic acid dioctyl ester, maleic acid dinonyl ester, and the like, and the allyl alkyl ether includes allyl ethyl ether and allyl n-octyl ether. However, examples of the diene compound include dicyclopentadiene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1,5-norbonadiene, and 1,3-cyclopentadiene. Hexadiene, 1,4-cyclohexadiene, 1,5-cyclohexadiene and 1,
3-cyclooctadiene and the like are each exemplified.

Incidentally, the vinyl type in the vinyl type monomer means not only vinyl but also polymerizable C = such as vinylidene.
This is a word meaning having a C bond.

Examples of the unsaturated carboxylic acid and / or its acid anhydride include acrylic acid, methacrylic acid, maleic acid, maleic anhydride and fumaric acid.

The copolymerization ratio of the monomer (b) with the unsaturated carboxylic acid and / or anhydride thereof is 90 to 99.9% for the monomer (b), preferably 92 to 99. 5
%, More preferably 95 to 99%. If the amount of the monomer (b) is less than 90%, the impact resistance and thermal stability decrease, and if the amount exceeds 99.9%, the impact resistance is still insufficient, and the weather resistance decreases. It is not preferable because the compatibility of the composition is reduced and a peeling phenomenon or the like may be observed on the surface of the molded product.

The reduced viscosity of the copolymer (B) is from 0.2 to
1.2 dl / g (dimethylformamide solution, 30 ° C.,
Concentration 0.3 g / dl), and further 0.3 to 0.9 dl /
g is preferable from the viewpoint of workability. If the reduced viscosity is less than 0.2 dl / g, the mechanical strength decreases, and
If it exceeds 1 / g, the fluidity tends to decrease.

Specific examples of the copolymer (B) include, for example, those used in Examples described later. These are used alone or in combination of two or more.

The mixing ratio (A) / (B) of the polycarbonate resin (A) and the copolymer (B) in the present invention is:
95/5 to 50/50 by weight ratio, preferably 92/8 to 50/50
55/45, more preferably 90/10 to 60/40
Range. When the weight ratio (A) / (B) is less than 50/50, the impact resistance and the flame retardancy are reduced, and the 95/5
Exceeding the range is not preferred because the moldability decreases and the solvent resistance of the resulting molded article decreases.

The organophosphorus flame retardant (C) used in the present invention is a component used as a flame retardant containing no chlorine or bromine. Examples of the organic phosphorus flame retardant (C) include phosphates, phosphonates, phosphinates,
Examples include phosphine oxide, phosphite, phosphonite, phosphinite, phosphine, phosphazene and the like. More specific examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, and tris (isopropylphenyl) phosphate. , Trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, phenyl dicresyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, 2- Acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate Feto, diphenyl -
2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, triphenyl phosphite, trisnonylphenyl phosphite, tristridecyl phosphite, dibutyl hydrogen diene phosphite, triphenyl phosphine oxide, tricresyl phosphine oxide, methane Examples include diphenyl phosphonate, diethyl phenylphosphonate, phenoxyphosphazene, and propoxyphosphazene.

Here, the organophosphorus flame retardant (C) is preferably represented by the general formula (1):

[0035]

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Wherein R ^{1 to} R ⁴ are a monovalent aromatic group or an aliphatic group, R ⁵ is a divalent aromatic group, m is 0 to 16, and m R ³ and R ⁵ Are preferably different from each other) because they can greatly improve moldability, have excellent flame retardancy, and are easy to handle. In the general formula (1), the condensed phosphoric acid ester in which m is 1 to 16 is more preferable from the viewpoint of low contamination to a metal part such as a mold during molding.

Specific examples of the phosphoric ester represented by the general formula (1) when m = 0 include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl Phosphate and the like.

Other specific examples of the condensed phosphate represented by the general formula (1) include a compound represented by the general formula (2):

[0039]

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A condensed phosphoric acid ester represented by the formula (where n = 0 to 15), a general formula (3):

[0041]

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(Where n = 0 to 15) a condensed phosphoric ester represented by the general formula (4):

[0043]

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A condensed phosphoric acid ester represented by the formula (n = 0 to 15), a general formula (5):

[0045]

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And the like. Condensed phosphoric esters represented by the formula (where n = 0 to 15) and condensates obtained by combining them.

The organic phosphorus-based flame retardants may be used alone or in combination of two or more.

The amount of the organic phosphorus-based flame retardant (C) is 0.1 to 30 parts, preferably 0.1 part, per 100 parts of the resin mixture composed of the polycarbonate resin (A) and the copolymer (B). 2 to 25 parts, more preferably 0.3 to 20 parts. If the addition amount of the organophosphorus flame retardant (C) is less than 0.1 part, the flame retardancy and molding processability will decrease. If it exceeds 30 parts, the resulting molded article will have impact resistance, heat resistance, Solvent resistance,
Thermal stability and weather resistance decrease.

The component (D) used in the present invention is an (olefin) unit having an alkyl group having 1 to 10 carbon atoms.
A copolymer composed of an alkyl acrylate unit and a (meth) glycidyl acrylate unit (hereinafter, referred to as a copolymer)
The copolymer (D) is a component used for the purpose of improving impact resistance without lowering the thermal stability of the composition of the present invention, improving solvent resistance, and further improving wet heat resistance. It is.

The copolymerization ratio of the olefin unit, the alkyl (meth) acrylate unit having 1 to 10 carbon atoms in the alkyl group and the glycidyl (meth) acrylate unit in the copolymer (D) is as follows: Olefin units are preferably from 40 to 94.% so that the total amount is 100%.
9%, more preferably 50 to 89%, and preferably 5 to 59.9%, more preferably 9 to 5%, alkyl (meth) acrylate units having 1 to 10 carbon atoms in the alkyl group.
Glycidyl (meth) acrylate unit is preferably 0.1 to 55%, more preferably 1 to 4%.
1%. If the (meth) acrylic acid alkyl ester unit is less than 5%, the impact resistance tends to decrease, and if it exceeds 59.9%, the thermal stability during melting such as molding tends to decrease. If the content of the glycidyl (meth) acrylate unit is less than 0.1%, the impact resistance is reduced. If the content exceeds 41%, molding of the obtained composition tends to be difficult. If the olefin unit is less than 40%, the solvent resistance tends to decrease, and if it exceeds 94.9%, the impact resistance tends to decrease.

The melt index (M) of the copolymer (D)
I) The value is 190 ° C, 2 kg load condition (JIS K67)
30), 0.2 to 1000 g / 10 min,
It is preferably from 0.3 to 500 g / 10 min, more preferably from 0.5 to 300 g / 10 min. MI value is 0.2g
If it is less than / 10 minutes, the molding processability of the obtained composition tends to decrease, and if it exceeds 1000 g / 10 minutes, the effect of improving the impact resistance of the obtained composition tends to decrease.

The copolymer (D) may be a random copolymer or a block copolymer.

The copolymer (D) generally comprises one or more olefins, one or more alkyl (meth) acrylates and one or more glycidyl (meth) acrylate as a radical initiator. It can be obtained by radical polymerization in the presence, but the polymerization method is not limited to this, and it can be produced using various generally known polymerization methods.

Specific examples of the olefin used for producing the copolymer (D) include olefins having 2 to 12 carbon atoms such as ethylene, propylene, 1-butene and 1-pentene. The olefins are used alone or in combination of two or more. Among the olefins, ethylene is preferred in that it is easy to produce and has excellent solvent resistance.

Specific examples of the alkyl (meth) acrylate having 1 to 10 carbon atoms in the alkyl group used for producing the copolymer (D) include methyl acrylate, ethyl acrylate, n-propyl acrylate, and the like.
i-propyl acrylate, n-butyl acrylate,
t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-
Examples include propyl methacrylate, n-butyl methacrylate and t-butyl methacrylate. These may be used alone or in combination of two or more.
Among the (meth) acrylic acid alkyl esters,
Methyl acrylate and ethyl acrylate are preferred because of their excellent impact resistance.

The alkyl group in the alkyl (meth) acrylate used in the production of the copolymer (D) has 1 to 10, preferably 8 or less, more preferably 6 or less carbon atoms. If the number of carbon atoms exceeds 10, the compatibility decreases, and the effect of improving impact resistance decreases, which is not preferable.

The glycidyl (meth) acrylate used in the production of the copolymer (D) is glycidyl acrylate and glycidyl methacrylate, which may be used alone or in combination of two kinds. Among the glycidyl (meth) acrylates, glycidyl methacrylate is preferable because of easy production.

Specific examples of the copolymer (D) as described above include those used in Examples described later, ethylene / glycidyl methacrylate / ethyl acrylate copolymer,
Examples include an ethylene / glycidyl methacrylate / methyl methacrylate copolymer, an ethylene / glycidyl methacrylate / butyl acrylate copolymer, and an ethylene / glycidyl methacrylate / ethyl methacrylate copolymer. These may be used alone or as copolymer components, MI
Those having different values are used in combination of two or more.
Among these, an ethylene / glycidyl methacrylate / methyl acrylate copolymer is preferred because of its excellent balance between impact strength and solvent resistance.

The amount of the copolymer (D) to be added depends on the resin mixture of the polycarbonate resin (A) and the copolymer (B).
0.1 to 15 parts, preferably 0.3 to 1 part with respect to 0 parts.
2 parts, more preferably 0.5 to 10 parts. If the added amount of the copolymer (D) is less than 0.1 part, impact resistance, solvent resistance and wet heat resistance are reduced, and if it exceeds 15 parts, molding becomes difficult and heat stability is increased. However, it is not preferable because flame retardancy is reduced.

In the copolymer (D), the olefin unit, the alkyl (meth) acrylate unit having 1 to 10 carbon atoms and the glycidyl (meth) acrylate unit having 1 to 10 carbon atoms satisfy the copolymerization ratio. Within the range, other copolymerizable monomer units can be further contained. Other copolymerizable monomer units include styrene, aromatic vinyl compounds such as α-methylstyrene, acrylonitrile, unsaturated nitrile compounds such as methacrylonitrile, acrylic acid, unsaturated acids such as methacrylic acid and the like. Metal salt compounds such as sodium salt, calcium salt, potassium salt and magnesium salt, maleimide compounds such as n-phenylmaleimide, diene compounds such as butadiene, maleic anhydride, vinyl acetate and the like. The copolymerization ratio of these monomer units is about 30% or less.

Further, the copolymer (D) may be, if necessary,
You may use together with another polyolefin resin.
Examples of the resin (D ′) that can be used in combination include: a copolymer comprising one or more olefin units and one or more alkyl (meth) acrylate units having 1 to 10 carbon atoms in the alkyl group; Copolymer consisting of one or more olefin units and one or more glycidyl (meth) acrylate units • One or more olefin units, one or more glycidyl (meth) acrylate units, and acetic acid Copolymer comprising vinyl unit-Copolymer comprising at least one olefin unit, at least one alkyl (meth) acrylate unit having 1 to 10 carbon atoms in the alkyl group, and carbon monoxide unit Coalescence ・ Various polyolefin resins are listed, but not limited to these.

The amount of the resin (D ′) to be added depends on the resin mixture of the polycarbonate resin (A) and the copolymer (B).
The amount is preferably 15 parts or less, more preferably 10 parts or less, and still more preferably 6 parts or less with respect to 0 parts.

In the present invention, (E1) silicone and (E1) are used as the component (E) in order to prevent the dripping phenomenon occurring during the combustion test and to impart high flame retardancy even to a thin-walled molded product.
2) One or more compounds selected from a silicate compound and (E3) a fluororesin are used. As the component (E), each of the components (E1) to (E3) may be used alone, or two of the components (E1) to (E3) may be used in any combination, and (E1) to (E3). All the components may be used in combination.

The silicone which is the component (E1) used in the present invention is not particularly limited. For example, R ₃ Si
O _0.5 , R ₂ SiO, RSiO _1.5 (wherein R is a saturated or unsaturated monovalent hydrocarbon group which may have a substituent, a hydrogen atom, a hydroxyl group, an alkoxyl group,
Represents an aryl group, a vinyl group, an allyl group, or another substitutable functional group, a plurality of Rs may be the same or different from each other, and some of Rs may be an epoxy group, an amino group, a hydroxyl group, a carboxyl group; (Which may be substituted with a reactive group such as a group, a mercapto group, a vinyl group, a phenol group, an acryl group, and a methacryl group), each unit of SiO ₂ , and a unit obtained by copolymerizing two or more of these units. Liquid, gum-like, varnish-like, powder-like, flake-like polymers having chemically bonded siloxy units can be mentioned.

Specific examples of the silicone (E1) include polydiorganosiloxanes mainly composed of R ₂ SiO units such as polydimethylsiloxane, polymethylphenylsiloxane and polydiphenylsiloxane, and hydrocarbon groups of polydiorganosiloxane. Modified polydiorganosiloxane, polymethylsilsesquioxane, in which some of the hydrogen atoms are substituted with reactive groups such as epoxy, amino, hydroxyl, carboxyl, mercapto, vinyl, phenol, acryl and methacryl groups Oxane, polyorganosilsesquioxane having RSiO _1.5 units as main constituent units such as polymethylphenylsilsesquioxane, silicone resin having R ₃ SiO _0.5 units and SiO ₂ units as main constituent components, and rubber elasticity. Polyorgano having Siloxane-based rubber and the like. These may be used alone or in combination of two or more. There is no particular limitation on how to combine two or more types.

The amount of the silicone (E1) used is 0.1 to 50 parts, preferably 0.1 to 50 parts, per 100 parts of the resin mixture of the polycarbonate resin (A) and the copolymer (B). 40 parts, more preferably 0.5 to 30 parts. If the used amount is less than 0.1 part, the flame retardancy becomes insufficient due to the lack of the dripping resistance, and if it exceeds 50 parts, the mechanical strength is reduced, and problems such as surface peeling of the molded article occur. It is not preferable because there is.

The silicate compound (E2) used in the present invention has the effect of improving the resistance to dripping and the flame retardancy. It can be improved. Such a silicate compound (E2) is typically a compound having a chemical composition of SiO ₂ units, and may be a natural product or a synthesized product. The shape is not particularly limited, but is typically in the form of powder, granules, needles, or plates.

The average particle size of the silicate compound (E2) is
It is preferably from 0.05 to 100 μm, more preferably from 0.1 to 50 μm. If it is less than 0.05 μm, handling becomes difficult, and if it exceeds 100 μm, the impact resistance tends to decrease.

Specific examples of the silicate compound (E2) include magnesium silicate, aluminum silicate, calcium silicate, talc, mica, wollastonite, kaolin, diatomaceous earth, smectite and the like. Among them, mica, talc, kaolin, and smectite are excellent in the effect of dramatically improving the flame retardancy of the molded product, and also have the effect of suppressing the anisotropy of the molded product, and the heat resistance and mechanical strength. It is preferable because it has an excellent improvement effect. These may be used alone or in combination of two or more. There is no particular limitation on how to combine two or more types.

The silicate compound (E2) may be treated with a surface treating agent such as a silane coupling agent and a titanate coupling agent. Examples of the silane coupling agent include an epoxy silane coupling agent, an amino silane coupling agent, and a vinyl silane coupling agent. Examples of the titanate coupling agent include a monoalkoxy coupling agent and a chelate. Type coupling agents, coordinate type coupling agents and the like.

The addition amount of the silicate compound (E2) is 0.1 to 100 parts, preferably 0.2 parts, per 100 parts of the resin mixture comprising the polycarbonate resin (A) and the copolymer (B). To 70 parts, more preferably 0.3 to 50 parts. If the addition amount of the silicate compound (E2) is less than 0.1 part, the effect of improving the flame retardancy of the obtained molded product is poor, and if it exceeds 100 parts, the impact resistance of the obtained molded product is poor.
Heat stability and surface properties are reduced, and handling becomes difficult such as difficulty in kneading with the resin during melt kneading, which is not preferable.

The fluororesin (E3) used in the present invention
Is a resin containing a fluorine atom, and is a component used to improve the anti-dripping property and the flame retardancy.

The molecular weight of the fluororesin (E3) is 100
It is preferably from 10,000 to 20,000,000, more preferably from 2,000,000 to 10,000,000, and the average particle size is preferably 700 µm or less. The average particle size here is the average particle size of the secondary particles formed by aggregating the primary particles of the fluororesin (E3).

The ratio of the density of the fluororesin (E3) to the bulk density (density / bulk density) is 6.0 or less. The density and the bulk density here are measured by the method described in JIS-K6891.

The fluororesin (E3) can be produced by a usual known polymerization method such as emulsion polymerization, suspension polymerization, bulk polymerization and solution polymerization.

Preferred among the fluororesins (E3) are fluorinated polyolefin resins,
Specific examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer, and polyvinylidene fluoride. can give. Further, as long as the physical properties such as the flame retardancy of the obtained molded article are not impaired, it is obtained by copolymerizing a monomer copolymerizable with a monomer used for producing the fluororesin as needed. May be used.

The fluororesin (E3) may be used alone or in combination of two or more. When two or more types are used in combination, there is no limitation on the combination method. For example, different types may be arbitrarily combined and used.

The amount of the fluororesin (E3) is 0.005 to 5 parts, preferably 0.01 to 5 parts, per 100 parts of the resin mixture of the polycarbonate resin (A) and the copolymer (B). 1 part, more preferably 0.02 to 0.5 part. When the amount is less than 0.005 part, the effect of improving the flame retardancy is small, and when the amount exceeds 5 parts, the molding processability,
It is not preferable because the surface appearance of the molded product is deteriorated.

When two or more components (E) are used in combination, the amount of each component used is not limited and can be arbitrarily combined.

The resin composition of the present invention may further contain other thermoplastic or thermosetting resins such as polyester resin, polyamide resin, rubbery polymer reinforced aromatic vinyl resin, polyphenylene sulfide resin, polyphenylene. Ether resins, polyacetal resins, polysulfone resins and the like may be added alone or in combination of two or more. The amount to be added is preferably within a range in which the object of the present invention is achieved, for example, 20 parts or less based on 100 parts of the resin mixture of the polycarbonate resin (A) and the copolymer (B).

In order to improve the performance of the resin composition of the present invention, an antioxidant such as a phenolic antioxidant and a thioether antioxidant, and a heat stabilizer such as a phosphorus stabilizer may be used alone or in combination. It is preferable to add two or more kinds in combination. Furthermore, if necessary, usually well-known stabilizers, lubricants, release agents, plasticizers, non-phosphorus-based flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes,
Additives such as antistatic agents, conductivity-imparting agents, dispersants, compatibilizers, and antibacterial agents may be added alone or in combination of two or more.

The method for producing the composition of the present invention is not particularly limited. For example, it can be produced by a method of drying the above components and other additives, resins and the like, followed by melt-kneading with a melt-kneading machine such as a single-screw or twin-screw extruder. When the compounding agent is a liquid, it can be manufactured by adding the compounding agent to the extruder using a liquid supply pump or the like.

The molding method of the composition of the present invention is not particularly limited, and molding methods generally used for thermoplastic resins, such as injection molding, blow molding, extrusion molding, vacuum molding, Each molding method such as a press molding method and a calendar molding method can be applied.

[0084]

EXAMPLES Hereinafter, the composition of the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

The raw materials used in the examples and comparative examples are summarized below.

Polycarbonate resin (A) PC (A1): bisphenol A type polycarbonate resin having a viscosity average molecular weight of about 23500 PC (A2): bisphenol A type polycarbonate resin having a viscosity average molecular weight of about 26500 Copolymer (B) Polymer (B1): Styrene comprising 50% of styrene, 47% of phenylmaleimide and 3% of maleic anhydride
Phenylmaleimide-maleic anhydride copolymer Copolymer (B2): Styrene-maleic anhydride copolymer composed of 98% styrene and 2% maleic anhydride Copolymer (B3): 75% α-methylstyrene, acrylonitrile Α- consisting of 20% and 5% methacrylic acid
Methylstyrene-acrylonitrile-methacrylic acid copolymer Organophosphorus flame retardant (C) Phosphate ester (C1): Triphenyl phosphate (TPP, trade name of Daihachi Chemical Co., Ltd.) Phosphate ester (C2): Resorcinol bis (J-
2,6-xylenyl) phosphate phosphate (C3): bisphenol A bis (dicresyl) phosphate copolymer (D) E / MA / GMA (D1): 64% ethylene, 30% methyl acrylate and 6% glycidyl methacrylate
E / BA / GMA (D2): 70% ethylene, butyl acrylate E-BA / GMA (D2): ethylene-methyl acrylate-glycidyl methacrylate copolymer having a MI of 9 g / 10 min (bond first 7M: trade name, manufactured by Sumitomo Chemical Co., Ltd.) 25% and glycidyl methacrylate 5%
Ethylene-butyl acrylate-glycidyl methacrylate copolymer having an MI of 19 g / 10 min. Silicone (E1) Silicone (E1-1): Si powder DC4-705
1 (trade name, manufactured by Toray Dow Corning Silicone Co., Ltd.) Silicate compound (E2) Talc (E2-1): talcan PK (trade name, manufactured by Hayashi Kasei Co., Ltd., average particle size: 13 μm) Mica (E2-2) ): A-21S (trade name, manufactured by Mika Yamaguchi Co., Ltd., average particle size: 20 μm) Fluorine-based resin (E3) PTFE (E3-1): Polytetrafluoroethylene (Polyflon FA-500, manufactured by Daikin Industries, Ltd.) Trade name) Others ABS (B'1): Graft ABS resin obtained by graft copolymerization of 73% of styrene-acrylonitrile copolymer composed of 71% of styrene and 29% of acrylonitrile, and 23% of styrene and 7% of acrylonitrile on 70% of butadiene. Mixture with 27% HIPS (B'2): High impact HIPS resin (Estyrene H-53, trade name of Nippon Steel Chemical Co., Ltd.) T (B'3): polyethylene terephthalate (Kanebo
EEA (D'1): Ethylene-ethyl acrylate copolymer having 35% ethyl acrylate content (EEA A7)
09, trade name manufactured by Mitsui Dupont Polychemical Co., Ltd.) LLDPE (D'2): linear low density polyethylene (moretech 0168N, trade name, manufactured by Idemitsu Petrochemical Co., Ltd.) HP-10: phosphite-based stabilizer ( AO-60: Phenolic stabilizer (trade name, manufactured by Asahi Denka Co., Ltd.) The resin composition was evaluated by the following method.

[Evaluation Method] The obtained pellet was heated at 110 ° C.
After drying for 5 hours, using a 150t injection molding machine, a cylinder temperature of 280 ° C., a mold temperature of 50 ° C., a thickness of 1.6 mm,
2.5mm, 3.2mm each bar (width 12mm, length 1
27 mm), a 150 mm square × 2.5 mm thick flat plate and 3.2 mm thick ASTM No. 1 dumbbell test piece were prepared and evaluated as follows.

(Flame Retardancy) The flame retardancy of a 1.6 mm thick bar was evaluated by the V test according to the UL-94 standard. When the flame retardancy was evaluated as V-0 or V-1 in this evaluation, the thickness was 2.5 mm according to the UL-94 standard.
Using a bar and a flat plate of 150 mm square x 2.5 mm thickness, the flame retardancy was evaluated by a 5V test.

(Impact resistance) Using a 3.2 mm thick bar,
Notched IZOD impact strength was measured and evaluated at 23 ° C. according to ASTM D-256.

(Solvent resistance) The obtained dumbbell test piece was evenly strained by 0.5%, and then left for 12 hours at 23 ° C. and 50% condition with regular gasoline applied to the test piece surface. did. Visually observe the test piece appearance after standing,
Evaluation was made according to the following criteria. ：: No change in the appearance of the test piece ○: Very few cracks with a length of 1 mm or less on the test piece △: Cracks of 1 mm to 10 mm on the test piece or many cracks of 1 mm or less on the test piece Occurrence ×: Test piece broken

(Thermal Stability) The obtained pellets were heated at 110 ° C.
After drying for 4 hours, using a 150t injection molding machine, 20 plate-shaped molded bodies of 150 mm × 150 mm × 2.5 mm were molded under the conditions of a cylinder temperature of 310 ° C., a molding cycle of 3 minutes, and a mold temperature of 50 ° C. 10 to 10th to 20th
The surface appearance of each of the molded products was visually observed and evaluated according to the following criteria. ：: good appearance △: poor appearance due to flash, silver, resin burning discoloration, etc. is seen in some molded products ×: poor appearance due to flash, silver, resin burning discoloration, etc. is seen on the entire surface of the molded product

(Weather Resistance) A flat plate was irradiated with xenon light of 0.35 W / m ² for 300 hours at 55 ° C. and 55%, and ΔE was calculated by measuring the color difference before and after the irradiation of xenon light.

Example 1 80 parts of PC (A1), 20 parts of copolymer (B1), 8 parts of phosphate (C1), 4 parts of copolymer (D1), 0.5 part of talc (E2-1) , PTFE (E3-1) 0.3
Parts, 0.2 parts of HP-10 and 0.2 parts of AO-60 were previously dry-blended, and then the cylinder temperature was increased to 260 ° C.
The resin composition was obtained by supplying to a hopper of a twin-screw extruder with vent (TEX44: trade name, manufactured by Nippon Steel Works Co., Ltd.) and melt-extruding to evaluate the resin composition. Table 1 shows the results
Shown in

Examples 2 to 10 Resin compositions were obtained and evaluated in the same manner as in Example 1 except that the components shown in Table 1 were used in the amounts shown in Table 1. Table 1 shows the results.

[0095]

[Table 1]

Comparative Examples 1 to 10 Resin compositions were obtained and evaluated in the same manner as in Example 1 except that the components shown in Table 2 were used in the amounts shown in Table 2. Table 2 shows the results.

[0097]

[Table 2]

In Comparative Example 1, since the copolymer (D) was not added, the impact resistance, solvent resistance, and thermal stability were significantly reduced. In Comparative Example 2, since the phosphate ester-based flame retardant (C) was not added, the flame retardancy was significantly reduced. In Comparative Example 3, since the copolymer (B) was not added, there was a problem that the solvent resistance was lowered and the surface of the obtained molded product was peeled off. In Comparative Example 4, since the addition amount of the copolymer (D) is out of the range of the present invention, the flame retardancy is significantly reduced, and the moldability is significantly decreased, and the moldability tends to be difficult. Can be seen. In Comparative Example 5, since the addition amount of the phosphate ester-based flame retardant (C) was out of the range of the present invention, the flame retardancy, impact resistance, solvent resistance, thermal stability,
Both weather resistances decrease. In Comparative Example 6, since the weight ratio of the polycarbonate resin (A) / copolymer (B) was out of the range of the present invention, all of the flame retardancy, impact resistance, and thermal stability were reduced. In Comparative Example 7, since the component (E) was not added at all, the flame retardant level was reduced. Comparative Examples 8 to 10
In Comparative Example 8, a copolymer outside the scope of the present invention was added instead of the copolymer (B). However, in Comparative Example 8, flame retardancy, solvent resistance, thermal stability, and weather resistance were reduced. In Comparative Example 9, Flame retardancy, impact resistance, solvent resistance, thermal stability, and weather resistance are reduced. In Comparative Example 10, the weather resistance is significantly reduced.

As apparent from the comparison between Table 1 as an example and Table 2 as a comparative example, all of the compositions of the present invention have flame resistance, impact resistance, solvent resistance and heat resistance. It can be seen that the stability and weather resistance are excellent.

[0100]

Industrial Applicability The flame-retardant resin composition of the present invention is a thermoplastic resin composition which is flame-retarded without using a compound containing chlorine or bromine, as compared with a conventionally known composition. A composition having high heat resistance and excellent impact resistance, solvent resistance, heat stability, weather resistance, and flame retardancy can be provided. These are very useful industrially.

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Claims (1)

[Claims] 1. A group consisting of (A) a polycarbonate resin and (B) aromatic vinyl, vinyl cyanide, alkyl (meth) acrylate, N-substituted maleimide and a vinyl monomer copolymerizable therewith. Consisting of a copolymer of 90 to 99.9% by weight of one or more monomers selected from the group consisting of 0.1 to 10% by weight of an unsaturated carboxylic acid and / or an acid anhydride thereof. Weight ratio (A)
/ (B) is 95/5 to 50/50, a resin mixture 10
0 parts by weight of (C) a phosphate ester-based flame retardant.
1 to 30 parts by weight, 0.1 to 15 parts by weight of a copolymer comprising (D) an olefin unit, an alkyl (meth) acrylate unit having 1 to 10 carbon atoms in an alkyl group and a glycidyl (meth) acrylate unit unit Part, (E1) 0.1 to 50 parts by weight of silicone as component (E1), (E2)
A flame-retardant thermoplastic resin composition comprising at least one member selected from the group consisting of 0.1 to 100 parts by weight of a silicate compound and 0.005 to 5 parts by weight of a (E3) fluororesin.