JPH06116459A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. excellent in flame retardance, mechanical strengths, and resistance to heat distortion by compounding an arom. polycarbonate resin, a specific styrenic resin, a flame retardant, and polytetrafluoroethylene each in a specified amt. CONSTITUTION:The compsn. is prepd. by compounding specified amts. of an arom. polycarbonate resin, a styrenic resin which comprises a copolymer component comprising a copolymer obtd. from a monomer mixture consisting of an arom. vinyl compd. (A), a vinyl cyanide compd. (B), an N-substd. maleimide compd. (C), and other monomers in a specified ratio and having a specified reduced viscosity and a copolymer obtd. from a monomer mixture consisting of monomer A, monomer B, an alkyl methacrylate (D), and other monomers in a specified ratio and having a specified reduced viscosity in a specified ratio of the former copolymer to the latter and a graft copolymer component comprising a graft copolymer obtd. by grafting a specified amt. of a monomer mixture consisting of monomer A, monomer B, monomer C, and other monomers to a rubberlike polymer (E) and a graft copolymer obtd. by grafting a specified amt. of a monomer mixture consisting of monomer A, monomer B, monomer D, and other vinyl monomers to polymer E in a specified ratio of the former graft polymer to the latter, a flame retardant, and polytetrafluoroethylene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel flame-retardant resin composition comprising an aromatic polycarbonate resin, a special styrene resin, a flame retardant and polyterafluoroethylene.

[0002]

2. Description of the Related Art A resin composed of a polycarbonate resin and a styrene resin is excellent in heat resistance, impact resistance and moldability and is widely used in machines, automobiles, electric and electronic parts and the like.
High flame retardancy is required for use in OA equipment and home electric appliance parts, and a method of flame retarding by adding a flame retardant such as a halogen compound or a phosphorus compound is known. However, from the viewpoint of safety, in recent years, the flame retardation regulations of the US UL organization for office automation equipment and home electric appliances have become strict. Further OA
Equipment manufacturers and home appliance manufacturers are gradually thinning parts and housings in order to reduce weight and increase efficiency. For this reason, there is a problem that the flame of the resin drops during combustion and damages other parts, and it is necessary to have a technique to prevent the dropping property (dripping property) of the burning resin as well as the burning property of the resin itself. It has become to. To prevent dripping,
There are a method of increasing the amount of the flame retardant, a method of adding an inorganic substance, and a method of adding an olefin polymer. However, the method of increasing the amount of the flame retardant uses a large amount of the flame retardant, so that mechanical properties such as impact strength are deteriorated, and there is a drawback that the cost is further increased. Has the disadvantage that it decreases. On the other hand, in the method of blending an olefin polymer (JP-A-3-182542), the dripping property is improved by adding polyvinylidene fluoride, but there is a problem that the improvement is insufficient.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a flame-retardant resin composition having high flame retardancy, excellent mechanical properties, and low dripping property.

[0004]

Means for Solving the Problems As a result of intensive investigations aimed at solving the above-mentioned problems, the present inventors have found that the use of a special styrene-based resin and the addition of polyterafluoroethylene together with a flame retardant makes it highly difficult. The present invention has been completed by finding that a flame-retardant resin composition that provides a molded article that is flammable and has a low dripping property and further has excellent mechanical strength can be obtained.

That is, in the present invention, a flame retardant (C) is added to 100 parts by weight of an aromatic polycarbonate resin (A) of 5 to 95% by weight and the following styrene resin (B) of 95 to 5% by weight. To 40 parts by weight and 0.05 to 5 parts by weight of (D) polytetrafluoroethylene.

The aromatic polycarbonate used in the present invention is preferably an aromatic polycarbonate produced by reacting a dihydric phenol compound with phosgene or a carbonic acid diester. As the divalent phenol compound, bisphenols are preferable, and 2,2-bis (4-hydroxyphenyl) propane, so-called bisphenol A is particularly preferable. It is also possible to substitute a fixed amount or the whole amount of bisphenol A with another dihydric phenol compound. Examples of divalent phenol compounds other than bisphenol A include hydroquinone, 4,4-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, and bis (4-
Examples thereof include compounds such as hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, and bis (4-hydroxyphenyl) ketone. A homopolymer composed of these dihydric phenol compounds, a copolymer composed of two or more kinds thereof, or a blended product thereof may be used.
Further, a phosphorus compound may be used for copolymerization or end capping in order to enhance flame retardancy.

Styrenic resin (B) used in the present invention
Is 5 to 100% by weight of the copolymer (Xa) and the copolymer (Xa).
b) Copolymer (X) consisting of 95 to 0% by weight, and graft copolymer (X) consisting of 5 to 100% by weight of graft copolymer (Ya) and 95 to 0% by weight of graft copolymer (Yb) ( Y). Styrene resin (B) is
From the viewpoint of mechanical strength, the copolymer (X) is 10 to 90% by weight,
The range of 90 to 10% by weight of the graft copolymer (Y) is preferable, and further the range of 30 to 85% by weight of the copolymer (X) and the range of 70 to 15% by weight of the graft copolymer (Y) are preferable.
The copolymer (Xa) is an aromatic vinyl compound in an amount of 5 to 80% by weight, preferably 15 to 70% by weight, a vinyl cyanide compound in an amount of 15 to 55% by weight, preferably 20 to 50% by weight.
-Substituted maleimide compound 5-40%, preferably 10-
35% by weight, and other monomers copolymerizable therewith
20 wt% and the reduced viscosity of the methyl ethyl ketone soluble component of the copolymer is 0.15 to 2.0 dl / g, preferably 0.2 at 30 ° C. in a dimethylformamide solution.
It is a copolymer in the range of 5 to 1.2 dl / g.

As a more preferable composition of the copolymer (Xa), an aromatic vinyl compound is 4.99 to 70% by weight, preferably 14.95 to 65% by weight, and a vinyl cyanide compound is 15 to 55% by weight, preferably 20-50% by weight, N-
Substituted maleimide compound 5 to 40% by weight, preferably 10
~ 35 wt%, vinyl compound containing epoxy groups 0.
01 to 10% by weight, preferably 0.05 to 5% by weight and 0 to 20% by weight of another monomer copolymerizable therewith, and the reduced viscosity of the methyl ethyl ketone soluble component of the copolymer is In a dimethylformamide solution at 30 ° C.
It is a copolymer of 15 to 2.0 dl / g, preferably 0.25 to 1.2 dl / g.

The copolymer (Xb) contains 40 to 90% by weight of an aromatic vinyl compound, preferably 50 to 80% by weight, and 10 to 60% by weight of a vinyl cyanide compound, preferably 20 to 20%.
50% by weight, 0 to 30% by weight of alkyl methacrylate and 0 to 20% by weight of another monomer copolymerizable therewith, and the reduced viscosity of the methyl ethyl ketone soluble component of the copolymer is a dimethylformamide solution. Medium, 0.15 to 2.0 dl / g at 30 ° C, preferably 0.25 to 1.2 dl
It is a copolymer in the range of / g. Copolymer (Xa), (X
If b) is outside the above range, the mechanical strength, flame retardancy or heat resistance will decrease.

The graft copolymer (Ya) of the present invention comprises a rubbery polymer 30 to 90% by weight, preferably 40 to 85% by weight, an aromatic vinyl compound 5 to 80% by weight, preferably 15 to 70% by weight. , Vinyl cyanide compound 15 to 55% by weight, preferably 20 to 50% by weight, N-substituted maleimide compound 5 to 40% by weight, preferably 10 to 35% by weight
And 70 to 10% by weight, preferably 60, of a monomer mixture consisting of 0 to 20% by weight of another monomer copolymerizable therewith.
It is a graft copolymer obtained by polymerizing 15 to 15% by weight.
A more preferable composition of the graft copolymer (Ya) is 30 to 90% by weight of a rubbery polymer, preferably 40 to
85% by weight, aromatic vinyl compound 4.99 to 70% by weight, preferably 14.95 to 65% by weight, vinyl cyanide compound 15 to 55% by weight, preferably 20 to 50% by weight, N-substituted maleimide compound 5 to 40% by weight, preferably 10 to 35% by weight, 0.01 to 10% by weight, preferably 0.05 to 5% by weight of an epoxy group-containing vinyl compound and other monomers copolymerizable therewith It is a graft copolymer obtained by polymerizing 70 to 10% by weight, preferably 60 to 15% by weight, of a monomer mixture consisting of 0 to 20% by weight. The graft copolymer (Yb) is a rubber-like polymer 30-
A graft copolymer obtained by polymerizing 90% by weight, preferably 40 to 85% by weight, of 70 to 10% by weight and 60 to 15% by weight of a monomer mixture consisting of the following formula group. 10 ≦ e + (f / 4) ≦ 40 h = 100−e−f−g e ≧ 0, f ≧ 0, 0 ≦ g ≦ 90, and 0 ≦ h ≦ 20 [wherein, e, f, g , And h are vinyl cyanide compound (e), alkyl methacrylate (f), aromatic vinyl compound (g), and another vinyl monomer (h) copolymerizable with them in a monomer mixture. The weight ratio (%) is shown. When the composition of the graft copolymers (Ya) and (Yb) is out of the above range, the mechanical strength and the flame retardancy are lowered.

As the aromatic vinyl compound in the styrene resin (B) of the present invention, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-
Methylstyrene, chlorostyrene, isopropenylnaphthalene, hydroxystyrene and the like are exemplified, and these are used alone or in combination of two or more kinds. As the aromatic vinyl compound, p-methylstyrene is preferably contained in the aromatic vinyl compound in an amount of 50% by weight or more, more preferably 65% by weight or more, from the viewpoint of flame retardancy.
Examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile, and examples of alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-.
Examples thereof include hydroxyethyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, which may be used alone or in combination of two or more. As the N-substituted maleimide compound, N-phenylmaleimide, N-
Methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, N-cyclohexylmaleimide, etc., can be mentioned alone or Used in combination of two or more.

Examples of the vinyl compound containing an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl allyl ether, and general formula (I).

[0013]

[Chemical 1]

(In the formula, Ar represents a C _{9 to} C ₂₃ aromatic hydrocarbon group having at least one reactive group selected from the group consisting of a glycidyloxy group and a glycidyl group, and R represents a hydrogen atom or a methyl group. The compound represented by the formula (1) can be used alone or in combination of two or more. The compound containing an epoxy group is represented by the following formula (II) from the viewpoint of mechanical strength.

[0015]

[Chemical 2]

The compounds represented by are particularly preferred. These compounds are described in detail in JP-A-60-130580. Other vinyl compounds that can be copolymerized include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-ethylhexyl (meth).
Acrylate, acrylic acid, methacrylic acid, etc. are illustrated, and these are used individually or in combination of 2 or more types.

Examples of the rubber-like polymer in the graft copolymers (Ya) and (Yb) include diene rubbers such as polybutadiene rubber, styrene-butadiene copolymer rubber (SBR) and acrylonitrile-butadiene rubber (NBR). , Acrylic rubber such as polybutyl acrylate, and ethylene-propylene-diene terpolymer rubber (E
Examples include polyolefin rubbers such as PDM) and silicone rubbers, which may be used alone or in combination of two or more.

Examples of the flame retardant (C) used in the present invention include phosphorus-based flame retardants, halogen-based flame retardants, nitrogen compounds, metal salts, metal oxides and the like, and these are used alone or in combination of two or more kinds. To be As the flame retardant (C),
Phosphorus flame retardants containing no halogen atom and having a melting point of 80 ° C. or higher are preferable in terms of safety and heat resistance of the resin. Among them, condensed phosphoric acid ester is more preferable. As the phosphorus-based flame retardant, triferni phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, Tris β-chloropropyl phosphate, tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, tris (tribromoneopentyl) phosphate, aromatic condensed phosphate ester, halogen-containing aromatic condensed phosphate ester, etc. To be Halogen-based flame retardants include carbonate oligomers of tetrabromobisphenol A, epoxy oligomers of tetrabromobisphenol A, tetrabromobisphenol A, bis (tribromophenoxy) ethane, decabromobiphenyl ether, octabromobiphenyl ether, hexabromobiphenyl ether. , Hexabromobenzene and the like. Examples of nitrogen-based flame retardants include ammonium polyphosphate, melamine and the like. Examples of the metal salts and metal oxides include sodium trichlorohenzene sulfonate, potassium diphenylsulfone sulfonate, sodium aluminum hexafluoride, antimony trioxide and the like.

The polyterafluoroethylene (D) used in the present invention is not particularly limited in its molecular weight and particle size.
The powder may be directly blended with the resin, or the suspension slurry or emulsified latex may be blended with the slurry or latex of the styrene resin for use. From the viewpoint of flame retardancy, the molecular weight is preferably 1 million or more and the particle size is 1000 μm or less, more preferably 700 μm.
m or less is good.

The flame-retardant resin composition of the present invention contains the aromatic polycarbonate (A) in an amount of 5 to 95% by weight, preferably 15 to 8%.
5% by weight, styrene resin (B) 95 to 5% by weight, preferably 85 to 15% by weight, based on 100 parts by weight of resin, flame retardant (C) 1 to 40% by weight, preferably 3 to 30%.
Parts by weight, and polyterafluoroethylene (D) 0.05
~ 5 parts by weight of the composition. If the aromatic polycarbonate resin (A) is less than 5% by weight, the flame retardancy is lowered, and 9
If it exceeds 5% by weight, the impact strength decreases. Flame retardant (C)
If less than 1 part by weight, the flame retardancy is lowered, and if more than 40 parts by weight, the impact strength is lowered. If the amount of polyterafluoroethylene (D) is less than 0.05 parts by weight, the flame retardancy will decrease, and if it exceeds 5 parts by weight, the impact strength will decrease.

The flame-retardant resin composition of the present invention contains not only antioxidants, heat stabilizers and lubricants which are well known, but also UV absorbers, pigments, antistatic agents, flame retardants and flame retardants as required. A combustion aid can also be used in combination. In particular, polycarbonate resins, phenolic antioxidants used in styrene resins, phosphite stabilizers, benzophenone-based, benzotriazole-based UV absorbers and fatty acid esters, internal and external lubricants such as hydrocarbon waxes, etc. The flame-retardant resin composition of the present invention can be used as a molding resin for higher performance. Further, the flame-retardant resin composition of the present invention can be used by blending a flame-retardant auxiliary agent such as a silicon compound such as polydimethylsiloxane or an aluminum compound such as alumina, depending on the degree of necessity of flame retardancy. . Further, reinforcing fibers such as glass fibers and carbon fibers, and fillers such as mica, talc, clay and glass beads can be used to improve mechanical properties such as elastic modulus and heat resistance.

[0022]

EXAMPLES The present invention will now be described in more detail with reference to specific examples, but these examples do not limit the present invention. In the following description, “parts” means parts by weight,
"%" Indicates% by weight. Example 1 (1) Synthesis of styrene-based resin (B) (a) Synthesis of copolymer (Xa) A reaction vessel equipped with a stirrer and a cooler was charged with the following substances in a nitrogen stream. Water 250 parts Sodium formaldehyde sulfoxylate 0.4 parts Ferrous sulfate 0.0025 parts Disodium ethylenediamine tetraacetate 0.01 parts Sodium dodecylbenzene sulfonate 3 parts After heating and stirring at 60 ° C in a nitrogen stream, the table The monomer mixture in the ratio shown in 1 was continuously added dropwise over 5 hours together with the initiator cumene hydroperoxide and the polymerization degree adjusting agent tertiary decyl mercaptan. After the dropping was completed, stirring was further continued at 60 ° C. for 1 hour to complete the polymerization. (B) Synthesis of copolymer (Xb) Polymerization having the composition shown in Table 1 was carried out by the same method as for the copolymer (Xa).

[0023]

[Table 1]

(C) Synthesis of Graft Copolymer (Ya) A reaction vessel equipped with a stirrer and a cooler was charged with the following substances in a nitrogen stream. Water 250 parts Sodium formaldehyde sulfoxylate 0.2 parts Ferrous sulfate 0.0025 parts Disodium ethylenediaminetetraacetate 0.01 parts Rubber polymer (used in latex state) Predetermined amount shown in Table 2 In nitrogen stream After heating and stirring at 60 ° C., the monomer mixture in the ratio shown in Table 2 was continuously added dropwise with the initiator cumene hydroperoxide over 5 hours. After the dropping was completed, stirring was further continued at 60 ° C. for 1 hour to complete the polymerization. (D) Synthesis of Graft Copolymer (Yb) Polymerization with the composition shown in Table 2 was carried out by the same method as for the copolymer (Ya).

[0025]

[Table 2]

The copolymers (Xa) and (Xb) obtained in (a) and (b) above, and the graft copolymers (Ya) and (Yb) obtained in (c) and (d) above. Latex of Table 3
The mixture was uniformly mixed in the proportion shown in (1), a phenolic antioxidant was added, and the mixture was coagulated with an aqueous calcium chloride solution, washed with water, dehydrated and dried to obtain a styrene resin (B) powder.

(2) Production of flame-retardant resin composition Styrene resin (B) and aromatic polycarbonate (A) (Taflon FN3000A manufactured by Mitsubishi Kasei Co., Ltd.) produced as described in (1) above and the difficulties shown in Table 3. The flame retardants (C) and (D) polyterafluoroethylene were added at the ratio of 201
Blending was carried out with a super mixer (Kawata Co., Ltd.) and pellets were prepared at a temperature of 230 ° C. with a 44 m / m co-directional twin-screw extruder (manufactured by Nippon Steel Co., Ltd.). A test piece was molded from the pellet with a 5 ounce injection molding machine (manufactured by Nissei Kogyo Co., Ltd.) under the conditions of a screw rotation speed of 80 rpm and a nozzle set temperature of 230 ° C.

Examples 2 to 10 and Comparative Examples 1 to 3 In the same manner as in Example 1 above, flame-retardant resin compositions having the compositions shown in Tables 1 to 3 and test pieces thereof were prepared. Using the test pieces prepared as described above, flame retardancy, tensile elongation and heat distortion resistance were measured by the following methods. The results are shown in Table 3. The flame retardancy was evaluated based on UL-94 standard. UL-9
In accordance with No. 4, after the standard gas flame was contacted with the 1/16 inch bar twice, V-0 (total combustion time of 50 seconds or less, maximum combustion time of 10 seconds or less, no melt dripping), V -1 (total burning seconds is 250 seconds or less, maximum burning seconds 30 seconds or less, no melt dripping), V-2 (total burning seconds 250 seconds or less, one burning maximum 30 seconds) Hereinafter, melt dripping was carried out), and the above non-standard was designated as B (Burning). Tensile elongation was evaluated in a tensile test based on ASTM D638. Heat distortion resistance is ASTM D648
Based on the above, it was evaluated by HDT of 18.6 kg / cm ² load.

[0029]

[Table 3]

From the results shown in Table 3, it can be seen that the flame-retardant resin composition of the present invention represented by Examples is excellent in flame retardancy, mechanical strength and heat distortion resistance.

The abbreviations used in Tables 1 and 2 represent the following substances, respectively. AN: acrylonitrile PMI: N-phenylmaleimide PMS: p-methylstyrene EX: compound represented by the formula (II) PBD: polybutadiene rubber, average 2500Å PBA: polybutyl acrylate rubber, average particle size 24
00Å

[0032]

As described above, the flame-retardant resin composition of the present invention is excellent in flame retardancy, mechanical strength and heat distortion resistance.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C08L 55/02 LMF 7142-4J 69/00 LPP 9363-4J (72) Inventor Masahiro Asada Suma Ward, Kobe City, Hyogo Prefecture No. 1 45-102 at 8-1, Yokoo

Claims (4)

[Claims] 1. An aromatic polycarbonate resin (A) 5-5
Flame retardant (C) 1 to 100 parts by weight of a resin composed of 95% by weight and 95 to 5% by weight of the following styrene resin (B).
40 parts by weight and (D) polytetrafluoroethylene 0.
A flame-retardant resin composition comprising 05 to 5 parts by weight. Styrenic resin (B): Copolymer (X) comprising 5 to 100% by weight of copolymer (Xa) and 95 to 0% by weight of copolymer (Xb), and graft copolymer (Ya) 5 to 100 The graft copolymer (Y) is composed of 95% by weight and 95 to 0% by weight of the graft copolymer (Yb). (Xa): 5 to 80% by weight of aromatic vinyl compound, 15 to 55% by weight of vinyl cyanide compound, 5 to 40% by weight of N-substituted maleimide compound, and 0 to 20% by weight of other monomer copolymerizable therewith. %, And the reduced viscosity of the methyl ethyl ketone soluble component of the copolymer is in the range of 0.15 to 2.0 dl / g at 30 ° C. in a dimethylformamide solution. (Xb): Obtained from 40 to 90% by weight of aromatic vinyl compound, 10 to 60% by weight of vinyl cyanide compound, 0 to 30% by weight of alkyl methacrylate, and 0 to 20% by weight of other monomer copolymerizable therewith. And a reduced viscosity of the methyl ethyl ketone soluble component of the copolymer in the dimethylformamide solution at 0.15 to 2.0 dl / g at 30 ° C. (Ya): 30 to 90% by weight of a rubber-like polymer, 5 to 80% by weight of an aromatic vinyl compound, and 15 of a vinyl cyanide compound.
-55% by weight, N-substituted maleimide compound 5-40% by weight and other monomers copolymerizable with these 0-20% by weight
A graft copolymer obtained by polymerizing 70 to 10% by weight of a monomer mixture consisting of. (Yb): a graft copolymer obtained by polymerizing 30 to 90% by weight of a rubber-like polymer with 70 to 10% by weight of a monomer mixture consisting of the following formula group. 10 ≦ e + (f / 4) ≦ 40 h = 100−e−f−g e ≧ 0, f ≧ 0 0 ≦ g ≦ 90, and 0 ≦ h ≦ 20 [wherein, e, f, g, And h are the weight of the vinyl cyanide compound (e), the alkyl methacrylate (f), the aromatic vinyl compound (g), and the other vinyl monomer (h) copolymerizable therewith in the monomer mixture. The ratio (%) is shown. ] 2. The flame-retardant resin composition according to claim 1, wherein the flame-retardant agent (C) is a phosphorus-based flame retardant having no halogen atom and a melting point of 80 ° C. or higher. 3. A styrene-based resin (B) copolymer (X
a) is an aromatic vinyl compound 4.99 to 70% by weight, a vinyl cyanide compound 15 to 55% by weight, an N-substituted maleimide compound 5 to 40% by weight, and an epoxy group-containing vinyl compound 0.01 to 10% by weight. % And 0 to 20% by weight of another monomer copolymerizable therewith, and the reduced viscosity of the methyl ethyl ketone soluble component of the copolymer is 0.15 to 2 at 30 ° C. in a dimethylformamide solution. The flame-retardant resin composition according to claim 1, which is in the range of 0.0 dl / g. 4. A styrene resin (B) graft copolymer (Ya) comprising a rubber polymer in an amount of 30 to 90% by weight, an aromatic vinyl compound in an amount of 4.99 to 70% by weight, and a vinyl cyanide compound in an amount of 15 to 90% by weight. 55% by weight, 5-40% by weight of N-substituted maleimide compound, 0.01-10% by weight of epoxy group-containing vinyl compound, and 0-20% by weight of other monomer copolymerizable therewith. The flame-retardant resin composition according to claim 1, which is obtained by polymerizing 70 to 10% by weight of the body mixture.