JPH08319388A - Flame retardant resin composition - Google Patents

Abstract

PURPOSE: To further improve the impact resistance while retaining excellent flame resistance by combining a polymer blend containing a styrene-based resin having a graft chain of a molecular weight within a specific range with a flame retardant component containing a phosphorus compound. CONSTITUTION: This flame retardant resin composition comprises respective components of (A) a polycarbonate resin, (B) a styrene-based resin containing (B-1) a graft copolymer prepared by grafting an aromatic vinyl compound and a vinyl cyanide compound onto a rubber-like polymer and (B-2) a copolymer obtained by copolymerizing an aromatic vinyl compound with a vinyl compound copolymerizable with the aromatic vinyl compound and (C) a phosphorus compound. A part of the graft copolymer (B-1) soluble in tetrahydrofuran has 95000-180000 weight-average molecular weight.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant resin composition. More specifically, the present invention relates to a flame-retardant resin composition having excellent impact resistance, which is obtained by blending a polymer blend containing a polycarbonate resin and a specific styrene resin with a flame retardant containing a phosphorus compound.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used industrially because they have excellent mechanical properties and thermal properties. However, since it has a problem of high melt viscosity and poor moldability, many polymer blends with other thermoplastic resins have been developed. Among them, styrene resins (acrylonitrile-butadiene-styrene (AB
Polymer blends with S) resins, etc.
It is widely used in the A equipment field, electronic and electrical fields, etc.
On the other hand, in recent years, there has been a strong demand for flame-retardant resin materials used mainly for applications such as office automation equipment and home electric appliances, and many flame-retardant resins have been developed and studied in order to meet these demands.
Conventionally, chlorine- or bromine-containing compounds have been mainly used for flame-retarding polymer blends containing polycarbonate-based resins and styrene-based resins, and in many cases, in addition to these flame-retardants, antimony trioxide etc. It is also used as an auxiliary agent. However, when such a chlorine- or bromine-containing compound is used, the effect of flame retardancy is relatively large, but in the event of a fire or incineration process, a toxic or harmful substance is generated, so emergency activities or fire extinguishing It has problems such as making activities difficult or causing environmental pollution. Therefore, it is desired to develop a flame-retardant resin containing no chlorine or bromine-containing compound or containing a small amount of chlorine or bromine-containing compound. Therefore, a flame retarding method using a phosphorus compound as a flame retardant other than the chlorine- or bromine-containing compound has been proposed. However, in this case, in order to obtain sufficient flame retardancy, the blending amount becomes large, so that there is a problem that physical properties such as impact resistance and heat resistance of the obtained flame retardant resin are significantly lowered. Had.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to retain excellent flame retardancy and to have good impact resistance. Another object of the present invention is to provide a flame-retardant resin composition having an excellent physical property balance.

[0004]

Means for Solving the Problems The inventors of the present invention have been earnestly studied to improve physical properties such as flame retardancy and impact resistance of a polymer blend containing a polycarbonate resin and a styrene resin. Remarkably, by combining a flame retardant component containing a phosphorus compound with a polymer blend containing a specific styrene resin, it is possible to dramatically improve impact resistance while maintaining excellent flame retardancy. The present invention has been achieved by discovering that That is, the present invention comprises (1) a flame-retardant resin composition containing the following components (A), (B) and (C). (A) Polycarbonate-based resin (B) Styrene-based resin containing the following components (B-1) and (B-2), (B-1) Rubber polymer, aromatic vinyl compound, and vinyl cyanide A graft copolymer obtained by grafting a compound, wherein the tetrahydrofuran-soluble component of the graft copolymer has a weight average molecular weight of 95,000 to 18,000.
0 graft copolymer (B-2) a copolymer obtained by copolymerizing an aromatic vinyl compound and a vinyl compound copolymerizable with an aromatic vinyl compound (C) phosphorus compound, (2) (1 ) In addition to the components (A), (B), and (C) described above, as the component (D), at least one selected from silicone, a fluororesin, and a phenolic resin.
A flame-retardant resin composition containing a seed, (3) a polycarbonate resin 99 to (A) as a component
5% by weight and 1 to 95 of styrene resin as component (B)
1 to 40 parts by weight of the organophosphorus compound as the component (C) and 0.01 to 5 parts by weight of the silicone and / or fluororesin as the component (D) with respect to 100 parts by weight of the polymer blend consisting of 1% by weight. (2) Flame-retardant resin composition according to (2), (4) Polycarbonate resin 99 to as component (A)
5% by weight and 1 to 95 of styrene resin as component (B)
1 to 40 parts by weight of the organophosphorus compound as the component (C) and 1 to 30 parts by weight of the phenolic resin as the component (D) with respect to 100 parts by weight of the polymer blend consisting of 2% by weight (2) ) The flame-retardant resin composition described above is provided.

The present invention will be described in detail below. The polycarbonate resin (A) used in the present invention is produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Typical examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A] and bis (4
-Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-
Bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, and the like, and an alkyl group on its aromatic ring, The thing in which the aryl group etc. were substituted is mentioned.
A preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane-based one, and more preferably one containing bisphenol A as a main raw material. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate, and the like, and specifically, phosgene, diphenyl carbonate, dimethyl carbonate,
The dihaloformates of dihydric phenols and mixtures thereof. In manufacturing polycarbonate resin,
One or more of these dihydric phenols can be used, and if necessary, an appropriate molecular weight modifier, a catalyst for accelerating the reaction and the like can be used. As the polycarbonate resin of the present invention, a branched polycarbonate resin obtained by copolymerizing a polyfunctional compound or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic difunctional carboxylic acid having 8 or more carbon atoms can also be used. . The polycarbonate-based resin thus obtained may be used alone or in combination of two or more. In the present invention, a halogen-free polycarbonate is preferably used.

Styrene resin (B) used in the present invention
Contains the following components (B-1) and (B-2). (B-1) An aromatic vinyl compound and a vinyl cyanide compound are indispensable to the rubbery polymer, and if necessary, a vinyl compound copolymerizable with the aromatic vinyl compound and / or the vinyl cyanide compound is grafted. The graft copolymer thus obtained, wherein the weight average molecular weight of the tetrahydrofuran-soluble component of the graft copolymer is 95,000 to 1800.
Graft Copolymer (B-2) Copolymer Obtained by Copolymerizing Aromatic Vinyl Compound and Vinyl Compound Copolymerizable with Aromatic Vinyl Compound Graft Copolymer in Styrenic Resin (B) (B-
The rubbery polymer used in 1) is a rubbery polymer having a glass transition temperature of 10 ° C. or lower, and examples thereof include polybutadiene, butadiene-styrene copolymer, butadiene-styrene block copolymer, and hydrogenated butadiene. -Styrene block copolymer, butadiene rubber such as butadiene-acrylonitrile copolymer, acrylic rubber,
Ethylene-propylene (diene component) copolymer, isobutylene-isoprene copolymer, styrene-isoprene block copolymer, hydrogenated styrene-isoprene block copolymer, polyurethane rubber, polyamide rubber,
Examples thereof include silicone rubber. Further, a composite rubber composed of silicone rubber and acrylic rubber or a composite rubber composed of butadiene rubber and acrylic rubber can be used. In the present invention, preferably polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-
Propylene (diene component) copolymer, silicone rubber and the like are used.

Examples of the aromatic vinyl compound used in the graft copolymer (B-1) include styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, hydroxystyrene, halostyrene and sodium styrenesulfonate. However, styrene, α-methylstyrene and the like are preferably used. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is preferably used. As the vinyl compound copolymerizable with the aromatic vinyl compound and / or the vinyl cyanide compound, methyl acrylate,
(Meth) acrylic acid esters such as ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-hexylmaleimide , N-cyclohexylmaleimide, N-phenylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (alkyl-substituted phenyl) maleimide and other maleimide compounds, and further unsaturated dicarboxylic acid anhydride compounds such as maleic anhydride. And preferably methyl methacrylate, N-phenylmaleimide, maleic anhydride or the like is used. Any of the above-mentioned aromatic vinyl compounds, vinyl cyanide compounds, aromatic vinyl compounds and / or vinyl compounds copolymerizable with vinyl cyanide compounds may be used alone or in combination of two or more. The proportion of the rubbery polymer in the graft copolymer (B-1) is preferably in the range of 5 to 95% by weight, more preferably 10 to 90% by weight. If the proportion of the rubbery polymer is less than 5% by weight, the impact resistance is not sufficient, and if it exceeds 95% by weight, the graft ratio, the surface gloss of the resin, the moldability and the flame retardancy are lowered. The proportion of the graft component in the graft copolymer (B-1) is preferably 5 to 95% by weight, more preferably 10 to 90.
% By weight.

The graft ratio of the graft copolymer (B-1) is preferably 5 to 150% by weight, more preferably 10%.
~ 120% by weight. When the graft ratio is less than 5% by weight, sufficient impact resistance cannot be obtained, and when it exceeds 150% by weight, dripping tends to occur during combustion.

Copolymerizable with the aromatic vinyl compound (x ₁ ), vinyl cyanide compound (x ₂ ), (x ₁ ), and / or (x ₂ ) used in the graft copolymer (B-1). The ratio of the vinyl compound (x ₃ ) is (x ₁ ) + (x ₂ ) + (x ₃ ) 10
0% by weight, (x ₁ ) is 10 to 95% by weight, (x ₁ )
₂ ) is 5 to 90% by weight, (x ₃ ) is preferably 0 to 85% by weight, more preferably (x ₁ ) is 50 to 90% by weight,
(X ₂ ) is in the range of 10 to 50% by weight, (x ₃ ) is in the range of 0 to 40% by weight, particularly preferably (x ₁ ) is in the range of 60 to 80% by weight and (x ₂ ) is in the range of 20 to 40% by weight. , (X ₃ ) is in the range of 0 to 20% by weight. Within the above range, a flame-retardant resin composition having more excellent physical properties such as impact resistance, heat resistance, and moldability can be obtained. Graft copolymer (B-1) of the present invention
May be used alone or in combination of two or more. If the graft copolymer (B-1) is produced by copolymerizing the above (x ₁ ) to (X ₃ ) in the presence of a rubbery polymer, the production method thereof is not particularly limited, and the bulk polymerization is not performed. Known methods such as solution polymerization, suspension polymerization and emulsion polymerization can be used.

The graft copolymer (B
-1) has a weight average molecular weight of the tetrahydrofuran-soluble component of the graft copolymer of 95,000 to 180,000, preferably 100,000 to 160000,
Particularly preferably, it is 100,000 to 140,000. The tetrahydrofuran-soluble component in the present invention means a component (non-graft polymer) which is not graft-reacted when the above-mentioned (x ₁ ) to (X ₃ ) are graft-copolymerized with the rubber polymer. is there.
The weight average molecular weight in the present invention refers to that obtained by gel permeation chromatography using tetrahydrofuran as a solvent in terms of polystyrene.
Specifically, one obtained by using one Shodex KF-80M (manufactured by Showa Denko KK) for the column and measuring on a polystyrene standard under the following conditions can be mentioned. Conditions Solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Detection: Ultraviolet detector Wavelength 272 nm Column temperature: 35 ° C. The flame-retardant resin composition of the present invention is characterized in that the tetrahydrofuran-soluble component has a weight average molecular weight of 95,000 to 180,000.
The use of the graft copolymer (B-1) characterized in that it is possible to achieve a high level of flame retardancy without significantly sacrificing impact resistance. However, when the graft copolymer (B-1) characterized in that the tetrahydrofuran-soluble component has a weight-average molecular weight within the above range is not used, the resulting resin composition has a markedly decreased impact resistance and a molded product. This is not preferable, since problems such as poor properties may occur, and the flame retardancy may decrease, such as the resin dropping during combustion and the burning time becoming longer.

The aromatic vinyl compound used in the copolymer (B-2) in the styrene resin (B) is styrene, α-methylstyrene, vinyltoluene,
Examples thereof include t-butyl styrene, hydroxystyrene, halostyrene, sodium styrene sulfonate, and the like, and styrene and α-methylstyrene are preferably used.
Examples of the vinyl compound copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate and butyl methacrylate. (Meth) acrylic acid ester such as maleimide, N-methylmaleimide, N
-Ethyl maleimide, N-propyl maleimide, N-hexyl maleimide, N-cyclohexyl maleimide, N
-Phenylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (alkyl-substituted phenyl) maleimide and other maleimide-based compounds, and maleic anhydride and other unsaturated dicarboxylic acid anhydride-based compounds and the like, and preferably acrylonitrile , Methyl methacrylate, N-phenylmaleimide, maleic anhydride and the like are used. The above aromatic vinyl compounds and vinyl compounds copolymerizable with the aromatic vinyl compounds may be used alone or in combination of two or more.

Aromatic vinyl compound (y ₁ ) used for the copolymer (B-2) in the styrene resin (B),
The proportion of the vinyl compound (y ₂ ) copolymerizable with (y ₁ ) is
When (y ₁ ) + (y ₂ ) is 100% by weight, (y ₁ ) is 1
0 to 95% by weight, (y ₂ ) is preferably 5 to 90% by weight, more preferably (y ₁ ) is 40 to 90% by weight, (y
₂ ) is in the range of 10 to 60% by weight, particularly preferably (y ₁ ) is 45 to 80% by weight and (y ₂ ) is 20 to 55% by weight.
Range. Within the above range, a flame-retardant resin composition having more excellent physical properties such as impact resistance, heat resistance, and moldability can be obtained.

As the copolymer (B-2) of the present invention, preferably used are α-methylstyrene / acrylonitrile copolymer, styrene / acrylonitrile copolymer, styrene / acrylonitrile / methyl methacrylate copolymer. , Α-methylstyrene / acrylonitrile /
Methyl methacrylate copolymer, α-methylstyrene / N
-Phenylmaleimide copolymer, styrene / N-phenylmaleimide copolymer, styrene / N-phenylmaleimide / acrylonitrile copolymer, α-methylstyrene / N-phenylmaleimide / acrylonitrile copolymer, styrene / N-phenylmaleimide / Maleic anhydride copolymer, α-methylstyrene / N-phenylmaleimide / maleic anhydride copolymer and the like, more preferably styrene / acrylonitrile copolymer, styrene / N.
-Phenylmaleimide / maleic anhydride copolymer, styrene / N-phenylmaleimide copolymer and the like. These polymers may be used alone or in combination of two or more.

There are no particular restrictions on the method for producing these polymers, and known methods such as bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization can be used. Further, a copolymer obtained by selecting a vinyl compound containing a maleimide compound as a vinyl compound copolymerizable with an aromatic vinyl compound, such as a styrene / N-phenylmaleimide / maleic anhydride copolymer, is In the first step, maleic anhydride in an amount corresponding to the maleimide compound is copolymerized in place of the maleimide compound, and in the second step, a part or most of the maleic anhydride residue in the polymer is converted into the desired maleimide compound. It can also be produced by imidization with an amino compound such as aniline or an aniline derivative corresponding to the compound structure.

According to the present invention, a resin composition having excellent flame retardancy and good impact resistance and having a good balance of physical properties can be obtained, but a more excellent balance of physical properties, which also imparts good heat resistance, is obtained. If you want to obtain a resin composition having
A copolymer obtained by selecting a maleimide compound as a vinyl compound copolymerizable with an aromatic vinyl compound (B-
It is particularly preferable to incorporate 2) into the styrene resin (B). By containing the copolymer (B-2) having a maleimide compound as a monomer unit structure, a resin composition having excellent flame retardancy, impact resistance and heat resistance and having a better physical property balance is obtained. be able to.

The content ratio of the graft copolymer (B-1) and the copolymer (B-2) in the styrene resin (B) is
Graft copolymer (B-1) + copolymer (B-2) 1
When it is set to 00% by weight, preferably the graft copolymer (B-1) / copolymer (B-2) = 5/95 to 95/5.
(Weight ratio), and more preferably 10/90 to 90 /
10 (weight ratio). Within the above range, a flame-retardant resin composition having a much better balance of physical properties such as flame retardancy, impact resistance and heat resistance can be obtained.

A typical composition preferable as the styrene resin (B) of the present invention is that the graft copolymer (B-1) has a weight average molecular weight of tetrahydrofuran soluble component of 95,000 to 180,000. And a graft copolymer obtained by graft-polymerizing a mixture of styrene and acrylonitrile on polybutadiene, a styrene / acrylonitrile copolymer as a copolymer (B-2), and a styrene / N-phenylmaleimide / maleic anhydride copolymer. Examples thereof include polymers and styrene resins containing at least one selected from styrene / N-phenylmaleimide copolymers.

In the present invention, the graft copolymer (B
It is also possible to use a core / shell type copolymer together with -1). In this case, the core is polybutadiene,
The rubber-like polymer in the graft copolymer (B-1) such as polyisoprene, acrylic rubber, and composite rubber composed of silicone rubber and acrylic rubber is included. The shell constituent material is preferably a copolymer obtained from a mixture of the aromatic vinyl compound and the (meth) acrylic acid ester, a polymer obtained from only the (meth) acrylic acid ester, but is not limited thereto. Not a thing. In the present invention, the blending ratio of the polymer blend of the polycarbonate resin and the styrene resin is in the range of polycarbonate resin / styrene resin = 99/1 to 5/95 (weight ratio), preferably 95/5 to 10 / 90
(Weight ratio) range, more preferably 90/10 to 20 /
The range is 80. If the ratio of the styrene resin exceeds 95% by weight, properties such as heat resistance and flame retardancy may not be sufficiently obtained, and if it is less than 1% by weight, good processability,
Moldability cannot be obtained.

The phosphorus compound used in the present invention is not particularly limited as long as it is a compound having a phosphorus atom, but an organic phosphorus compound represented by the general formula (I) is preferably used.

Embedded image (In the formula, R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or an organic group, except when R ₁ = R ₂ = R ₃ = H. X is a divalent or higher valent organic group. , Y is an oxygen atom or a sulfur atom, Z is an alkoxy group or a mercapto group, p is 0 or 1, q is an integer of 1 to 30, and r is r.
Is an integer of 0 or more, and n is 0 or 1. However, it is not limited to these. )

In the above formula, the organic group is, for example, an alkyl group which may be substituted or not, a cycloalkyl group, an aryl group and the like. When it is substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, and the like, and a group in which these substituents are combined (for example, an arylalkoxyalkyl group) or these substituents are oxygen. A group in which an atom, a sulfur atom, a nitrogen atom or the like is bonded and combined (eg, an arylsulfonylaryl group) may be used as a substituent. The divalent or higher valent organic group means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to carbon atoms from the above-mentioned organic groups. Examples include alkylene groups, and preferably (substituted) phenylene groups, those derived from polynuclear phenols such as bisphenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred are hydroquinone, resorcinol, bis (4-hydroxyphenyl) methane,
2,2-bis (4-hydroxyphenyl) propane [bisphenol A], dihydroxydiphenyl, p, p '
-Dihydroxydiphenyl sulfone, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone and the like.

Illustrating these phosphorus compounds, examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate. , Trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (o-phenylphenyl) phosphate, tris (p-phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xylenyldiphenylphosphate, diphenyl (2- Ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, o-phenylphenyl dicresylphos Eto, dibutyl phosphate,
Monobutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, etc. And condensates thereof, such as resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dixylenyl phosphate), hydroquinone bis (diphenyl phosphate), hydroquinone bis (dicresyl phosphate), hydroquinone bis (diquin). Silenyl phosphate), biphenol bis (dixylenyl phosphate), bisphenol Bis (diphenyl phosphate), bisphosphate and polyphosphate oligomers such as bisphenol A bis (dicresyl phosphate), and the like.

A hydroxyl group-containing aromatic phosphate ester containing one or more phenolic hydroxyl groups in triphenyl phosphate, tricresyl phosphate, condensed phosphate ester thereof or the like can also be used as the phosphorus compound. . Examples of the hydroxyl group-containing aromatic phosphate ester include diphenyl resorcinol phosphate, phenyl diresorcinol phosphate, dicresyl resorcinol phosphate, and the like.

Examples of the phosphite include trimethylphosphite, triethylphosphite, tributylphosphite, tri (2-ethylhexyl) phosphite, tributoxyethylphosphite, trioleylphosphite, triphenylphosphite, tricresylphosphite. Fight, trixylenylphosphite, tris (isopropylphenyl) phosphite, trisnonylphenylphosphite, tris (o-phenylphenyl) phosphite, tris (p-phenylphenyl) phosphite, trinaphthylphosphite, cresyldiphenyl Phosphite, xylenyl diphenyl phosphite, diphenyl (2-ethylhexyl) phosphite, di (isopropylphenyl) phenyl phosphite, o-phenylphenyl dicresi Phosphite, dibutyl phosphite, monobutyl phosphite, di-2-ethylhexyl phosphite, monoisodecyl phosphites and condensates thereof and the like.

Other phosphorus compounds include triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, phosphazene compounds and red phosphorus.

In the present invention, a phosphoric acid ester is preferably used as the organic phosphorus compound, and among them, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, cresyl diphenyl phosphate and xyle are particularly preferable. Examples thereof include monophosphates such as nildiphenyl phosphate and di (isopropylphenyl) phenyl phosphate, and bisphosphates such as resorcinol bis (diphenyl phosphate) and bisphenol A bis (dicresyl phosphate). These phosphorus compounds may be used alone or in combination of two or more.

The blending amount of these phosphorus compounds is 1 to 40 parts by weight, preferably 3 to 100 parts by weight of the component (A).
30 parts by weight, more preferably 5 to 25 parts by weight. 1
If it is less than 40 parts by weight, a sufficient flame retardant effect cannot be obtained, and if it is more than 40 parts by weight, the heat resistance and impact resistance of the resulting composition are remarkably lowered, and the volatile content during molding is increased. And the like. For the purpose of preventing the phenomenon that the molten resin burned when the resin is burned is dropped, silicone, fluorine resin, and phenol resin all work effectively.

In the present invention, a resin composition having both flame retardancy and impact resistance can be obtained by containing the above-mentioned (A) polycarbonate resin, (B) styrene resin, and (C) phosphorus compound. In the case of imparting even more excellent flame retardancy, it is desirable to contain at least one selected from the above (D) silicone, a fluororesin, and a phenolic resin.

The silicone used in the present invention is, in principle, in the molecular structure thereof.

Embedded image There is no particular limitation as long as it has a skeleton. Examples of the silicone used in the present invention include polydimethylsiloxane, polymethylphenylsiloxane, amino-modified silicone, mercapto-modified silicone, and epoxy-modified silicone. These may be used alone or in combination of two or more. Furthermore, these silicones can be used in a wide range of molecular weights of several hundreds to several millions, and their forms are oily, varnish-like, gum-like,
It may be in any form such as resin. In the present invention, polydimethylsiloxane is preferably used.

The fluororesin used in the present invention is not particularly limited as long as it is a resin containing a fluorine atom. Examples of the fluorine-based resin used in the present invention include polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and tetrafluoroethylene-ethylene. Examples thereof include copolymers, polytrifluorochloroethylene, and polyvinylidene fluoride. You may use only 1 type of these,
You may use it in combination of 2 or more type. The form of the fluororesin is emulsion, suspension, microfibril,
It may be in the form of powder, particles or the like. In the present invention, polytetrafluoroethylene is preferably used.

When silicone or a fluororesin is used in the present invention, its addition amount is 100 parts by weight of the component (A).
0.01-5 parts by weight, preferably 0.05-3 parts by weight,
It is more preferably 0.1 to 2 parts by weight. silicone,
When the amount of the fluorine-based resin is less than 0.01 parts by weight, sufficient anti-dripping effect cannot be obtained, and when it exceeds 5 parts by weight, the appearance of molded products of the compounded resin composition is poor and defective phenomena such as increase in melt viscosity occur. May occur.

The phenolic resin used in the present invention is
It is obtained by reacting phenols and aldehydes under an acidic or alkaline catalyst. Examples of phenols include phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, amylphenol, nonylphenol, phenylphenol, phenoxyphenol, hydroquinone, resorcinol, dihydroxydiphenyl, bis (hydroxyphenyl) pentane, bis (4-hydroxyphenyl). ) Methane, bis (4-hydroxyphenyl) butane, bis (4
-Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl)
Examples include sulfide, dihydroxynaphthalene, bis (4-hydroxyphenyl) propane, and the like, and mixtures thereof.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, glyoxal and the like. Further, an aromatic monoaldehyde having at least one phenolic hydroxyl group in one molecule can also be used. Examples of such aromatic monoaldehydes include o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, β-resorcylaldehyde and vanillin.

Examples of the ketones include acetone and the like. These aldehydes and / or ketones may be used alone or in combination of two or more.

In the present invention, both a resol type resin and a novolac type phenolic resin can be used, but a novolac type phenolic resin is preferably used. The novolac-type phenol resin used in the present invention is obtained by reacting the above-mentioned phenols with the above-mentioned aldehydes and / or ketones under an acid catalyst by a known method.
Further, in the present invention, a novolac type phenol resin obtained by substituting a part or all of the above aldehyde and / or ketone with dicyclopentadiene and reacting with the above phenol can also be used. Further, in the present invention, a novolac type phenol resin obtained by replacing a part or all of the aldehyde and / or ketone with an aralkyl halide and / or an aralkyl alcohol derivative and reacting with the phenol can be used. The aralkyl halide and / or aralkyl alcohol derivative in the present invention has the general formula (II)

Embedded image (In the formula, R is a compound which is a halogen atom such as chlorine or bromine, a hydroxyl group, or an alkoxy group.) As the alkoxy group, a lower alkoxy group having 4 or less carbon atoms is preferable.
The aralkyl halide preferably used is α,
α'-dichloro-p-xylene, α, α'-dibromo-
P-xylene, α, α′-diiodo-p-xylene and the like can be mentioned, and preferable aralkyl alcohol derivatives are α, α′-dihydroxy-p-xylene and α, α′-dimethoxy-p-. Xylene, α, α '
-Diethoxy-p-xylene, α, α'-dipropoxy-p-xylene, α, α'-di-n-butoxy-p-xylene, α, α'-di-sec-butoxy-p-xylene, α, Examples include α'-di-isobutoxy-p-xylene.

When the phenolic resin is used in the present invention, the addition amount thereof is 1 to 30 with respect to 100 parts by weight of the component (A).
Parts by weight, preferably 1 to 20 parts by weight, particularly preferably 1
The range is from 15 to 15 parts by weight. The amount of phenolic resin is 1
When the amount is less than the amount by weight, the anti-dripping effect is not sufficiently obtained and the flame retardance is poor, and when the amount is more than 30 parts by weight, the resulting resin composition may have a remarkable decrease in light resistance and impact resistance. There is.

In the present invention, silicone, fluorine resin,
Both of the phenolic resin and the phenolic resin effectively act to prevent the resin from dripping during combustion, but when a flame-retardant resin composition having excellent light resistance is obtained, a fluororesin and / or
Alternatively, it is preferable to use silicone.

In the present invention, if necessary, a thermoplastic resin other than the polycarbonate-based resin and the styrene-based resin may be contained as long as the physical properties such as flame retardancy and impact resistance are not impaired. Typical examples of them are polyester resins (polybutylene terephthalate (PBT), polyethylene terephthalate (PET),
(Polyarylate, liquid crystalline aromatic polyester, etc.), (modified) polyethylene, (modified) polypropylene, (modified) ethylene / propylene copolymer resin, polyamide resin, polyphenylene sulfide, polyphenylene ether, polyacetal, polyetheresteramide , Polyetherimide, polyetheretherketone, polymethylmethacrylate and the like. These resins can be used in combination of two or more kinds.

The flame-retardant resin composition of the present invention does not use a compound containing bromine or chlorine as a flame-retardant component,
Although it exhibits an excellent flame retardant effect, a commonly used known flame retardant additive may be used in combination. The flame retardant additive is not particularly limited as long as it has a flame retardant effect, chlorine or bromine-containing compounds, antimony compounds, nitrogen compounds, thermally expandable graphite, carboxylic acid metal salts, sulfonic acid metal salts, Flame retardant additives such as boric acid metal salt, metal oxide, metal hydroxide, ferrocene, guanamine resin, melamine resin and urea resin can be used. These flame retardant additives may be used alone or in combination of two or more.

There is no special limitation on the method of mixing the resin and the flame retardant, and any means can be adopted as long as they can be mixed uniformly. For example, mixing, kneading, and the like using various mixing machines such as an extruder, a Henschel mixer, a Banbury mixer, a kneader, and a heating roll can be appropriately adopted. At the time of kneading, each component may be kneaded at once, or any component may be kneaded and then the remaining components may be added and kneaded. A preferable kneading method is a method using an extruder, and a twin-screw extruder is particularly preferable as the extruder.

At this time, if necessary, various fillers, additives and the like can be blended in an amount such that the effect is exhibited within the range of not impairing the flame retardancy. Examples thereof include glass fibers, asbestos, carbon fibers, aromatic polyamide fibers, potassium titanate whisker fibers, metal fibers, ceramic fibers, fibrous fillers such as boron whisker fibers, mica, silica, talc, clay, calcium carbonate, Glass beads,
Fillers such as glass balloons and glass flakes, release agents, lubricants, plasticizers, dispersants, UV absorbers, light stabilizers,
Examples thereof include additives such as antioxidants, heat resistance stabilizers, antioxidants, and dyes (face). Further, an impact strength improver for improving the properties of the polymer blend, a compatibilizing component and the like can be added.

[0041]

The following examples are provided to further illustrate the present invention, but these examples are not intended to limit the invention in any way. The following are those used in the compounding formulations of Examples and Comparative Examples. Polycarbonate resin: Teijin Chemicals Panlite K-
1285 Styrenic resin: The following were used as the graft copolymer (B-1) and the copolymer (B-2) constituting the styrene resin. Component (B-1) Graft Copolymer: (b-1-1) to (b-1-5) Using a reactor equipped with a stirrer, the amount of the components shown in Table 1 was determined by a known emulsion polymerization method. In the presence of polybutadiene rubber Table 1
The mixture consisting of styrene and acrylonitrile in the amount shown in was polymerized with cumene hydroperoxide as a polymerization initiator to complete the reaction. At this time, t as a molecular weight regulator
-Dodecyl mercaptan was used accordingly. The polymer latex obtained is coagulated with calcium chloride, washed with water, filtered,
After drying, the graft copolymers (b-1-1) to (b-1-)
5) was obtained. The tetrahydrofuran-soluble component of the graft copolymer was obtained by the following method. That is, 18 g of tetrahydrofuran was added to 1 g of the graft copolymer (B-1), and the mixture was stirred well at room temperature for 3 hours, centrifuged to take out a supernatant liquid, and subsequently, a resin component in the supernatant liquid was precipitated with methanol. Dried. The resin component thus obtained was dissolved in tetrahydrofuran, and the weight average molecular weight (Mw) of the tetrahydrofuran-soluble component was measured by gel permeation chromatography, using one Shodex KF-80M (manufactured by Showa Denko KK) as a column. The polystyrene standard was measured under the following conditions. Conditions Solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Detection: Ultraviolet detector Wavelength 272 nm Column temperature: 35 ° C. Weight average of tetrahydrofuran-soluble components of graft copolymers (b-1-1) to (b-1-5) The molecular weight (Mw) is shown in Table 1.

[0042]

[Table 1]

In Table 1, the graft ratio is s (g) as the amount of the rubber component in 1 g of the graft copolymer (B-1) and t as the tetrahydrofuran insoluble content in 1 g of the graft copolymer (B-1). If it is (g), it is a value calculated by the following equation (1).

[Equation 1] Copolymer of component (B-2): (b-2-1) Styrene / acrylonitrile (weight ratio 7
0/30) A copolymer obtained by emulsion polymerization of the mixture. Reduced viscosity (in methyl ethyl ketone, concentration 0.01 g / ml, 3
Measured at 0 ° C.) is 0.52 dl / g. (B-2-2) Copolymer obtained by solution polymerization of a styrene / N-phenylmaleimide (weight ratio 47/53) mixture.
Reduced viscosity (in methyl ethyl ketone, concentration 0.01 g / m
1, measured at 30 ° C.) is 0.38 dl / g. (B-2-3) A copolymer obtained by solution polymerization of a mixture of styrene / N-phenylmaleimide / maleic anhydride (weight ratio 47 / 52.8 / 0.2). Reduced viscosity (measured at 30 ° C. in methyl ethyl ketone at a concentration of 0.01 g / ml) is 0.40 dl / g. Phosphorus compound (1): Triphenyl phosphate manufactured by Daihachi Chemical Co., Ltd. Phosphorus compound (2): Resorcinol bis (diphenyl phosphate) CR-733S manufactured by Daihachi Chemical Co., Ltd. Fluorine-based resin: Polytetrafluor made by Mitsui DuPont Fluorochemical Ethylene Teflon 6J Silicone: Toray Dow Corning Silicone Polydimethylsiloxane SH-200 oil (viscosity 30000cs) Phenolic resin: Meiwa Kasei Novolac phenolic resin MEH7800 Weight average molecular weight 1,000, average structural formula is general formula (III) It is represented by.

[Chemical 4] Examples 1 to 10 and Comparative Examples 1 to 8 Each component shown in Table 2 and Table 3 was mixed in a blending ratio shown in Table 2 and Table 3 with a Henschel mixer and then a 30 mmφ twin-screw extruder (PCM manufactured by Ikegai Tekko KK, PCM). -30) is used and 250-
The mixture was melt-kneaded and extruded at 280 ° C., and pelletized by a pelletizer. After sufficiently drying the pellets thus obtained, a test piece was prepared by injection molding, and the flame retardancy of the resin composition was evaluated by a UL combustion test. Izod impact strength was measured as an index of impact resistance of the resin composition, and heat distortion temperature (HDT) was measured as an index of heat resistance. The results are also shown in Tables 2 and 3. Flame retardancy is 127mm x 12.7m by injection molding from the obtained pellets.
Combustion test piece measuring mx 1.6 mm was prepared and subject 94 of Underwriters Laboratory, Inc., USA
(UL94) Measured according to the vertical burning test. For Izod impact strength, a notched test piece with a width of 3.2 mm and a notched test piece with a width of 6.4 mm were prepared, and
It was measured according to SK-7110. Heat distortion temperature (HD
T) was measured according to JIS K7207 under a load of 18.5 kgf / cm ² .

[0044]

[Table 2]

[0045]

[Table 3]

From Tables 2 and 3, the graft copolymer (B-1) used in the styrene resin has a weight average molecular weight of 9 which is the tetrahydrofuran-soluble component of the graft copolymer.
It can be seen that a resin composition having good Izod impact strength and high flame retardancy can be obtained by having the characteristic of being 5,000 to 180,000. On the other hand, a graft copolymer (B-
When 1) is used, the Izod impact strength of the resulting resin composition is significantly reduced, which is not preferable. Further, as shown in Table 3, copolymers ((b-2-2), (b-2), (b-2), which have a maleimide compound as a monomer unit structure as a copolymer (B-2) component in a styrene resin. -2-3)) is more preferable because a resin composition having an excellent balance of physical properties, which exhibits excellent flame retardancy and impact resistance as well as good heat resistance, can be obtained.

[0047]

According to the present invention, excellent flame retardancy is maintained by combining a flame retardant component containing a phosphorus compound with a polymer blend containing a styrene resin having a graft chain having a molecular weight in a specific range. In addition, the impact resistance can be further improved.

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Claims (4)

[Claims] 1. A flame-retardant resin composition comprising the following components (A), (B), and (C). (A) Polycarbonate-based resin (B) Styrene-based resin containing the following components (B-1) and (B-2), (B-1) Rubber polymer, aromatic vinyl compound, and vinyl cyanide A graft copolymer obtained by grafting a compound, wherein the tetrahydrofuran-soluble component of the graft copolymer has a weight average molecular weight of 95,000 to 18,000.
(B-2) A copolymer obtained by copolymerizing an aromatic vinyl compound and a vinyl compound copolymerizable with the aromatic vinyl compound (C) Phosphorus compound 2. The component (A), (B), and (C) according to claim 1, and at least one selected from silicone, a fluororesin, and a phenolic resin as a component (D). A flame-retardant resin composition comprising a seed. 3. A polymer blend consisting of 99 to 5% by weight of a polycarbonate resin as the component (A) and 1 to 95% by weight of a styrene resin as the component (B), and an organic phosphorus as the component (C). The flame-retardant resin composition according to claim 2, wherein the compound is 1 to 40 parts by weight and the component (D) is 0.01 to 5 parts by weight of a silicone and / or a fluororesin. 4. A polymer blend comprising 99 to 5% by weight of a polycarbonate resin as the component (A) and 1 to 95% by weight of a styrene resin as the component (B), and an organic phosphorus as the component (C). The flame-retardant resin composition according to claim 2, wherein the compound is 1 to 40 parts by weight and the component (D) is 1 to 30 parts by weight of a phenolic resin.