JP2000239544A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition which has high flame retardancy and extremely reduced mold deposits generated in its molding process and furthermore excels in flowability and mechanical properties by including a thermoplastic resin and a specific organophosphorus compound at a specific ratio. SOLUTION: This composition is obtained by including (A) 100 pts.wt. of a thermoplastic resin, (B) 0.1-30 pts.wt. of an organophosphorus compound of the formula (X is a bivalent or higher valent organic group; Ra to Rd are each an alkyl, cycloalkyl, aryl and at least one of them is an alkyl or cycloalkyl, n is a natural number; j, k, l, and m are each 0 or 1) and if necessary, (C) polytetrafluoroethylene (D) an inorganic filler, etc. The component A is e.g. a polycarbonate resin, a blend of a polycarbonate resin and rubber-reinforced resin, a polyphenylene ether resin, a blend of polyphenylene ether resin and polystyrene resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has high flame retardancy, has very little occurrence of mold deposits (MD) adhering to a mold surface during molding, and has excellent fluidity and mechanical properties. The present invention relates to a flame-retardant resin composition.

[0002]

2. Description of the Related Art Thermoplastic resins are generally light, water-resistant,
It is widely used as a building material, a material for electric / electronic / consumer electronics, a material for automobiles, a fiber material, etc. because of its excellent chemical resistance, electric insulation, mechanical properties, etc., and easy molding process. . In particular, polycarbonate resin has excellent mechanical properties, heat resistance, and transparency, and is widely used as a housing material for OA equipment such as electrical appliances, computers, printers, and copiers. There is a strong demand for a material having both high fluidity for light weight and thinness and high impact resistance at the same time.

For the purpose of making polycarbonate resin flame-retardant, Japanese Patent Publication No. 6-45747 discloses a blend composition of a polycarbonate resin and a monophosphorus compound such as triphenyl phosphate (TPP). In addition to the low heat resistance of the resin, there is a problem that a phosphorus compound adheres to the surface of a mold during molding, that is, a mold deposit (MD) tends to occur. In addition, in the composition described in Japanese Patent Publication No. 18336/1990, a blend composition of a polycarbonate resin and an oligomeric phosphate ester is disclosed, but the oligomeric phosphate ester is more molded than a monophosphoric compound such as TPP. The MD generated at the time decreases, but on the other hand, more flame retardant must be blended than the monophosphorus compound in order to secure the required flame retardancy, so that the fluidity and mechanical properties However, there still remains a disadvantage that it is difficult to obtain an excellent resin composition.

Also, a blend composition of polycarbonate and a rubber-reinforced resin such as an ABS resin has excellent mechanical properties and heat resistance, and is widely used as a housing material for OA equipment such as electric products, computers and word processors. However, similarly, a material having both high flame retardancy, high fluidity, and high impact resistance has been strongly demanded. In response to such demands, polycarbonate resin and AB
An organic phosphorus compound is added to a blend composition of a rubber-reinforced resin such as an S resin to impart flame retardancy. For example, JP-A-2-32154 discloses a rubber reinforced resin represented by a polycarbonate resin and an ABS resin and a TPP.
However, there is a problem that the heat resistance of the resin is low and MD during molding is likely to occur. In the composition described in JP-A-2-115262, a blend composition of a rubber reinforced resin represented by a polycarbonate resin and an ABS resin and an oligomeric phosphate ester is disclosed. However, there is a drawback that the impact resistance of the resin composition is lowered because more flame retardant is required to be blended than the monophosphorus compound in order to secure the required flame retardancy.

Further, Japanese Patent Application Laid-Open Nos. 4-285655, 4-298554, 4-300
937, JP-A-6-192553, JP-A-6-228364, JP-A-6-240127, JP-A-7-11119, JP-A-7-2612
9, JP-A-7-33971, JP-A-7-8
2466, JP-A-7-145307, JP-A-7-150028, JP-A-7-199681, JP-A-7-196873, and JP-A-7-19
6873, JP-A-7-196874, JP-A-7-331045, JP-A-7-331051, JP-A-8-3397, JP-A-8-34991
6, JP-A-8-34926, JP-A-8-6
No. 7810, JP-A-8-120169, JP-A-8-127686, JP-A-8-165392, JP-A-8-225737, JP-A-8-27
No. 7344, JP-A-8-209772, JP-A-9-3312, JP-A-9-48912,
JP-A-9-95610, JP-A-9-104811
JP, JP-A-9-124920, JP-A-9-1433
No. 57, Japanese Patent Application Laid-Open No. 9-165518, Japanese Patent Application Laid-Open
-176471, JP-A-9-183893, JP-A-9-188808, JP-A-9-194
No. 713 discloses that an oligomeric phosphate ester flame retardant is added to a blend system of a polycarbonate and a styrene rubber reinforced resin. In any of the compositions, a monophosphorus compound is used as a flame retardant. As compared with the case, there is a problem in maintaining a high balance between impact resistance and flame retardancy.

Further, polyphenylene ether resins have properties such as excellent mechanical properties, electrical properties, acid resistance, alkali resistance, heat resistance, etc., and low water absorption and good dimensional stability. It is widely used as a material for housings and chassis of office automation equipment such as computers and word processors, and these materials often require high flame retardancy. Although polyphenylene ether resin originally has excellent flame retardancy, it is generally used as an alloy with a styrene resin because of poor processability, but the flame retardancy is impaired by that amount. Triphenyl phosphate, cresyl diphenyl phosphate, to improve the flame retardancy of polyphenylene ether resin,
It is disclosed that a monophosphorus compound such as tricresyl phosphate and isopropylphenyl phosphate, or an oligomeric phosphate ester is blended as a flame retardant. However, there remains a problem in solving the problem of MD during molding and maintaining a balance between the impact resistance and the flame retardancy of the resin composition.

As described above, by using an oligomeric phosphate ester flame retardant, a polycarbonate resin, a blend composition of polycarbonate and a styrene rubber reinforced resin, a polyphenylene ether resin, or a polycarbonate and a styrene rubber reinforced resin can be used. MD at the time of molding to a thermoplastic resin represented by a blend composition of
Generation can be suppressed and flame retardancy can be imparted. However, the oligomeric phosphate ester flame retardant must be blended more than the monophosphorus compound in order to obtain the required flame retardancy, and the mechanical properties, In particular, it was inevitable that the impact resistance and the elongation at break decreased.

[0008]

The problem to be solved by the present invention is that the flame retardancy is high and the MD generated during molding is high.
An object of the present invention is to provide a flame-retardant resin composition having extremely low flowability and excellent both fluidity and mechanical properties.

[0009]

In order to maintain favorable mechanical properties of the resin, a flame retardant which can provide an effective flame retardant effect by adding a small amount of a flame retardant is preferable. According to our research and analysis, it has been found that the flame retardancy of a resin composition using a conventional oligomeric phosphate compound is almost dependent on the content of phosphorus element in the resin composition. For example, thickness 1
In order to meet the UL94 5VB test on a / 10 inch test piece, it was necessary to blend the oligomeric phosphate compound so that the phosphorus element content in the resin composition was approximately 1 wt%. Was done. On the other hand, when TPP which is a monophosphorus compound is used, the content of the phosphorus element in the resin composition required to meet the UL94 5VB test in a 1/10 inch thick test piece is 0.8 to 0. 9.9 wt%, which was favorable for balancing the flame retardancy and mechanical properties of the resin composition at a higher level. However, the use of TPP has a problem that MD tends to occur during molding.

The oligomeric phosphoric ester compound used as a flame retardant for a resin is usually one whose all substituents are aryl groups for the purpose of improving thermal stability. However, when all of the substituents are aryl groups, the phosphorus content in the flame retardant decreases. In order to obtain an effective flame retardant effect by adding a small amount of a flame retardant, it is preferable that the phosphorus content in the flame retardant is higher. The present inventors have studied an oligomeric phosphate compound in which an alkyl group or a cycloalkyl group is partially introduced without replacing all of the substituents with an aryl group in order to solve the above problem. The acid ester has a high phosphorus content, a low viscosity, and is found to have thermal stability that can withstand melt-kneading. Further, by blending with various thermoplastic resins, the conventional oligomeric phosphate ester compound is obtained. Required flame retardancy is obtained with a phosphorus element content lower than in the case of a composition using
The present inventors have found that a flame-retardant resin composition with a small decrease in impact resistance can be obtained, and have reached the present invention.

That is, the present invention relates to 100 parts by weight of a thermoplastic resin (A) and 0.1 to 30 parts by weight of one or more organic phosphorus compounds (B) represented by the following formula (1):

Embedded image (Where X is a divalent or higher valent organic group, R ^a , R ^b , R ^c , R ^d
Is an alkyl group, a cycloalkyl group, or an aryl group, at least one of which is an alkyl group or a cycloalkyl group, and n is a natural number, j, k, l, and m are each independently 0 or 1. ). Hereinafter, the present invention will be described in detail.

The thermoplastic resin (A) used in the present invention
Are polystyrene resin, polyolefin resin, polyamide resin, polyoxymethylene resin, polyphenylene ether resin, polycarbonate resin, polyester resin, polymethyl methacrylate resin, polybutadiene, polyisoprene, polychloroprene, butadiene styrene Copolymers, conjugated diene rubbers such as butadiene / acrylonitrile copolymer, and acrylic rubbers such as ethylene propylene rubber, ethyl acrylate, and butyl acrylate can be exemplified. These can be used alone or in combination. These include so-called rubber-reinforced resins reinforced with elastomers.

Among the above, preferred are polycarbonate resins, blends of polycarbonate resins and rubber-reinforced resins, polyphenylene ether resins, and blends of polyphenylene ether resins and polystyrene resins. The polycarbonate resin that can be preferably used as the component (A) of the present invention has a main chain composed of a repeating unit represented by the following formula (2).

[0014]

Embedded image (In the formula, Ar is a divalent aromatic residue, for example, phenylene, naphthylene, biphenylene, pyridylene,
One represented by the following formula (3) is given. )

[0015]

Embedded image (Wherein, Ar ¹ and Ar ² are each an arylene group. For example, phenylene, naphthylene, biphenylene,
Represents a group such as pyridylene, and Y is an alkylene group or a substituted alkylene group represented by the formula (4). )

[0016]

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a lower alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and optionally a halogen atom,
^May be substituted with an alkoxy group, k is an integer of 3 to 11, R ⁵ and R ⁶ are individually selected for each X, and are each independently a hydrogen atom or a lower alkyl group;
X is an aryl group, which may be optionally substituted with a halogen atom or an alkoxy group, and X represents a carbon atom. In addition, a divalent aromatic residue represented by the following formula (5) may be contained as a copolymer component.

[0017]

Embedded image (In the formula, Ar ¹ and Ar ² are the same as in the formula (3). Z is a mere bond or —O—, —CO—, —S—, —SO ₂
—, —CO ₂ —, —CON (R ¹ ) — (R ¹ is the formula (4)
Same as above). Examples of these divalent aromatic residues include the following formula (6)
And the formula (7).

[0018]

Embedded image

[0019]

Embedded image (Wherein, R ⁷ and R ⁸ are each independently hydrogen, halogen, a C ₁ -C ₁₀ alkyl group, a C ₁ -C ₁₀ alkoxy group, a C ₁ -C ₁₀ cycloalkyl group or a phenyl group. And n is an integer of 1 to 4, and when m is 2 to 4, each R ⁷ may be the same or different, and when n is 2 to 4, each R ⁸ may be the same. A different one may be used.) Among them, one represented by the following formula (8) is a preferable example. In particular, those containing 85 mol% or more of a repeating unit represented by the following formula (8) as Ar are preferable.

[0020]

Embedded image Moreover, the polycarbonate which can be used in the present invention may contain a trivalent or higher aromatic residue as a copolymerization component. Although the molecular structure of the polymer terminal is not particularly limited, a phenolic hydroxyl group, an aryl carbonate group,
One or more terminal groups selected from alkyl carbonate groups can be bonded. The aryl carbonate terminal group is represented by the following formula (9), and specific examples include, for example,
Equation (10) is given.

[0021]

Embedded image (In the formula, Ar ³ is a monovalent aromatic residue, and the aromatic ring may be substituted.)

[0022]

Embedded image The alkyl carbonate terminal group is represented by the following formula (11), and specific examples include the following formula (12).

[0023]

Embedded image (In the formula, R ⁹ represents a linear or branched alkyl group having 1 to 20 carbon atoms.)

[0024]

Embedded image

Of these, phenolic hydroxyl groups, phenyl carbonate groups, pt-butylphenyl carbonate groups, p-cumylphenyl carbonate and the like are preferably used. In the present application, the ratio of the phenolic hydroxyl group terminal to the other terminal is not particularly limited, but the phenolic hydroxyl group terminal ratio for all terminals is preferably in the range of 20 to 80 mol%.

The method for measuring the phenolic hydroxyl group terminal amount is as follows:
In general, a method using NMR, a titanium method,
It can be determined by the V or IR method. The weight average molecular weight (Mw) of the polycarbonate used in the present invention is:
Generally, the weight average molecular weight is preferably in the range of 5,000 to 50,000, more preferably 10,000.
~ 40,000, more preferably 15,000
~ 30,000, particularly preferably 18,000 ~
25,000. If it is less than 5,000, the impact resistance is insufficient, and if it exceeds 50,000, the fluidity is insufficient, which is not preferable.

The measurement of the weight-average molecular weight (Mw) in the present invention is carried out using gel permeation chromatography (GPC). The measurement conditions are as follows: tetrahydrofuran is used as a solvent, polystyrene gel is used.
It is determined from the constitutive curve of the standard monodisperse polystyrene using a reduced molecular weight calibration curve according to the following equation. ^{_{M PC = 0.3591M PS 1.0388 (M}} PC molecular weight of the polycarbonate, M _PS molecular weight of polystyrene) These polycarbonates can be prepared by known methods. Specifically, a known method for reacting an aromatic dihydroxy compound with a carbonate precursor, for example, an interfacial polymerization method (phosgene method) in which an aromatic dihydroxy compound is reacted with phosgene in the presence of an aqueous sodium hydroxide solution and a methylene chloride solvent. , An ester exchange method in which an aromatic dihydroxy compound is reacted with diphenyl carbonate (melting method), and a method in which a crystallized carbonate prepolymer is solid-phase polymerized (Japanese Patent Laid-Open No.
271426, 3-68627, etc.).

Preferred polycarbonate resins include:
A polycarbonate resin containing substantially no chlorine atom, which is produced from a dihydric phenol (aromatic dihydroxy compound) and a carbonic acid diester by a transesterification method, may be mentioned. The rubber reinforced resin that can be used in the present invention refers to a rubbery polymer and all rubber reinforced resins containing one or more vinyl compounds as components.

As the rubbery polymer which is a component of the rubber reinforced resin, any one having a glass transition temperature of 0 ° C. or less can be used. Specifically, polybutadiene, styrene / butadiene copolymer rubber, diene rubber such as acrylonitrile / butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, polyisoprene, polychloroprene, ethylene / propylene rubber, ethylene / propylene Block copolymers such as diene terpolymer rubber, styrene / butadiene block copolymer rubber, styrene / isoprene block copolymer rubber, and hydrogenated products thereof can be used. Among these polymers, preferred are polybutadiene, styrene / butadiene copolymer rubber, acrylonitrile / butadiene copolymer rubber, polybutyl acrylate, and the like.

The ratio of the rubbery polymer in the rubber reinforced resin is 1
It is used in the range of up to 95% by weight, but is determined according to the required mechanical strength, rigidity and moldability. Preferably, it is 5 to 45% by weight, more preferably 10 to 40% by weight.
% By weight. Examples of the vinyl compound which is a component of the rubber-reinforced resin include aromatic vinyl compounds such as styrene, α-methylstyrene, and paramethylstyrene; alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, butyl acrylate, and ethyl acrylate;
(Meth) acrylic acids such as acrylic acid and methacrylic acid; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; α, β-unsaturated carboxylic acids such as maleic anhydride; N-phenylmaleimide; N-methylmaleimide; Maleimide monomers such as N-cyclohexylmaleimide, and glycidyl group-containing monomers such as glycidyl methacrylate are exemplified, but aromatic vinyl compounds, alkyl (meth) acrylates, vinyl cyanide monomers, and maleimide Styrene, acrylonitrile, N-phenylmaleimide, and butyl acrylate.

These vinyl compounds can be used alone or in combination of two or more. Preferably,
It is a combination of an aromatic vinyl compound and a non-aromatic vinyl compound. In this case, the aromatic vinyl compound and the non-aromatic vinyl compound are used in an arbitrary ratio, but the preferable ratio of the non-aromatic vinyl compound is 5 to 80% by weight based on the total amount of the vinyl compound alone. Range.

The method for producing the rubber-reinforced resin is not particularly limited. For example, by graft-polymerizing one or more of the above-mentioned vinyl compounds in the presence of a rubbery polymer, One or more rubber-based graft copolymers containing one or more vinyl compounds described above as a graft polymerization component, and one or more vinyl compounds separately produced. It can also be obtained by blending a copolymer. Examples of such a resin include ABS resin (acrylonitrile / butadiene / styrene resin), AAS resin (acrylonitrile / butyl acrylate / styrene resin), and HIPS (high impact polystyrene resin).

When the polycarbonate resin (X1) and the rubber reinforced resin (Y1) are blended and used, the ratio is as follows:
It is determined according to the required mechanical strength, rigidity, moldability and heat resistance. Preferably, the component (X1) is 20 to 9
5 parts by weight, 80 to 5 parts by weight of the component (Y1), more preferably 30 to 90 parts by weight of the component (X1), and 70 to 10 parts by weight of the component (Y1). Also, a blend of a polycarbonate resin and a rubber-reinforced resin requires a polycarbonate resin, a copolymer of one or more vinyl compounds, and one or more rubber-based graft polymers. Blends can be used in a composition ratio.

In the present invention, a copolymer containing a polycarbonate resin, an aromatic vinyl monomer component and a vinyl cyanide monomer component, and / or an aromatic vinyl monomer component and a vinyl cyanide monomer Rubber-based graft polymer obtained by grafting a vinyl-based monomer onto a composite rubber containing a polyorganosiloxane and a polyalkyl (meth) acrylate on a copolymer containing the component and an alkyl (meth) acrylate monomer , A silicone acrylic composite rubber) can be suitably used as the component (A). The composition can be suitably used as a flame-retardant resin composition having both high fluidity and impact resistance.

Here, the copolymer containing an aromatic vinyl monomer component and a vinyl cyanide monomer component is styrene, α
A copolymer comprising, as constituents, an aromatic vinyl monomer component (a) such as methylstyrene and paramethylstyrene and a vinyl cyanide monomer component (b) such as acrylonitrile and methacrylonitrile; (A) / in copolymer
The composition ratio of (b) is not particularly limited, but preferably (a) is 95 to 50% by weight, (b) is 5 to 50% by weight, more preferably (a) is 92 to 65% by weight,
(B) is 8 to 35% by weight. Preferred examples of the copolymer containing an aromatic vinyl monomer component and a vinyl cyanide monomer component that can be used in the present invention include styrene.
Acrylonitrile copolymer resin (SAN) is exemplified.

Further, a copolymer containing an aromatic vinyl monomer component, a vinyl cyanide monomer component and an alkyl (meth) acrylate monomer component includes styrene, α-methylstyrene, paramethylstyrene and the like. An aromatic vinyl monomer component (a), preferably styrene, and a vinyl cyanide monomer component (b) such as acrylonitrile and methacrylonitrile, preferably acrylonitrile, methyl methacrylate, methyl acrylate, butyl acrylate;
A copolymer containing an alkyl (meth) acrylate monomer component (c) such as ethyl acrylate, preferably butyl acrylate, as a component. The composition ratio of each component in the copolymer is not particularly limited, but preferably (b)
15 to 35% by weight of a vinyl cyanide monomer component, (c)
The content of the alkyl (meth) acrylate monomer component is preferably in the range of 2 to 20% by weight.

A copolymer containing an aromatic vinyl monomer component and a vinyl cyanide monomer component, and / or an aromatic vinyl monomer component, a vinyl cyanide monomer component and an alkyl (meth) acrylate monomer Examples of the method for producing the copolymer containing a monomer component include generally known production methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. In that case, a monomer copolymerizable with these components can be used in addition to the components (a), (b) and (c) as long as the gist of the present invention is not hindered. Examples of such copolymerizable monomers include (meth) acrylic acids such as acrylic acid and methacrylic acid, and α, such as maleic anhydride.
β-unsaturated carboxylic acid, N-phenylmaleimide, N-
Examples include maleimide monomers such as methylmaleimide and N-cyclohexylmaleimide, and glycidyl group-containing monomers such as glycidyl methacrylate. These monomers can be used alone or in combination of two or more.

A composite rubber-based graft copolymer (silicone acrylic composite rubber) obtained by grafting a vinyl monomer onto a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate is a polyorganosiloxane rubber. 10 to 90% by weight of the component and 90 to 10% by weight of the polyalkyl (meth) acrylate rubber
(00% by weight) is a graft copolymer formed by graft polymerization of one or two or more vinyl compounds onto a composite rubber having a structure in which they are intertwined with each other.

Here, as the vinyl compound, styrene,
Aromatic vinyl compounds such as α-methylstyrene and paramethylstyrene, alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate, (meth) acrylic acids such as acrylic acid and methacrylic acid, acrylonitrile,
Vinyl cyanide monomer such as methacrylonitrile, α, β-unsaturated carboxylic acid such as maleic anhydride, maleimide monomer such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, glycidyl Glycidyl group-containing monomers such as methacrylates may be mentioned, but are preferably aromatic vinyl compounds, alkyl (meth) acrylates, vinyl cyanide monomers, and maleimide monomers, more preferably styrene, Acrylonitrile, N-phenylmaleimide, butyl acrylate, and methyl methacrylate.

These vinyl compounds can be used alone or in combination of two or more. The polyorganosiloxane rubber and the polyalkyl (meth) acrylate rubber, which are components of the composite rubber, have a structure that cannot be substantially separated, and the preferred particle diameter is 0.08 to 0.6 μm. The production of a composite rubber having such a structure is described in, for example, JP-A-64-79257 and JP-A-1-19074.
No. 6 can be used. Also, for example, Mitsubishi Rayon Co., Ltd.
-2001 (trade name) is available.

In the present invention, a copolymer containing (a-1) a polycarbonate resin, (a-2) an aromatic vinyl monomer component and a vinyl cyanide monomer component, and / or an aromatic vinyl monomer A resin composition obtained by blending a copolymer containing a body component, a vinyl cyanide monomer component and an alkyl (meth) acrylate monomer component, and (a-3) a silicone acrylic composite rubber is used as the component (A). When the components are used, the component (a-1) is 65 to 90 parts by weight, the component (a-2) is 35 to 10 parts by weight, and the components (a-1) and (a-
Component (a-3) is used in an amount of 1 to 3 based on a total of 100 parts by weight of 2).
Although it is 0 parts by weight, the component (a-1) is preferably 70 to 8 in balance of mechanical strength, rigidity, moldability and heat resistance.
5 parts by weight, 30 to 15 parts by weight of component (a-2), (a-
Component (a-) is added to 100 parts by weight of the total of (1) and (a-2).
3) is 2 to 20 parts by weight, and more preferably the component (a)
-1) is 75 to 83 parts by weight, and component (a-2) is 25 to 1
Component (a-3) is 3 to 10 parts by weight based on 7 parts by weight, and 100 parts by weight in total of (a-1) and (a-2). Also,
The silicone acrylic composite rubber also has an action as an anti-dripping agent during combustion.

The polyphenylene ether resin preferably used as the component (A) in the present invention is represented by the following formula (1)
3) and / or a homopolymer or a copolymer having a repeating unit represented by the formula (14).

Embedded image

[0043]

Embedded image

(Where R ¹⁰ , R ¹¹ , R ¹² , R ¹³ ,
R ¹⁴ and R ¹⁵ independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, or hydrogen. However, R ¹⁴ and R ¹⁵ are not simultaneously hydrogen. Representative examples of the homopolymer of the polyphenylene ether resin include poly (2,6-dimethyl-
1,4-phenylene) ether, poly (2-methyl-6)
-Ethyl-1,4-phenylene ether, poly (2,6
-Diethyl-1,4-phenylene) ether, poly (2
-Ethyl-6-n-propyl-1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1) , 4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6) -Chloroethyl-1,4-phenylene) ether and the like.

Among them, poly (2,6-dimethyl-1,1
4-Phenylene) ether is particularly preferred. The polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main unit. For example,
Copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymer of 2,6-dimethylphenol and o-cresol, or 2,6-dimethylphenol and 2,3,6- Examples include a copolymer with trimethylphenol and o-cresol.

In the polyphenylene ether-based resin of the present invention, various other phenylene ether units which have conventionally been proposed to be allowed to exist in the polyphenylene ether resin without departing from the gist of the present invention are used. It may be included as a partial structure. Japanese Patent Application No. 63-1 / 1988 discloses an example of a proposal for coexistence in a small amount.
2- (dialkylaminomethyl) -6-methylphenylene ether unit and 2- (N-alkyl-N-phenylaminomethyl) -6-methyl described in JP-A-2698 and JP-A-63-301222. And phenylene ether units. Also included are polyphenylene ether resins in which a small amount of diphenoquinone or the like is bonded in the main chain. Further, for example, Japanese Patent Laid-Open No. 2-27
No. 6823, JP-A-63-108059, JP-A-59-59724 and the like also include polyphenylene ethers modified with compounds having a carbon-carbon double bond.

The method for producing the polyphenylene ether resin used in the present invention is not particularly limited. For example, US Pat. No. 4,788,277 (Japanese Patent Application No. Sho 62).
In the presence of dibutylamine, 2,6-xylenol can be produced by oxidative coupling polymerization according to the method described in US Pat. Further, the molecular weight and the molecular weight distribution are not particularly limited. A polystyrene resin can be blended with the polyphenylene ether resin at an arbitrary ratio. Preferably, 10 to 99% by weight of polyphenylene ether resin
Of the polystyrene-based resin in an amount of 90 to 1% by weight.

The polystyrene resin as used herein is a vinyl aromatic polymer or a rubber-modified vinyl aromatic polymer.

Examples of the vinyl aromatic polymer include styrene, o-
Methylstyrene, p-methylstyrene, m-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, p
Polymers such as core-alkyl-substituted styrenes such as -tert-butylstyrene, α-methylstyrene, α-alkyl-substituted styrenes such as α-methyl-p-methylstyrene, and at least one of at least one of these and other vinyl compounds And copolymers of two or more of these. Examples of the compound copolymerizable with the vinyl aromatic compound include methyl methacrylate, methacrylic esters such as ethyl methacrylate, acrylonitrile, unsaturated nitrile compounds such as methacrylonitrile, and acid anhydrides such as maleic anhydride. .

Particularly preferred among these polymers are polystyrene and styrene / acrylonitrile copolymer. Examples of the rubber used for the rubber-modified vinyl aromatic polymer include polybutadiene, styrene / butadiene copolymer, polyisoprene, butadiene / isoprene copolymer, natural rubber, and ethylene / propylene copolymer. In particular, polybutadiene and styrene-butadiene copolymer are preferable, and as the rubber-modified aromatic polymer, rubber-modified polystyrene (HIPS) and rubber-modified styrene-acrylonitrile copolymer (ABS resin) are preferable.

The component (B) used in the present invention has the formula (1)
The organic phosphorus compound represented by

Embedded image

(Where X is a divalent or higher valent organic group, R ^a ,
R ^b , R ^c , and R ^d are an alkyl group, a cycloalkyl group, or an aryl group, at least one of which is an alkyl group or a cycloalkyl group, and n is a natural number, j, k, l, m
Each is independently 0 or 1. The component (B) is a compound represented by the formula (1) in which the substituents ^Ra , ^Rb and ^Rc
And at least one of R ^d is an alkyl group or a cycloalkyl group, and the other R is selected from an alkyl group, a cycloalkyl group, and an aryl group.

The preferred alkyl group or cycloalkyl group is an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group, and the cycloalkyl group may have a substituent such as an alkyl group or a halogen. More preferably, it is an alkyl group having 1 to 4 carbon atoms. Among them, a methyl group and an ethyl group are particularly preferable because the phosphorus content in the compound can be increased and the viscosity of the compound can be reduced. The aryl group may or may not be substituted with one or more hydrogens.

When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, and a halogenated aryl group. (Eg, an arylalkoxyalkyl group) or a group obtained by combining these substituents with an oxygen atom, a sulfur atom, a nitrogen atom, or the like (eg, an arylsulfonylaryl group) may be used as the substituent. Particularly preferred aryl groups are phenyl, cresyl, xylyl, propylphenyl, and butylphenyl.

In the component (B), when all of the substituents R ^a , R ^b , R ^c and R ^d in the formula (1) are an alkyl group or a cycloalkyl group, the kneading with the thermoplastic resin is not required. Heat resistance may decrease. Further, the substituent R
^{When all of a} , R ^b , R ^c and R ^d are aryl groups, the heat resistance of the compound improves, but the phosphorus content decreases and the viscosity increases. In order to increase the phosphorus content of the component (B) as much as possible, to lower the viscosity, to further improve the compatibility with the resin, and to suppress the generation of MD during molding as much as possible, ^Ra , R in the formula (1) ^b , R ^c ,
And it is preferable that the number ratio of the alkyl group and / or a cycloalkyl group to the total number of R ^d is 0.1 to 0.8, more preferably Ku is 0.2 to 0.6.

In the formula (1), X is a divalent or higher valent organic group, and the divalent or higher valent organic group may be an alkylene group which may or may not be substituted, and preferably a phenylene group or a polynuclear phenol. And the relative positions of two or more free valences are arbitrary. Particularly preferred are hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane (bisphenol A), dihydroxydiphenyl,
p, p'-Dihydroxydiphenyl sulfone, dihydroxynaphthalene and the like.

Component (B) is usually a mixture of compounds having different values of n in formula (1) and different proportions of alkyl, cycloalkyl and aryl groups.
In the case of a mixture of compounds having different values of n, the weight average value of n is generally an average value of 1 to 5. According to our research analysis, the smaller the weight average of n, the higher the compatibility with the resin and the flame retardancy. Among them, the compound of n = 1 is preferable because the balance between the flame retardancy and the mechanical properties of the resin composition is particularly excellent. Accordingly, in the component (B), the proportion of the compound represented by n = 1 is preferably 50% by weight or more, and the weight average value of n is preferably in the range of 1 to 3, and represented by n = 1. It is particularly preferred that the proportion occupied by the compound is at least 60% by weight of the component (B) and the weight average value of n is in the range of 1-2.

The compound of the component (B) of the present invention is, for example,
Phosphorus halide compounds such as phosphorus oxyhalide or derivatives thereof; dihydric phenol compounds such as bisphenol A, hydroquinone and resorcinol; phenol compounds such as 2,6-xylenol and phenol; and methyl alcohol, ethyl alcohol and isopropyl alcohol An alkyl alcohol such as butyl alcohol and cyclohexanol or a cycloalkyl alcohol compound can be synthesized as a raw material.

The degree of condensation n of the component (B), the composition of the substituents, and the identity of the components were determined by gel permeation chromatography (GPC), liquid chromatography (LC), and liquid chromatography / mass spectrum (LC / M
S). The content of component (B) is determined according to the required level of flame retardancy.
It is necessary that the amount is 0.1 to 30 parts by weight based on part by weight of the component (A). If the amount is less than 0.1 part by weight, the required flame retardant effect is not exhibited. If it exceeds 30 parts by weight, the mechanical strength of the resin will be reduced. It is preferably in the range of 0.5 to 20 parts by weight, and particularly preferably in the range of 5 to 15 parts by weight.

In the resin composition of the present invention, the component (B)
Other organophosphorus compounds (hereinafter collectively referred to as component (C)) may be contained within a range not inconsistent with the gist of the present invention. The normally acceptable content of component (C) is
And 30% by weight or less per compound with respect to the total amount of component (C) and 40% by weight or less as a whole of component (C). If the component (C) is contained in excess of the above value, it becomes difficult to keep the MD during molding at a low level.

Further, it is effective and preferable to use an anti-dripping agent in combination with the component (B). Examples of the anti-dripping agent include perfluoroalkane polymers such as polytetrafluoroethylene, silicone rubber, polycarbonate / diorganosiloxane copolymer, siloxane polyetherimide, liquid crystal polymer, and the above-mentioned silicone acrylic composite rubber. Particularly preferred is polytetrafluoroethylene, which is preferably in the range of 0.01 to 3 parts by weight when component (A) is 100 parts by weight,
More preferably, it is 0.05 to 2 parts. If less than 0.01 parts by weight, the effect of preventing dripping during combustion is insufficient,
High flame retardancy cannot be obtained. On the other hand, when the amount exceeds 3 parts by weight, the formability and rigidity are reduced.

Further, other flame retardants other than the components (B) and (C) may be used in combination with the component (B), for example,
Nitrogen-containing organic compounds such as melamine, inorganic compounds such as magnesium hydroxide and aluminum hydroxide, metal oxides such as antimony oxide, bismuth oxide, zinc oxide and tin oxide, red phosphorus, phosphine, hypophosphorous acid, and phosphorous acid , Metaphosphoric acid, pyrophosphoric acid, inorganic phosphorus compounds such as phosphoric anhydride,
Expanded graphite, silica, a silica-based glass melt, and the like may be contained within a range not contrary to the gist of the present invention.

The resin composition of the present invention may contain glass fibers, glass flakes, or the like for the purpose of modifying the resin composition.
Inorganic fillers such as glass beads, calcium carbonate, talc and mica, and reinforcing agents such as carbon fiber and charcoal can be added. The preferable addition amount is the thermoplastic resin (A).
The amount is 0.01 to 60 parts by weight, more preferably 5 to 55 parts by weight, per 100 parts by weight. Furthermore, if necessary, ordinary additives, that is, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a coloring agent, titanium oxide, a surface modifier,
Dispersants, plasticizers, stabilizers and the like can be added.

The method for producing the resin composition of the present invention is not particularly limited, and the resin composition can be produced by a usual method, for example, melt blending by extrusion kneading. Further, at that time, it is optional to add additives such as known antioxidants, ultraviolet absorbers, lubricants, release agents, antistatic agents, coloring agents, fillers, etc., within a range not to impair the gist of the present invention. . Further, the molding method of a molded article made of these thermoplastic resin compositions includes extrusion molding, compression molding, injection molding, gas assist molding and the like, and is not particularly limited.

[0064]

The present invention will be described in detail with reference to the following examples. The materials used are shown below. 1. Resin (Component (A)) (Polycarbonate: PC) A bisphenol A-based polycarbonate produced from bisphenol A and diphenyl carbonate by a melt transesterification method. Mw = 20,500 Hydroxy group terminal amount = 35% (acrylonitrile / butadiene / styrene resin: AB
S) An ABS resin composed of 29.7 wt% of butadiene units, 19.0 wt% of acrylonitrile units, and 51.3 wt% of styrene units. (Butyl acrylate / acrylonitrile / styrene resin: BAAS) butyl acrylate unit 10.0 wt
%, Acrylonitrile unit 27.0 wt%, and styrene unit 63.0 wt%. Mw = 110,000

(Polyphenylene ether resin: PPE)
U.S. Pat. No. 4,788,277 (Japanese Patent Application No. 62-7)
No. 7570) produced by oxidative coupling polymerization of 2,6-xylenol in the presence of dibutylamine according to the method described in No. 7570), η _{sp / c} = 0.42, and the melt viscosity is 280. It is 49,000 poise when measured at 140 ° C. at a shear rate of 140 sec ⁻¹ . (High Impact Polystyrene: HIPS) A HIPS resin comprising a butadiene rubber component of 12% by weight and a styrene unit of 88% by weight. (Silicone acrylic composite rubber) methyl methacrylate
Butyl acrylate / dimethyl siloxane copolymer (trade name METABLEN S-2001 (manufactured by Mitsubishi Rayon Co., Ltd.)) A powdery resin having a residual of 10 mesh of less than 90%. (Fluorine-based resin: PTFE) Teflon 30J (manufactured by Mitsui DuPont Fluorochemicals) Water-based PTFE dispersion

2. Organic Phosphorus Compound (Component (B)) (Organic phosphorus compound (B1)) 131 g (0.575) of dried bisphenol A using a 3 liter glass round bottom flask equipped with a stirrer and a condenser.
Mole), 243 g of phenylphosphoric acid dichloride
(1.15 mol) and 0.82 g of magnesium chloride
(0.0086 mol), and the mixture was stirred while gradually heating with an oil bath, heated to 130 ° C., and further reacted for 8 hours.

Hydrochloric acid by-produced in the reaction was introduced into an alkali trap for treatment. Phenyl phosphoric acid dichloride was removed from the obtained reaction mixture under reduced pressure for 6 hours while stirring at 130 ° C. and 1 mmHg. Thereafter, 230 g (2.3 mol) of cyclohexanol and 91 g (1.
15 mol) and 540 g of benzene were gradually added with stirring, and reacted at 25 ° C. for 10 hours. After completion of the reaction, the reaction mixture was washed once with a 0.1N hydrochloric acid solution at 60 ° C.
Subsequently, a batch washing treatment was performed three times at 60 ° C. with pure water.

From the reaction product after washing, benzene, moisture and water were sufficiently removed by a rotary evaporator to obtain the compound of the formula (1)
Wherein X is a diphenyloldimethylmethane group, the substituent R is a cyclohexyl group and a phenyl group, and the ratio of the number of cyclohexyl groups to the total number of the substituents R is 0. And an organic phosphorus compound (B) having an average value of the repeating number n of 1.21.
1) was obtained.

(Organic phosphorus compound (B2)) An organic phosphorus compound represented by the formula (1), wherein cyclohexanol is replaced with methanol and X is diphenyl A roll dimethylmethane group, wherein the substituent R comprises a methyl group and a phenyl group, and the ratio of the number of methyl groups to the total number of the substituents R is 0.5;
An organic phosphorus compound (B2) having an average number of repetitions n of 1.20 was obtained.

(Organic phosphorus compound (B3)) An organic phosphorus compound represented by (1), wherein bisphenol A is replaced by resorcinol and the method of synthesizing organic phosphorus compound B2, wherein X is a resorcinol group Wherein the substituent R comprises a methyl group and a phenyl group, the ratio of the number of methyl groups to the total number of the substituents R is 0.5, and the number of repetitions n
An organic phosphorus compound (B3) having an average value of 1.22 was obtained. (Organic phosphorus compound (B4)) CR733S (manufactured by Daihachi Chemical Industry) (Organic phosphorus compound (B5)) CR741 (manufactured by Daihachi Chemical Industry) (Organic phosphorus compound (B6)) PX-200 (Dahachi Chemical Industry) (Organic phosphorus compound (B7)) TPP (Daichi Chemical Co., Ltd.)

[0071]

Examples 1 to 8 and Comparative Examples 1 to 12 The resin compositions were blended in the compositions (parts by weight) listed in Tables 1 and 2, and a twin screw extruder (ZS) set at a cylinder temperature of 250 ° C.
K-25, manufactured by W & P Co.), and a flame retardant was injected with a pump from the middle of the extruder and granulated to obtain pellets of the resin composition. (1) Measured at 220 ° C. under a load of 10 kg according to MFR ASTM D1238. (2) Flame retardancy test The obtained pellets were dried, and the cylinder temperature was 260 ° C.
Molding was performed using an injection molding machine (Autoshot 50D, manufactured by FANUC) set at a mold temperature of 65 ° C. to prepare a test piece shaped molded body (thickness 1/10 inch) for a combustion test. Flame retardancy evaluation was performed based on the UL94 standard vertical combustion test (UL94 5VB), and the total extinction time (unit: second) performed on five test pieces was evaluated.

(3) Izod Impact Test A 1/8 inch, notched measurement was made according to ASTM D256. The test piece was molded by an injection molding machine set at a cylinder temperature of 260 ° C. and a mold temperature of 65 ° C. (Unit: kgf · cm / cm) (4) Evaluation of mold deposit (MD) Injection pressure was 905 kgf / cm ² using an injection molding machine (NIIGATA CN75) set at a cylinder temperature of 260 ° C. and a mold temperature of 40 ° C. Under the conditions of a time of 3 seconds, a cooling time of 1.2 seconds, a rest time of 2 seconds, and a molding cycle of 8.3 seconds, a molded body having a test piece weight of 4 g was continuously molded, and the surface state of the mold after 200 shots was visually observed. . ：: MD is hardly observed. Δ: MD is slightly observed. ×: MD is clearly observed.

The results are shown in Tables 1 and 2. Examples 1 to 8
Indicates that the flame retardant performance is effectively obtained with a relatively small amount of the flame retardant. Furthermore, the impact resistance is excellent. In addition, from the comparison between Examples 5, 6, and 8 and Comparative Examples 1 to 12, the resin composition of the present invention has the same phosphorus content as the resin composition using the conventional oligomer phosphate ester. It can be seen that the flame retardant effect is high when compared between the compositions. FIG. 1 shows the results. In addition, MD was hardly observed in the resin composition of the present invention. When TPP was used, the flame retardant effect was higher than when a conventional oligomeric phosphate ester was used, but MD was remarkable.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

As described above, the flame-retardant resin of the present invention has high flame retardancy, hardly any mold deposit, and high impact resistance.

[Brief description of the drawings]

FIG. 1 is a diagram showing the relationship between the phosphorus concentration in a resin composition and the total quenching time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) // (C08L 69/00 25:12 51:04)

Claims (15)

[Claims] A flame-retardant resin comprising 100 parts by weight of a thermoplastic resin (A) and 0.1 to 30 parts by weight of one or more organic phosphorus compounds (B) represented by the following formula (1): Composition. Embedded image (Where X is a divalent or higher valent organic group, R ^a , R ^b , R ^c , R ^d
Is an alkyl group, a cycloalkyl group, or an aryl group, at least one of which is an alkyl group or a cycloalkyl group, and n is a natural number, j, k, l, and m are each independently 0 or 1. ) 2. The ratio of the number of alkyl groups and / or cycloalkyl groups to the total number of R ^a , R ^b , R ^c and R ^{d in the} formula (1) is 0.1 to 0.8. 2. The flame-retardant resin composition according to 1. 3. The ratio of the number of alkyl groups and / or cycloalkyl groups to the total number of R ^a , R ^b , R ^c and R ^{d in the} formula (1) is from 0.2 to 0.6. 2. The flame-retardant resin composition according to 1. 4. Component (B) is a mixture of two or more organophosphorus compounds having different values of n, wherein the proportion of the compound represented by n = 1 is 50% by weight or more and the weight of n The flame-retardant resin composition according to any one of claims 1 to 3, wherein the average value is in the range of 1 to 3. 5. The composition according to claim 1, wherein in the component (B), the proportion of the organic phosphorus compound represented by n = 1 is 60% by weight or more, and the weight average value of n is in the range of 1-2. The flame-retardant resin composition according to the above. 6. The formula (1) wherein R ^a , R ^b , R ^c , and R ^d are C ₁ -C _4.
The flame-retardant resin composition according to any one of claims 1 to 5, further comprising an alkyl group. 7. The flame-retardant resin composition according to claim 1, wherein X in the formula (1) is diphenyloldimethylmethane. 8. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polycarbonate. 9. A rubber-reinforced resin comprising a thermoplastic resin (A) containing 1 to 99% by weight of a polycarbonate resin, a rubbery polymer and one or more vinyl compounds as components.
The flame-retardant resin composition according to any one of claims 1 to 7, which is a resin composition comprising 1% by weight. 10. A thermoplastic resin comprising: (a-1) 65 to 95 parts by weight of a polycarbonate resin; and (a-2) an aromatic vinyl monomer component and a vinyl cyanide monomer component. And / or 35 to 5 parts by weight of a copolymer containing an aromatic vinyl monomer component, a vinyl cyanide monomer component and an alkyl (meth) acrylate monomer component,
For a total of 100 parts by weight of (a-1) and (a-2),
(A-3) Composite rubber-based graft copolymers 1 to 3 in which a vinyl-based monomer is grafted on a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate
The flame-retardant resin composition according to any one of claims 1 to 7, which is a resin composition comprising 0 parts by weight. 11. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyphenylene ether resin. 12. A thermoplastic resin (A) comprising 10 to 99% by weight of a polyphenylene ether resin and 90% by weight of a polystyrene resin.
The flame-retardant resin composition according to any one of claims 1 to 7, which is a resin composition comprising 1 to 1% by weight. 13. The flame-retardant resin composition according to claim 8, 9 or 10, wherein the polycarbonate resin is produced by a transesterification method. 14. The flame-retardant resin composition according to claim 1, further comprising 0.01 to 3 parts by weight of polytetrafluoroethylene. 15. The flame-retardant resin composition according to claim 1, further comprising 0.01 to 60 parts by weight of an inorganic filler.