JPS619450A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To give excellent flame retardancy without deteriorating the excellent characteristics of each component resin, by incorporating specified phosphonate compounds into a resin composition comprising a polyphenylene ether resin and a styrene resin. CONSTITUTION:A phosphonate compound of formula I (where R<1>, R<2>, R<3>, R<4>, and R<5> each are a 1-4C alkyl, phenyl or phenoxy) (e.g. a compound of formula II) or a phosphonate compound of formula III (where R<6> is a 1-4C alkyl or phenyl; R<7>, R<8>, and R<9> each are a 1-4C alkyl, phenyl or phenoxy) (e.g. compound of formula IV) solely or in combination with the other or also with an aromatic phosphate (e.g. triphenyl phosphate) in an amount of 0.2-20pts.wt. are incorporated into 100pts.wt. resin composition comprising a polyphenylene ether resin and a styrene resin to give an aimed flame retardant resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a flame-retardant resin composition in which a specific flame retardant is blended into a resin composition consisting of a polyphenylene ether resin and a styrene resin.

In this blasting process, the general formula (A) (R'',
R2+ R3+ R' + R5 represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a phenoxy group. )
Alternatively, the general formula (B) R' (R6 represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R', R8, and R9 represent an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a phenoxy This invention relates to an extremely flame-retardant (excellent resin composition) in which a phosphonate compound represented by the following group is used alone or in combination, or further in combination with an aromatic phosphoric acid ester.

[Conventional technology]

Resin compositions made of polyphenylene ether resins and styrene resins have excellent mechanical, thermal, and electrical properties, and are widely used in home appliance parts, power distribution parts, automobile parts, etc., and the demand for them has increased in recent years. It is an extremely useful material.

On the other hand, one of the performance demands of the industry for resins is flame retardancy. The flame retardant regulations for resins are becoming more and more strict, and compliance with these regulations is required, and polymer compositions of polyphenylene ether resins and styrene resins are no exception, as is the case with UL standards in the United States.

In order to meet this demand, a product in which an aromatic phosphate ester is blended with the polymer composition (Japanese Patent Publication No. 53=418
, Japanese Patent Application Publication No. 1983. -73248), organic halides,
Or, a combination of an organic logenide and antimony trioxide (JP-A-48-7945, JP-A-5'
l-74038, JP-A-52-128946) and those containing elemental phosphorus (USF 3,663°654)
Although such technologies have been disclosed, they cannot be said to be sufficient. That is, the heat resistance temperature decreases when aromatic phosphate esters are used, the impact resistance decreases when organic loge/compounds and antimony trioxide are used, and antimony trioxide is a deleterious substance surrounding pharmaceuticals. No flame retardant has been developed that is fully satisfactory due to poor workability and red coloring of the resin when elemental phosphorus is used. Do not impair performance (
There is a strong demand for flame retardancy.

[Problem that the invention seeks to solve]

The present invention was made in view of the above points, and provides a resin composition consisting of a polyphenylene ether resin and a styrene resin that has excellent flame retardancy without impairing the excellent performance of each component resin. This is what we provide.

[Means and effects for solving the problems] The present invention is based on the general formula (A): j (n', R2, R3, R4, R11 have 1 to 4 carbon atoms)
represents an alkyl group, a phenyl group, or a phenoxy group. ) or general formula (B) ■t' (Ra represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R7, R8, and R9 are an alkyl group having 1 to 4 carbon atoms,
Or represents a phenyl group or a phenoxy group. ) When used alone or in combination, or further in combination with an aromatic phosphate ester, when blended into a resin composition consisting of a polyphenylene ether resin and a styrene resin, extremely excellent flame retardancy can be achieved. This was based on the discovery that

Furthermore, the present invention provides a reduction in heat distortion temperature, which is seen when an aromatic phosphate ester is blended alone, and when an organic halide or an organic halide and antimony trioxide are blended together. We are developing a resin composition that can achieve flame retardancy without causing the decrease in thermal and mechanical properties that occur when flame retardant resin is made, such as a decrease in impact resistance and a decrease in thermal stability. provide.

That is, according to the present invention, with respect to 100 parts by weight of a resin composition consisting of a polyphenylene ether resin and a styrene resin, the general formula (A) )t+ (R1, R2, 1113, R4, R6 has 1 to 4 carbon atoms ) or the general formula (B) R' (R6 represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R7゜几8.R9 represents an alkyl group having 1 to 4 carbon atoms,
A flame-retardant resin composition containing a phosphonate compound represented by f, or a tsubonyl group or a phenoxy group, alone or in combination, or further in combination with an aromatic phosphate ester, is blended with 02 to 20 parts. provided.

The polyphenylene ether resin referred to in the present invention has the general formula (wherein, RIol R"l R121R13, R14
1R15 is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, or hydrogen, and R44 and R16 are not hydrogen at the same time. ) is a repeating unit, and the constitutional unit is [C] or a homopolymer consisting of [C] and [D],
Alternatively, copolymers can be used.

A typical example of a homopolymer of polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene).
ether; f”) C2-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-glopyl-1゜4-phenylene) ether; 4-Fueni177) 1-Full, poly(
2-Methyl-6-chloro-1,4-phenylene)ether, poly(2-methyl-6-hydroxyethyl-1,4)
-phenylene) ether, homopolymers such as poly(2-methyl-6-chloroethyl-1,4-phenylene) ether)'-.

The polyphenylene ether copolymer has the general formula (where B
+2, RI3. R14 and RI5 have the same meanings as above. ) and an alkyl-substituted phenol such as 2,3,6-trimethylphenol and, for example, O-
It includes polyphenylene ether copolymers mainly having a polyphenylene ether structure obtained by copolymerizing cresol and the like.

The styrenic resin that can be used in the present invention has specific examples (in the formula,
几represents hydrogen, lower alkyl or halogen1. ．． 2 is selected from the group consisting of vinyl, hydrogen, chlorine and lower alkyl, and p is an integer from θ to 5).
It is something that you have. As used herein, the term "styrenic resin" is defined in the above formula and includes, by way of example, homopolymers such as polystyrene and polychlorostyrene, modified polystyrenes such as rubber-modified polystyrene, and styrene-containing copolymers such as styrene-acrylonitrile. copolymers (SAN), styrene-butadiene copolymers, styrene-acrylonitrile-butadiene copolymers (ABS), polyα-methylstyrene, copolymers of ethylvinylbenzene and divinylbenzene, and the like.

Styrenic resin components suitable for the present invention are rubber-modified impact styrenic resins, such as polystyrene modified with natural or synthetic rubber. The rubber-modified impact-resistant styrene resin referred to herein includes those obtained by graft polymerizing styrene onto rubber and those obtained by simply mechanically kneading rubber and polystyrene.

The synthetic rubber for modification is composed of, for example, polybutadiene, polyisoprene, diene and other comonomers such as styrene, acrylonitrile, acrylic ester, etc.
Rubbery copolymers including block copolymers of the -B-A and AB types (A is a vinyl aromatic, e.g. styrene, B is a diene, e.g. butadiene) and ethylene-propylene-genterpolymer (EPDM) rubbers.

It is also preferred to modify polystyrene with butadiene rubber.

In the present invention, the mixing ratio of the polyphenylene ether resin and the styrene resin may be arbitrary, but it is preferably 10 to 90 parts by weight of the styrene resin to 90 to 10 parts by weight of the polyphenylene ether resin, and more preferably , for 70 to 30 parts by weight of polyphenylene ether resin,
It is preferable to use 30 to 70 parts by weight of the styrene resin. If the polyphenylene ether resin is 90 parts by weight or more, the processability of the mixed composition of the resin and styrene resin will be extremely reduced, making it impractical, and if the styrene resin is 90 parts by weight or more, the heat distortion temperature will be sufficiently satisfactory. It doesn't become something to float on.

Further, the phosphonate compound used in the present invention has the general formula (A
) a (R1, R2, R3, R4, R5 represent an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a phenoxy group)
) or general formula (B) (R6 represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R7, R8, and R9 are an alkyl group having 1 to 4 carbon atoms,
or a phenyl group or a noenoxy group. ) is used alone or in combination,
The most typical case is that R1-R9 are methyl groups.

In the present invention, the aromatic phosphate esters include, as representative examples, triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, cresyl diphenyl phosphate, and xylenyl diphenyl. Phosphates, etc. are used.

In addition, in the present invention, phosphonate compounds represented by general formula (A) and general formula (, 13) are used alone or in combination, or Furthermore, when used in combination with an aromatic phosphate ester, 0.2 to 20 parts by weight are added.
If the amount is less than 2 parts by weight, flame retardancy cannot be imparted to the resin;
If the amount is 0 parts by weight or more, it is not preferable because when the resin is molded, the appearance of the molded product becomes poor and the impact resistance is lowered.

Furthermore, the addition of antioxidants, ultraviolet absorbers, and other stabilizers that are commonly used to stabilize resins, and the use of glass fibers and other inorganic fillers to strengthen resins, impede the present invention. Not a thing.

The method for producing the flame-retardant resin composition of the present invention may be any method in which a resin is normally melted, plasticized, granulated, and processed. For example, a polystyrene-ethyl resin, a styrene resin, a bosbonate compound represented by the general formula (A) and a general formula (B), and an aromatic phosphoric acid ester are tri-blended, and the mixture is processed using an extruder, heating roll, or Banbury mixer. ,
For kneaders, etc. (using a method of melting the resin and dispersing the phosphonate compound, or using an extruder with a vent,
A method of adding a phosphonate compound through a vent hole may also be used.

EXAMPLES Below, in order to further clarify the present invention, examples will be given and explained, but the scope of the present invention is not limited thereby.

Examples 1-3 - Solution of chloroform (5wt,/vat at 30°C
%) has an intrinsic viscosity of 0.60. di/g po IJ (2
, 6-dimethyl-1,4-phenylene) ether, rubber-modified polystyrene containing 14% by weight of polyfridiene, and phosphonate compounds represented by formulas (E) and (F) in the formulation shown in Table 1. After mixing in a Henschel mixer, pellets were obtained without melt extrusion at 280'C using a vacuum vented twin screw extruder. Using this pellet, injection molding was performed at 280"C to obtain a test piece.
erwriters Laboratory (UL
) The flame retardation properties of the 16 dragon thickness specimens were evaluated according to Bulletin A 94. In addition, physical properties were evaluated according to ASTM standards. The results are shown in Table-1. As is clear from Table 1, the composition exhibited good flame retardancy, and there was no decrease in heat resistance due to the addition of the phosphonate compound.

Comparative Example 1 The same poly(2,6-dimethyl-1,4-phenylene) ether and rubber modified polystyrene as in Example 1 were added to Table 1.
Table 1 shows the results of mixing, granulation, molding, and evaluation using the formulation shown in Table 1 as a comparative example.

Comparative Example 2 In addition to the same poly(2,6-dimethyl-1,4-phenylene) ether and rubber-modified polystyrene as in Example 1, triphenyl phosphate was mixed, granulated, and mixed in the formulation shown in Table 1. The molded and evaluated results are shown in Table 1 as a comparative example.
Shown in 1.

Examples 4 to 7, Comparative Examples 3 and 4 Using the same poly(2,6-dimethyl-1,4-phenylene), :r-thyl, rubber-modified polystyrene, and phosphonate compound as in Example 1, the results shown in Table 2 were Table 2 shows the results of mixing, granulating, molding, and evaluating the formulations shown in Example 1 in the same manner as in Example 1.

Good self-extinguishing properties were exhibited when the phosphonate compound was blended in an amount of 0.2 parts or more, but no effect was obtained with 0.2 parts or more of the phosphonate compound.

Examples 8 to 11, Comparative Example 5 In addition to the same poly(2,6-dimethyl-1,4-phenylene) ether and phosphonate compound as in Example 1, polybutadiene content 4Qwt% and AN content 15wt
% of emulsion type ABS resin was mixed, granulated, and molded in the same manner as in Example 1 in the formulation shown in Table 3, and the evaluation results are shown in Table 3. Evaluation,
The test specimens for the Izot impact test were observed and evaluated with the naked eye.

When the content of the phosphonate compound is 10 parts, 15 parts, and 20 parts, good self-extinguishing properties, impact resistance, and appearance are exhibited, but when the content is 25 parts, the impact resistance is significantly reduced and the appearance is poor. It's coming.

Examples 12-14 Same as Example 8! J(2,6-dimethyl-1.
In addition to +4-phenylene) ether, ABS resin, and phosphonate compounds, polystyrene (Asahi Kasei Styron Gp
680) and triphenyl phosphate were mixed, granulated, and molded in the same manner as in Example 1 using the formulations shown in Table 4, and the evaluation results are shown in Table 4.

The workability was evaluated as f+Ui 6, and the transportability from the hopper to the extruder was evaluated.

The phosphonate compounds listed in the table are in a viscous liquid state at room temperature, so if they are added to the resin in large quantities, they may cause blocking phenomena in which the resins aggregate, or sag during transport from the hopper to the extruder. , a bridging phenomenon occurs in which the mobility of the blended composition deteriorates. As is clear from Table 4, by using triphenyl phosphate in combination,
Workability can be improved while maintaining good self-extinguishing properties.

〔Effect of the invention〕

As mentioned above, the resin composition of the present invention can impart excellent flame retardancy without impairing the excellent performance of the phorophenylene ether resin and the styrene resin. , has great industrial significance.

Claims (8)

[Claims] (1) For 100 parts by weight of a resin composition consisting of a polyphenylene ether resin and a styrene resin,
) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R^1, R^2, R^3, R^4, R^5 have 1 carbon number
~4 alkyl group, phenyl group, or phenoxy group. ) Or general formula (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (R^6 represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, R^7, R^8, R^9 represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a phenoxy group.)
A flame-retardant resin composition containing 0.2 to 20 parts by weight of a phosphonate compound represented by the following, either alone or in combination, or in combination with an aromatic phosphate ester. (2) Polyphenylene ether resin has formula [C]▲mathematical formula, chemical formula, table, etc.▼[D]▲mathematical formula, chemical formula,
There are tables, etc. ▼ (In the formula, R^1^0, R^1^1, R^1^2, R^1
^3, R^1^4, R^1^5 are monovalent residues such as an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen, and hydrogen, and R^1^4, R^1^ 5 is not hydrogen at the same time. )
is the repeating unit, and the constituent unit is [C] or [C]
The composition according to claim 1, which is a homopolymer or copolymer consisting of and [D]. (3) The polyphenylene ether resin is poly(2,6
-dimethyl-1,4-phenylene) ether. (4) The composition according to claim 2, wherein the polyphenylene ether resin is a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol. (5) The composition according to claim 1, wherein the styrenic resin is rubber-modified high-impact polystyrene. (6) The composition according to claim 1, wherein the styrenic resin is polybutadiene-modified high-impact polystyrene. (7) Claim 1, wherein the styrenic resin is a terpolymer of acrylonitrile-butadiene-styrene.
Compositions as described in Section. (8) The aromatic phosphate ester is triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, diphenyl cresyl phosphate, dicresyl phenyl phosphate, diphenylxylenyl phosphate, or dixylenylphenyl phosphate alone or in combination.
A composition according to claim 1 selected from the above combinations.