JPS5925822B2 - Flame retardant polyphenylene ether resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to flame retardant polyphenylene ether resin compositions.

More specifically, the present invention is a resin composition in which a styrene polymer is added to polyphenylene ether or a polyphenylene ether obtained by graft copolymerizing a styrene compound, and a novel organic phosphorus compound is mixed therein. The present invention relates to a flame retardant resin composition. Polyphenylene ether has become extremely popular in recent years due to its excellent mechanical properties, electrical properties, chemical resistance, heat resistance, etc., as well as low water absorption and good dimensional stability. This resin is attracting attention.

Furthermore, polyphenylene ether has excellent slow-flaming properties, and is self-extinguishing according to ASTM test method D635 and Underwriters Laboratories' standard rot 94 (hereinafter abbreviated as UL-94). Rated as non-trip property. However, it has been pointed out from an early stage that polyphenylene ether has poor processability.
This was the biggest drawback. As an improvement method, there are many known methods of adding styrenic polymers, for example,
Japanese Patent Publication No. 43-17812, U.S. Patent No. 338
No. 3435 and other publications disclose blend compositions of polyphenylene ether and styrenic polymers.
Also, Special Publication No. 47-1210, Special Publication No. 46-2780
No. 9, JP-A-49-98446, JP-A-50-511
No. 50, US Pat. No. 3,586,736, US Pat. No. 3,929,931, etc. disclose resin compositions containing a graft copolymer of a styrene compound onto polyphenylene ether.

However, these resin compositions and styrene-based polymers with improved processability of polyphenylene ether are neither self-extinguishing nor non-trip, and completely burn when ignited. The disadvantage is that the material is unsuitable for a wide range of industrial applications.

An object of the present invention is to provide a polyphenylene ether resin composition with improved processability and flame retardancy.

That is, the present invention is based on the general formula (R1, R2, R3, R4, R5, R6 are the same or different alkyl groups having 1 to 4 carbon atoms excluding tert-butyl groups,
A monovalent residue such as an aryl group, monologen, hydrogen, etc.
R5 and R6 are not hydrogen at the same time.

) as a repeating unit, and the constituent unit is [1], or a polyphenylene ether component consisting of [1] and [] is 20 to 8
A resin portion of 80 to 98% by weight, which is a mixture of polyphenylene ether or polyphenylene ether obtained by graft copolymerizing a styrene compound with a styrene polymer so that the ratio is 0% by weight (based on the weight of the resin part) % (based on the total composition), - general formula and = general formula (wherein, the residues X & ζ 〉, R3, R4, R5 are hydrogen, halogen, alkyl group having 1 to 8 carbon atoms,
At least one compound selected from the group consisting of novel organic phosphorus compounds represented by an aralkyl group, a cyclohexyl group, or a phenyl group, X is an integer of 1 to 6, and y is an integer of 1 to 4. The present invention provides a flame retardant composition characterized in that the flame retardant composition is more substantially 2 to 20% by weight.

Representative examples of the polyphenylene ether homopolymer of the present invention 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-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-chloro-1,4-phenylene)ether, poly(2
-Methyl-6-hydroxyethyl-1,4-phenylene)ether, poly(2-methyl-6-chloroethyl-1)
- Homopolymers such as 4-phenylene) ether can be mentioned.

The polyphenylene ether copolymer has the general formula (where R
3, R4, R5, and R6 are monovalent residues such as an alkyl group having 1 to 4 carbon atoms excluding a tert-butyl group, an aryl group, rogene, and hydrogen, and R5 and R6 are not hydrogen at the same time.

), or a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure obtained by copolymerizing with an alkyl-substituted phenol such as 2,3,6-trimethylphenol or o-cresol. The most advantageous polyphenylene ethers for the purposes of the present invention are:
Poly(2,6-dimethylphenylene-1,4-ether). This polymer has excellent miscibility with the ζ-styrene polymer, making it easy to create resin compositions with various ratios, and also exhibits excellent flame retardancy through synergy with organic phosphorus compounds. do. The number average molecular weight of the polyphenylene ether preferred in carrying out the present invention is 6,000 to 30,000, more preferably 7,000 to 30,000.
Selected from a range of 25,000.

If a polyphenylene ether with a number average molecular weight of 6,000 or less is used, the physical properties of the resin composition, especially the creep properties, will be markedly reduced, which is undesirable. If a polyphenylene ether is used with a number average molecular weight of 30,000 or more, the processability will be markedly reduced, and styrene This is not preferable because it causes deterioration of the system polymer and the balance of physical properties cannot be maintained. In the polyphenylene ether graft-copolymerized with a styrene compound used in the present invention, the styrene compound includes styrene and derivatives such as alkylated products and mono-logonated products of styrene, and specific examples thereof include styrene , α-methylstyrene, 2●4-dimethylstyrene, monochlorostyrene, dichlorostyrene, p-methylstyrene, ethylstyrene, and the like.

These can be copolymerized with copolymerizable vinyl compounds such as methyl methacrylate, acrylonitrile, methacrylonitrile, butyl acrylate, etc. during polymerization, or copolymerized and grafted with two or more styrene compounds coexisting. But that's fine.

A preferred composition of the graft copolymer used in the composition of the present invention is one in which a styrene compound is graft-polymerized in a range of 20 to 200 parts by weight based on 100 parts by weight of polyJG nylene ether.

20 parts by weight or less is not much different from polyphenylene ether homopolymer 1, and graft polymerization of 200 parts by weight or more causes a decrease in the physical properties of the composition, particularly impact strength, so it is preferable. The system polymer preferably has a number average molecular weight of 50,000 to 20,000.
0 More preferably, it refers to a polymer mainly composed of a styrene compound having a molecular weight in the range of 60,000 to 150,000.

The styrenic compound referred to herein is the same as the compound that can be used in the graft copolymerization described above, and the styrenic polymer also includes commonly known rubber-reinforced resins. For example, rubber-reinforced polystyrene resins, acrylonitrile-butadiene-styrene copolymer resins, and the like are also included within the scope of the present invention. The proportion of the styrene polymer in the total resin portion (including those chemically bonded to the polyphenylene ether by graft copolymerization) is 20 to 80% by weight, and Preferably &@. It is selected from the range of 25 to 75% by weight. 2
If the content is less than 0% by weight, sufficient processability cannot be imparted to the composition, and if more than 80% by weight is added, depending on the mixture with the organic phosphorus compound of the present invention,
It is difficult to make a flame retardant composition.

If the number average molecular weight of the styrenic polymer is less than 50,000, it is undesirable because the resin properties, especially impact strength, creep properties, etc., will deteriorate, and if it is more than 200,000, moldability will be adversely affected, and during processing. This leads to undesirable phenomena such as thermal deterioration of the composition and a decrease in the impact resistance of the molded product due to residual strain. Specific examples of the component X contained in the organic phosphorus compound of the present invention represented by general formula (B) or (Q) are shown below in the form of structural formulas.

Furthermore, both of (old) and (C) can be used alone or in a mixture of two or more.

The organic phosphorus compound represented by the general formula (8) or (0) used in the present invention is a compound newly invented by the present inventors, and on the same date, the joint patent applicant has been A patent application (Japanese Unexamined Patent Publication No. 53-5181) has been filed and a technology related to the production method has been disclosed, and it is based on the general formula (where R3, R4, R5 are hydrogen, halogen, alkyl having 1 to 8 carbon atoms). This is a novel organic phosphorus compound obtained by dehydration condensation of an organic phosphorus compound represented by an aralkyl group, an aralkyl group, a cyclohexyl group, or a phenol group (see Japanese Patent Publication No. 17979/1983) and melamine or benzoguanamine.

The content of the organic phosphorus compound that exhibits the effects of the present invention is 2 to 20% by weight, preferably 3 to 15% by weight, based on the total composition.
selected from a range of weight %.

When the amount of organic phosphorus compounds is less than 2%, UL-94
It is not preferred because it is difficult to provide self-extinguishing and non-trip performance using the test method. Another 20%
If it is added in a larger amount, the physical properties of the resin, particularly the heat distortion temperature and impact strength, cannot be maintained within a practically usable range, which is not preferable. The method for obtaining the composition of the present invention is not particularly limited, and mixing may be performed by any method.

To give an example of a preferred method, the resin and the organic phosphorus compound to form the composition are thoroughly mixed in a dry blender, then melt-kneaded using an extruder and cut into pellets. The composition of the present invention may contain other additives, if necessary.
For example, it goes without saying that plasticizers, pigments, reinforcing agents, fillers, extenders, stabilizers, and the like may be included.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, parts and % represent parts by weight and % by weight, respectively. Actual Portrait 11rhoCuri 1 Put 77 parts of a phosphorus compound represented by the following formula and 29 parts of benzoguanamine into a four-piece flask equipped with a stirrer and a thermometer,
Heat on an oil bath to raise the internal temperature to 170°C.

While stirring, the internal temperature was raised to 230° C. over 1 hour, and the produced water was removed under reduced pressure (internal pressure 30 mmHg).
When the reaction is carried out for 2 hours at 230° C. under reduced pressure, no water is distilled off, so the product is taken out, cooled and ground.

The product is M. p. The infrared absorption spectrum showed a decrease in OH groups and N mountain groups, and elemental analysis confirmed that an organic phosphorus compound of the following formula had been obtained. 35 parts, rubber-reinforced styrene-acrylonitrile copolymer 65 with an average acrylonitrile content of 4% and a styrene-butadiene copolymer rubber content of 9.0%.
1 part and 8 parts of the above organic phosphorus compound were thoroughly mixed in a blender, and then melt-kneaded using an extruder maintained at 220 to 270 DEG C. to form pellets.

The mixed resin thus obtained was heated to 600k9/250°C.
It can be injection molded under the conditions of Cd, and its physical properties include tensile strength of 440k9/Cd (the same applies below 1 according to ASTM D638), and Izot impact strength of 12.0kg・C7n/
Cln (same below 1 according to ASTM D256), heat distortion temperature 88.2°C (same below 1 according to ASTM D648)
It was hot.

The flammability of the mixed resin of this example was examined using the UL-94 method. Maximum burn time is 7.5 seconds, average 2.8 seconds
It was hot in seconds. Tensile creep test at 23℃, 210℃
When carried out using a second load, the amount of deformation after 1000 hours was:
It was 0.99%. Example 2 60 parts of poly(2,6-dimethylphenylene-1,4-ether) having a number average molecular weight of 21,000, 40 parts of rubber-reinforced polystyrene containing 8% polybutadiene rubber, and the same materials used in Example 1 Six parts of an organic phosphorus compound were mixed in a blender and melt-kneaded using an extruder maintained at 230-280°C to obtain pellets.

Mixed resin & human thus obtained 260℃, 700k9/C
It can be injection molded with d, and its physical properties are tensile strength 6
20kg/CdlIzotsu impact strength 10.5kg・C
rfL/CT! 1, and the heat distortion temperature was 109.0°C.
Flammability according to UL-94 is maximum 5.5 seconds, average 1.8
It was rated V-0 in seconds. Tensile creep test was carried out at 60℃, 105K9 load and 23℃, 2
When carried out under a load of 10k9, the amount of deformation after 1000 hours was 0.58% and 1.01%, respectively.
Example 3 Dou
20 parts of polystyrene-grafted polybutadiene containing poly(2,6-dimethylphenylene-1,4-ether)65-L4O% polybutadiene with a number average molecular weight of 9,500 and 15 parts of polystyrene with a number average molecular weight of 105,000. The resin part consisting of 220~2
The mixture was melt-kneaded using an extruder maintained at 80°C to obtain mixed resin pellets. 100 parts of these pellets and 4.5 parts of the organic phosphorus compound used in Example 1 were thoroughly mixed in a blender, and then melt-kneaded using an extruder maintained at 200-260°C. This resin composition was heated at 240°C and 450k
It can be injection molded under the conditions of 9/Cd, and its physical properties include tensile strength of 660 kg/Crii, Izod impact strength of 18.5 k9 (V7Z/Cln, heat distortion temperature of 120°C).
It was hot. In the UL-94 combustion test, the maximum burning time was 4.2 seconds and the average burning time was 2.6 seconds, giving it a V-0 grade. Tensile creep test at 60℃, 105
When carried out with a load of 1<9 and a load of 210k9 at 23°C, the amount of deformation after 1000 hours was 0.51, respectively.
% and 0.83%. Example 4 The method for producing the organic phosphorus compound in Example 1 was
Repeated using 1 part.

It was confirmed that an organic phosphorus compound of 100% was obtained.

5 parts of this phosphorus compound were added to 100 parts of the mixed resin pellets obtained in Example 3, mixed well in a blender, and then melt-kneaded in an extruder. The obtained resin composition was heated at 240°C,
It can be injection molded under the conditions of 500 kg/Cd, and its physical properties include tensile strength of 590 kg/Cd, Izod impact strength of 16.8 kg/C7n/(177Z, heat distortion temperature of 1
The temperature was 16.5°C. In the combustion test according to UL-9411C, the maximum combustion time was 3.5 seconds, the average was 1.6 seconds, and the V
-0 grade. Example 5 50 parts of poly(2,6-dimethylphenylene-1,4-ether) having a number average molecular weight of 9700, 20 parts of styrene
and 1.0 part of di-t-butyl peroxide were heated to 150 DEG C. in 10 minutes and 240' CVC over 10 minutes, and the reaction product was pelletized using an extruder.

The polystyrene content in the obtained graft copolymer was 26%. Take 2.0y of this polymer and 40m
1 was dissolved in methylene chloride and left at 30°C. Even after standing for 6 hours, no precipitate was observed, and it was confirmed that no homopolymer of polyphenylene ether remained.

50 parts of this graft copolymer, 20 parts of polystyrene grafted polybutadiene containing 40% polybutadiene, and 30 parts of polystyrene with a number average molecular weight of 88,000.
5.0 parts of the organic phosphorus compound used in Example 1 was thoroughly mixed with the resin part consisting of 200 to 2 parts in a blender.
The mixture was melt-kneaded using an extruder maintained at 60°C.

This resin composition can be injection molded under the conditions of 220°C and 450 kg/Cd, and its physical properties include tensile strength of 43
0kσ/Cdl Izotsu impact strength 22.5kg・(:
1T1/Cln, and the heat distortion temperature was 106.5°C. U
In the combustion test using L-94, the maximum combustion time was 8.
It took 8 seconds, averaged 4.2 seconds, and was rated V-0. Example 6 60 parts of the graft copolymer obtained in Example 5, 30 parts of rubber-reinforced polystyrene containing 8% polybutadiene rubber, 10 parts of polystyrene grafted polybutadiene containing 40% polybutadiene, and the copolymer used in Example 4. After thoroughly mixing 3.5 parts of an organic phosphorus compound in a blender,
Melt kneading was carried out using an extruder maintained at 200 to 260°C.

This resin composition can be injection molded under the conditions of 230°C and 450k9/Cd, and its physical properties include tensile strength of 46
0kg/Cdl Izotsu impact strength 23.0k9/
The heat distortion temperature was 112°C. In the UL-94 flammability test, the maximum burning time was 11.8 seconds, the average burning time was 6.8 seconds, and it was ranked as V-1 grade. Example
7-10>, an organic phosphorus compound was produced according to the method of Example 1 using the derivative thereof.

These compounds were made into a resin composition by the method of Example 4. The resulting composition was subjected to a UL-94 combustion test. The results are summarized in Table-1. Example 11
~13 Example 5 by changing the amount of styrene used during graft polymerization
The steps were repeated to obtain a final resin composition.

The results of these combustion tests are summarized in Table 2. Examples 14-18 Example 6 was repeated by changing the amount of the organic phosphorus compound added.

The combustion test results of the obtained resin composition are summarized in Table 3. Example 19 Melamine 9.7 instead of benzoguanamine in Example 1
The synthesis of organophosphorus compounds was repeated using

The product is M. p. The infrared absorption spectrum showed a decrease in 0H groups and NH2 groups, and elemental analysis confirmed that an organic phosphorus compound of the following formula had been obtained. 4.0 parts of this organic phosphorus compound and 100 parts of the mixed resin pellets used in Example 3 were thoroughly mixed in a blender, and then melt-kneaded using an extruder maintained at 200-260°C.

Claims (1)

[Claims] 1 General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼, [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_1, R_2, R_3, R_4, R_5, R_6 are the same or a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, a halogen, hydrogen, etc., excluding a tert-butyl group, and R_5 and R_6 are not hydrogen at the same time) as a repeating unit, and the structure Unit is [I] or [I]
Polyphenylene ether (PPE) consisting of and [II]
20-80% by weight and 20-80% by weight of styrenic polymer
80 to 98% by weight of the mixed resin consisting of the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (C) (Here,
is the residue ▲which has mathematical formulas, chemical formulas, tables, etc.▼, and R_3, R_4, and R_5 are hydrogen, halogen, and carbon number 1.
-8 alkyl group, aralkyl group, cyclohexyl group, or phenyl group, x is an integer of 1 to 6, and y is an integer of 1 to 4. A flame-retardant polyphenylene ether resin composition, characterized in that the composition comprises 2 to 20% by weight of a flame-retardant polyphenylene ether resin composition. 2 In the residue described in claim 1, R_3
, R_4, and R_5 are all hydrogen. 3 In the residue described in claim 1, R_4
and R_5 are chlorine, and R_3 is hydrogen. 4 In the residue described in claim 1, R_3
, R_4, and R_5 are all t-butyl groups. 5 In the residue described in claim 1, R_5
is a phenyl group, and R_3 and R_4 are hydrogen. 6 In the residue described in claim 1, R_3
, R_5 is a methyl group, and R_4 is a t-butyl group. 7 Organic phosphorus compound (B) according to claim 1
A resin composition comprising a mixture of organic phosphorus compounds in which x is 1 to 6. 8 Organic phosphorus compound (C) according to claim 1
The resin composition is a mixture of organic phosphorus compounds in which y is 1 to 4. 9. The resin composition according to any one of claims 1 to 8, wherein R_1 and R_2 are methyl groups. 10 General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼, [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (R_1, R_2, R_3, R_4, R_5, R_6 are the same or different tert-butyl It is a monovalent residue such as an alkyl group with 1 to 4 carbon atoms, an aryl group, a halogen, or hydrogen, excluding groups, and R_5 and R_6 are not hydrogen at the same time.) is the repeating unit, and the structural unit is [I], or [I]
Polyphenylene ether (PPE) consisting of and [II]
It consists of a graft copolymer in which 20 to 200 parts by weight of a styrene compound is grafted onto 100 parts by weight, and a styrene polymer, and the polyphenylene ether component is 20 to 200 parts by weight.
Resin part 80~80% by weight (resin part weight basis)
98% by weight, and the general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(B) and the general formula▲There are mathematical formulas, chemical formulas, tables, etc.▼(C) (Here,
is a residue that has mathematical formulas, chemical formulas, tables, etc.
R_3, R_4, R_5 are hydrogen, halogen, and carbon number 1
-8 alkyl group, aralkyl group, cyclohexyl group, or phenyl group, x is an integer of 1 to 6, and y is an integer of 1 to 4). A flame-retardant polyphenylene ether resin composition comprising more substantially 2 to 20% by weight of one kind of flame-retardant polyphenylene ether resin composition. 11 In the residue described in claim 10, R
A resin composition in which _3, R_4, and R_5 are all hydrogen. 12 In the residue described in claim 10, R
A resin composition in which _4 and R_5 are chlorine and R_3 is hydrogen. 13 In the residue described in claim 10, R
A resin composition in which _3, R_4, and R_5 are all t-butyl groups. 14 In the residue described in claim 10, R
A resin composition in which _5 is a phenyl group, and R_3 and R_4 are hydrogen. 15 In the residue according to claim 10, R
A resin composition in which _3 and R_5 are a methyl group and R_4 is a t-butyl group. 16. A resin composition which is a mixture of organic phosphorus compounds according to claim 10, wherein x is 1 to 6. 17. A resin composition which is a mixture of organic phosphorus compounds according to claim 10, wherein y is 1 to 4. 18. The resin composition according to any one of claims 10 to 17, wherein R_1 and R_2 are methyl groups.