JPS6361047A - Flame-retardant polyphenylene ether composition - Google Patents

Abstract

PURPOSE:To obtain a flame-retardant composition having excellent heat- resistance, solvent resistance and mechanical properties, by compounding a resin composed of a polyphenylene ether and a polyamide with a rubbery material, a specific compound, a brominated polystyrene and an antimony compound. CONSTITUTION:100pts.wt. of a resin composed of (A) 30-70wt% polyphenylene ether and (B) 70-30% polyamide is compounded with (C) 0.1-10pts. of (i) a compound containing C=C or CidenticalC and a group selected from carboxyl, acid anhydride, acid amide, imide carboxylic acid ester, epoxy, amino and OH in one molecule and/or (ii) a compound having oxirane ring in the molecule and/or condensed polymer of a dihydric phenol and epichlorohydrin (phenoxy resin), (D) 3-30pts. of a rubbery material and (E) 3-30pts. of a brominated polystyrene and 1-20pts. of an antimony compound.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a flame-retardant polyphenylene ether composition having excellent heat resistance, solvent resistance, and mechanical properties. It has excellent rock fishing properties and mechanical properties, as well as low water absorption and good dimensional stability. However, polyphenylene ether is also known to have poor solvent resistance, which limits its use in certain applications. A composition with good solvent resistance by blending polyphenylene ether with Bo'J7 was published in Japanese Patent Publication No. 60-11966.
presented in the issue.

However, it is also known that compositions obtained by blending polyamide with polyphenylene ether do not lose their self-extinguishing properties and require the addition of flame retardants. For example, in contrast to a composition of polyphenylene ether and polyamide (2), JP-A No. 60-58463 proposes using an aromatic phosphate ester. However, the composition obtained by carrying out this proposal has a heat-resistant The problem is that it reduces the

(Summary of the Invention i) The present inventors have conducted intensive studies to obtain a flame-retardant composition based on polyphenylene ether and polyamide, which has excellent heat resistance, solvent resistance, and mechanical properties. It has been reached.

That is, the present invention provides (a) polyphenylene ether and (b)
) polyamide, (c) rubbery material, (d) carbon in the molecule.
Carbon-carbon unsaturated bonds (carbon-carbon double bonds or carbon-
carbon triple bond) and carboxyl group, acid anhydride group, acid amide group, imide group, carboxylic acid ester group, epoxy group,
A compound in which one or more groups selected from amino groups and hydroxyl groups coexist, and/or a compound having an oxirane ring in the molecule, and/or a condensed polymer of dihydric phenol and epichlorohydrin. It was discovered that a flame retardant composition with good heat resistance, solvent resistance, and mechanical properties could be obtained by blending a predetermined amount of halogenated polystyrene and an antimony compound. It is something.

(Structure of the Invention) The polyphenylene ether as component (a) in the present invention is a homopolymer or copolymer having units of general formula-1.

R, , R, , Rs and R1 in general formula-I are each independently selected from the group consisting of hydrogen, halogen, and hydrocarbon groups, and n represents the total number of monomer units, preferably about 20 or more, and preferably It is an integer of 50 or more.

The method for producing polyphenylene ether is not particularly limited, but it can be obtained, for example, by reacting raw material phenol with oxygen in the presence of a complex of copper and manganese.

Specific examples of polyphenylene ethers that can be used in the present invention include poly(2,6-dimethyl-1.4-)unisine) ether, poly(2,6-ethyl-1,4-)unisine) ether, Poly(2,6-cyclo-1,4-)
Unishin] ether, poly(2,6-dipromu 1.4
-7 enylene) ether, poly(2-methyl-6-nityl-1,4-)unisine) ether, poly(2-chloro-6-methyl-1,4-)unisine) ether, BoI7
(2-Methyl-6-i-n-propyl-1,4-)unicine ether, poly(2,6-di-n-propyl-1,
4-) unishin) ether; f'1J (2-chloro-
6-bromo-1,4-)unicine] ether, poly(2
-chloro-6-ethyl-1,4-phenylene) ether, poly(2-chloro-6-ethyl-1,4-phenylene) ether, poly(2-methyl-1,4-7 enylene)
Ether, poly(2-7enyl-1.4-7enylene)
Ether, poly(2-methyl-6-7enyl) 1.4
-) Unishin] ether, poly(2-bromo-6-7enyl-1,4-phenylene)ether and 2,3.6
- for example with alkyl-substituted phenols such as trimethylphenol. Examples include polyphenylene ether copolymers mainly composed of polyphenylene ether mR obtained by copolymerizing with -cresol and the like. Furthermore, these may be grafted with a monomer mainly composed of styrene.

The polyamide component (b) used in the present invention is:
Any polymer can be used as long as it has a 10-Nf(- bond in its raw polymer chain and can be melted by heating).

Typical examples include 4-nylon, 6-nylon, 6,6-nylon, 12-nylon, 6,10-nylon, polyamides made from terephthalic acid and trimethylhexamethylene diamine, adipic acid and metaxylylene diamine. Polyamides from amines, polyamides from adipic acid and azelaic acid and 2,2-bis(p-aminocyclohexyl)-propane, polyamides from terephthalic acid and 4,4'-diaminodicyclohexylmethane, etc.0 Polyphenylene ethers and The blending ratio of polyamide is 3 parts polyphenymphetyl per 100 parts by weight of both.
0 to 0 parts by weight of polyamide and 70 to 30 parts by weight of polyamide are suitable. If the amount of polyamide is less than 30 parts by weight, solvent resistance decreases, which is not preferable. On the other hand, polyamide is 70wt
%, it is not preferable because heat resistance tends to be poor, such as a decrease in heat distortion temperature.

The rubber-like material of component (c) in the present invention includes natural and synthetic polymeric materials that are elastic at room temperature.

Specific examples include natural rubber, butadiene polymers, butadiene-styrene copolymers (random copolymers, graft copolymers, styrene-butadiene-styrene block copolymers (hereinafter abbreviated as SBS)), and the like. ], isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, inbutylene polymer, inbutylene-butadiene copolymer, inbutylene-isoprene copolymer, acrylic Acid ester polymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, thio-
rubber, polysulfide rubber, polyurethane rubber, polyether rubber (eg, polypropylene oxytonato), epichlorohydrin rubber, styrene-isoprene copolymer, and the like.

These rubbery bodies can be produced by any manufacturing method (e.g., emulsion polymerization, solution polymerization), any catalyst (e.g., peroxide, trialkylaluminum, etc.), lithium chloride,
It may also be made from a nickel-based catalyst. Furthermore, those having various degrees of crosslinking, those having various proportions of microstructures (for example, cis structure, trans structure, vinyl group, etc.), or those having various average rubber particle sizes are also used.

Furthermore, various copolymers such as random copolymers, block copolymers, and graft copolymers can all be used as the rubber-like material of the present invention.

Furthermore, when producing these rubber-like bodies, other olefins, dienes, aromatic vinyl compounds, acrylic acid,
Copolymerization with monomers such as acrylic esters and methacrylic esters is also possible.

Any methods such as random copolymerization, block copolymerization, and graft copolymerization can be used for their copolymerization. Specific examples of these 4L-mers include Tatoeha, ethylene, propylene, styrene, chlorostyrene, α-methylstyrene, butadiene, isoprene, chlorobutadiene, butene, imbutylene, methyl acrylate, acrylic acid, and ethyl acrylate. , butyl acrylate, methyl methacrylate, acrylonitrile, etc. Further, partially modified rubber-like bodies in the present invention are also within the scope of the present invention, such as hydroxy- or carboxy-terminated polybutadiene, partially hydrogenated styrene, etc.
Examples include butadiene block copolymers.

The amount of the rubber-like material used is preferably 3 to 30 parts by weight per 100 parts by weight of the polyphenylene ether and polyamide. If it is less than 3 parts by weight, it will not be as good as light in terms of impact resistance,
If the amount is less than 30M parts, copper properties, heat resistance, flame retardance, etc. will deteriorate, which is undesirable. Component (d) in the present invention contains a carbon-carbon double bond or a carbon-carbon triple bond and a carboxyl group in the molecule. Specific examples of compounds in which one or more groups selected from , acid anhydride groups, acid amide groups, imide groups, carboxylic ester groups, epoxy groups, amino groups, and hydroxyl groups coexist include maleic anhydride; Acid, maleic acid, fumaric acid, maleimide, maleic hydrazide,
Reactant of maleic anhydride and diamine, methylnadic anhydride, dichloromaleic anhydride, maleic acid amide, soybean oil, tung oil, castor oil, linseed oil, hempseed oil, cottonseed oil,
Natural oils and fats such as sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil, sardine oil, epoxidized natural oils and fats such as epoxidized soybean oil, acrylic acid, butenoic acid, crotonic acid, vinyl acetic acid, methacrylic acid, Pentenoic acid, angelic acid, tipric acid, 2-pentenoic acid, 3-pentenoic acid, α-ethyl acrylic acid, β-methylcrotonic acid, 4-
Pentenoic acid, 2-hexenoic acid, 2-methyl-2pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid acid, 4-decenoic acid, 9-cundecenoic acid,
10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid, 9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, icosenoic acid, dococe:, y acid, x Lucic acid, tetracosenoic acid 1. mycolipenic acid, 214-pentadienoic acid,
2.4-hexadienoic acid, diallylacetic acid, geranic acid, 2,4-decadienoic acid, 2,4-dodecadienoic acid, 9
．． 12-Hexa' Decadienoic acid %9-12-Octadecadienoic acid, Hexadecatrienoic acid, Linoleic acid, Rilunic acid, Octadecatrienoic acid, Icosadienoic acid, Icosaterienoic acid, Icosatetraenoic acid, Ricinoleic acid, Unsaturated carboxylic acids such as rheostearic acid, oleic acid, icosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetraenoic acid, hexadienoic acid, hexacosenoic acid, oftacosenoic acid, and traaconthenic acid. , or esters, acid amides, anhydrides of these unsaturated carboxylic acids, acrylic alcohol, crotyl alcohol, methyl vinyl carbinol, allyl carbinol,
Methylglobenylcarbinol, 4-penten-1-ol, 10-landecen-1-ol, propargyl alcohol, 1.4-pentadien-3-ol, 1.4
-Hexadien-3-ol, 3.5-hexadiene-
2-ol, 2.4-hexadien-1-ol, general formula CnH2n-3OH1C (IHzn-tOH%CnH
Alcohol represented by 2B-@OH (where n is a positive integer), 3-butene-1,2-diol, 2,5-dimethyl-3-hexene-2,5-diol, 1,5-hexadiene -3,4-diol, 2,6-ocdadiene-4
．． Unsaturated alcohols such as 5-diol, unsaturated amines in which the OH group of such unsaturated alcohols is replaced with -NH groups, or low polymers such as butadiene and imprene (for example, average molecular weight of 500 to 1000)
or a polymer with maleic anhydride or phenols added to it (for example, one with an average molecular weight of 1000 or more), or an amino group, a carboxylic acid group,
Examples include those into which hydroxyl groups, epoxy groups, etc. are introduced.

Particularly preferred among these compounds are epoxy groups,
or a compound having a dicarboxylic acid group,
The present inventors have discovered.

Specific examples of compounds having an oxirane ring as the other component (d) in the present invention include compounds obtained by condensing polyhydric phenols and epichlorohydrin in various ratios, and typical examples thereof include bisphenol A and epichlorohydrin. condensates, (as products, for example,
Oily shell epoxy condensate, condensate of hydroquinone and epichlorohydrin, tetrabromobisphenol A
and epichlorohydrin, glycidyl etherification of phenol novolak or talezol novolak (for example, Sumitomo Chemical Yono Sumiepoxy ESC)
N-220 series, etc.].

A condensate of polyhydric alcohol and epichlorohydrin, typical examples of polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolethane, trimethylolpropane, penta Examples include erythritol.

Examples include glycidyl etherified products of monohydric phenol or -hydric alcohol, such as phenyl glycidyl ether, butyl glycidyl ether, cresyl glycidyl ether, and the like.

Examples include glycidylated amine compounds (for example, Sumiepoxy ELN-125, which is a diglycidylated aniline commercially available from Sumitomo Chemical Co., Ltd.), epoxidized higher olefins, and epoxidized cycloalkenes.

As yet another component (d) in the present invention, phenoxy resin is a typical product that is easily available as a commercially available condensed polymer of dihydric phenol and epichlorohydrin. 0 In the present invention, it is also possible to use the above-mentioned component (d) alone or in combination of two or more. The amount of the compound (d) added in the present invention is 0.1 to 10 parts by weight per 100 parts by weight of the total of polyphenylene ether and polyamide, and if it is less than 0.1 part, the impact resistance will decrease. This is not preferable, and if it exceeds 10 parts by weight, the heat resistance decreases, which is not preferable.

The bromine compound used as component (e) in the present invention is a polymer, and more specifically, it is a brominated polystyrene having a structural unit of the general formula -2.

The upper ζ1, R2, R2 and R3 in the general formula -■ are a hydrogen atom, a bromine atom, an alkyl group having 1 to 5 carbon atoms, or a brominated alkyl group having 1 to 5 carbon atoms, and R1- R
At least one of 5 is a bromine atom. n represents the total number of monomer units, and is an integer of about 50 or more, preferably 150 or more, more preferably 250 or more, particularly preferably 350 or more.

The bromine content of the brominated polystyrene used in the present invention is particularly preferably 40 wt% or more (by weight; the same applies hereinafter) from the viewpoint of flame retardancy.

The brominated polystyrene used in the present invention may be obtained by polymerizing styrene that has been brominated in advance, or may be obtained by polymerizing styrene and then brominating it, and it may be used in -m or two or more types. You can also do it.

Specific examples of brominated polystyrene that can be used in the present invention include poly(2,6-dibromo)styrene, poly(214
Examples include 16-dolibromo)styrene, poly(2,6-dibromo-4-methyl)styrene, and poly(pentabromo)styrene.

The amount of brominated polystyrene added is determined depending on the target degree of flame retardancy, but usually the total amount of the polyphenylene ether as the component (a) and the polyamide as the component (b) is 10
If the amount is less than 0.3 parts by weight (3 to 30 parts by weight per 0.0 parts by weight), almost no flame retardant effect will be obtained, and even if it exceeds 30 parts by weight, the effect will not increase.

The antimony compound used as component (e) in the present invention can be either an inorganic compound or an organic compound.

Examples include antimony oxide, antimony chloride, antimony phosphate, and triphenylantimony.

A particularly preferred antimony compound is antimony oxide.

The amount of antimony compound added is determined depending on the target degree of flame retardancy; Add 1 to 20 parts by weight per 100 parts. If the amount is less than 1 part by weight, almost no flame retardant effect will be obtained, and if it is more than 20 parts by weight, the effect will not increase.

The composition of the present invention can be obtained using an extruder, a kneader, etc.
, a roll mixer, a Banbury mixer, or the like is used. In the case of melt mixing, all the components may be mixed at the same time, or one or more components may be mixed in advance, and then the remaining components may be added and mixed.

In practicing the invention, other polymers, glass fibers,
It is also possible to add fillers such as carbon fiber, carbon black, silica, and titanium oxide, plasticizers, pigments, and the like. In particular, it is preferable to add a styrene polymer to further improve processability. Specific examples include polystyrene homopolymers, rubber-modified polystyrene resins using various rubbers, styrene-acrylonitrile copolymers, butadiene-styrene-acrylonitrile copolymers, butadiene-styrene-methyl methacrylate copolymers, and styrene-acrylonitrile copolymers. Examples include ethylene copolymers.

Furthermore, the present invention provides a novel material that is excellent in heat resistance, solvent resistance, predetermined mechanical properties, and flame retardance by configuring the composition as shown on paper. Accordingly, the composition material of the present invention can be used for the following purposes.

In other words, automotive electrical components such as combination switches, ignitions, distributor parts, fuse cases, junction boxes, connectors, coil bobbins, sockets, switches, tuner parts, terminal boards, flyback transformer cases, computer and copy machine housings, etc. Conceivable specific uses include electrical and electronic components, flooring materials, and building materials such as satsusi.

(Examples) Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these.

In the examples, parts indicate parts by weight. In addition, physical property values were measured by the following method.

Heat resistance: AsT using 1/4' thick injection molded specimens.
The heat distortion temperature (hereinafter abbreviated as HDT) was measured at a load of 18.5 kf/d according to MD-648.

Izod impact strength was measured at 23°C.

Flammability: A UL94 direct flammability test was conducted using injection molded test pieces.

Solvent resistance: A sheet with a length of 80 m, a width of 100 vm, and a thickness of 2 sheets was injection molded, and the sheet was immersed in trichlene at room temperature for 168 hours, and the change in appearance was evaluated.

Flexural Modulus: Measured according to ASTM-D-790 using 14 inch thick injection molded specimens.

Tensile strength: using injection molded specimens with a thickness of 14 inches,
Measured according to ASTM-D-638.

Example 1 Using the specific components listed in Table 1, 5 parts of polyphenylene ether (PPE), 6-6 polyamide (
6-6PA) 50 parts, styrene-butadiene-styrene block copolymer (888,310 parts, maleic anhydride (
Mah30.5 parts, brominated polystyrene (brominated PS)
After uniformly mixing 15 parts of antimony trioxide (Sb) and 0.35 parts of antimony trioxide (Sb) in a drum blender, extrusion granulation was performed at 280°C using a 45 part m twin screw extruder to obtain composition pellets.

This was injection molded at 270° C. using a 6-ounce injection molding machine to obtain a test piece, which was subjected to a test and the results shown in Table 1 were obtained.

Comparative Example 1 A test was conducted in the same manner as in Example 1 except that 15 parts of brominated polystyrene and 5 parts of antimony trioxide were used. The results are also listed in Table-1.

Comparative Example 2 In Example 1, 15 parts of brominated polystyrene and 5 parts of antimony trioxide were replaced with triphenyl phosphate (TPP).
), and the test was conducted in the same manner as in Example 1. The results are also listed in Table-1.

Examples 2 to 4 After mixing the same polyphenylene ether, polyamide, SBS, maleic anhydride, brominated polystyrene, maleic anhydride, brominated polystyrene, and antimony trioxide as in Example 1 in the proportions shown in Table 2, 45 (2) Extrusion granulation was performed at 80°C using a twin-screw extruder to obtain a composition pellet. This was injection molded at 270° C. using a 6-ounce injection molding machine to obtain a test piece, which was subjected to a test and the results shown in Table 2 were obtained.

Comparative Example 3 A test was conducted in the same manner as in Example 2 except that polyphenylene ether and polyamide were replaced with 20 parts and 80 parts, respectively. The results are also listed in Table-2.

Comparative Example 4 In Example 2, polyphenylene ether and polyamide were replaced with 80 parts and 20 parts, respectively, and a test was conducted in the same manner as in Example 2. The results are also shown in Table 2.

Examples 5 to 10 Using the specific components listed in Table 3, 21 ul of fruit was prepared.
50 parts of the same polyphenylene ether as J1, 50 parts of 6-6 polyamide or 6-polyamide (6-PA),
5 parts of BSIO, 18 parts of brominated polystyrene, 6 parts of antimony trioxide, maleic anhydride, epoxidized soybean oil, oleyl alcohol, linseed oil, butyl glycidyl ether, and a condensate of bisphenol A and epichlorohydrin, as shown in Table 3. The pellets obtained by blending 0.5 part or 1.0 part were tested in the same manner as in Example 1, and the results shown in Table 3 were obtained.

Example 11 In Example 5, 6-6 polyamide (6,6-PA)
Pellets were obtained by replacing 50 parts with 6-polyamide, and tested in the same manner as in Example 1.

The results are also listed in Table-3.

Comparative Example 5 Pellets prepared in Example 5 except for 0.5 part of maleic anhydride were obtained and tested in the same manner as in Example 1. The results are also listed in Table-3.

Examples 12 to 14 The same polyphenylene ether, 6-6 polyamide, maleic anhydride, brominated polystyrene, and antimony trioxide as in Example 1 were mixed with SBR as a rubber in the proportions shown in Table 4, and then 45I111 280 using a screw extruder
Extrusion granulation was performed at °C to obtain composition pellets. This was injection molded at 270° C. using a 6-ounce injection molding machine to obtain a test piece, which was subjected to a test and the results shown in Table 4 were obtained.

Comparative Example 6 Pellets were obtained by blending in Example 11 except for SBR, and a test was conducted in the same manner as in Example 11. Display the results -
Also listed in 4.

Comparative Example 7 Pellets prepared by replacing 5 parts of SBR in Example 11 with 40 parts were obtained and tested in the same manner as in Example 11. The results are listed in Table 4 (0 below)

Claims (1)

[Scope of Claims] (a) 30 to 70% by weight of polyphenylene ether and (b)
) per 100 parts by weight of a resin consisting of 70 to 30% by weight of polyamide, (c) 3 to 30 parts by weight of a rubber-like material, (d) a carbon-carbon unsaturated bond, a carboxyl group, an acid anhydride group in the molecule, Compounds containing one or more groups selected from acid amide groups, imide groups, carboxylic acid ester groups, epoxy groups, amino groups, and hydroxyl groups, and/or
or 0.1 to 10 parts by weight of a compound having an oxirane ring in the molecule and/or a condensed polymer of dihydric phenol and epichlorohydrin; (e) 3 to 30 parts by weight of brominated polystyrene and 1 to 10 parts by weight of an antimony compound; A flame-retardant polyphenylene ether composition, characterized in that it contains 20 parts by weight.