JPS61108658A - Flame-retardant polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To provide a resin compsn. having excellent flow characteristics and improved flame retardance while retaining the mechanical characteristics of moldings, containing a polyphenylene ether resin, an acid-modified petroleum resin, an inorg. filler and a flame retarder. CONSTITUTION:A resin compsn. consists of 20-100pts.wt. polyphenylene ether resin (a), 0-80pts.wt. arom. vinyl polymer, 1-60pts.wt. (per 100pts.wt. of the combined quantity of components a and b) acid-modified petroleum resin (c), 5-200pts.wt. (per 100pts.wt. of the combined quantity of component a, b and c) inorg. filler (d) and an effective quantity of a flame retarder (e). A preferred example of the polyphenylene ether resin is poly(2,6-dimethyl-1,4-phenylene) ether. As the petroleum resin to be modified by an acid, arom. petroleum resins are preferred. The acid-modified petroleum resin is obtd. by adding an alpha,beta-unsaturated carboxylic acid to a petroleum resin.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether resin composition having excellent fluidity and flame retardancy, which is characterized by containing a modified petroleum resin.

BACKGROUND OF THE INVENTION Polyphenylene ether resins are widely used as molding material resins because of their excellent mechanical and electrical properties. By adding an inorganic filler such as glass fiber to the poly7-ethylene ether resin, the shaped articles made therefrom have extremely high elastic modulus and dimensional stability Qt. However, when an inorganic filler is added, the fluidity deteriorates when the resin composition is melted for molding, and when a flame retardant is added to the resin composition, the average level of flame retardancy decreases and variations occur. The disadvantages of being large are rare.

A technique for lowering the melt viscosity of a polyphenylene ether resin composition by adding a petroleum-derived low molecular weight resin, rosin, etc. is known (Japanese Patent Application Laid-Open No. 118956/1983).

In addition, aromatic hydrocarbon resin t obtained by polymerizing an unsaturated hydrocarbon mixture containing highly unsaturated hydrocarbon components in cracked naphtha obtained from petroleum cracking, the main component of which is unsaturated aromatic hydrocarbons. It is known that in addition to polyphenylene ether, a resin composition with extremely good melt flowability can be made (Japanese Patent Publication No. 57-13584).

Furthermore, an aromatic hydrocarbon resin obtained from petroleum naphtha is added to the polyphenylene ether resin composition containing an inorganic filler.
The applicant previously filed a patent application for an invention that improves fluidity reduction caused by filler addition by adding terpene phenolic resin or coumaron indene resin derived from coal tar (Japanese Patent Laid-Open No. 59-126460). )
.

However, none of these techniques is effective against the problem of lowering the average level of flame retardancy and widening the variation that occurs when an inorganic filler is added to a resin composition with a flame retardant formulation.

Structure of the Invention The present inventor has researched ways to solve this problem and found that by adding acid-modified petroleum resin, the flammability of the resulting molded product can be improved while maintaining its mechanical properties. They also discovered that the heat distortion temperature increases, and completed the present invention.

That is, the present invention consists of: a polyphenylene ether resin of 20 to 100 parts by weight fk b vinyl aromatic polymer Q of 0 to 80 parts by weight! L
+l) total 100! 1 to 60 parts by weight of acid-modified petroleum resin d per part i; 5 to 200 parts by weight for a total of 100 parts by weight of a+b+c
Parts by weight of inorganic filler e A flame retardant polyphenylene ether resin composition is provided comprising an effective amount of a flame retardant.

Here, the poly(7-functional)lene ether resin is known per se, and has a general formula (in the formula, R1r, R2*, R3 and R4 are hydrogen) - rogene, an alkyl group, an alkoxy group, a halogen atom and a phenyl ring. represents a monovalent substituent selected from haloalkyl groups and haloalkoxy groups having at least 2 carbon atoms and containing no tertiary α-carbon, where n is an integer representing the degree of polymerization. The term "coalescence" refers to a single type of polymer represented by the above general formula, or a copolymer in which two or more types are combined. Preferred embodiments include R1 and R.

is an alkyl group having 1 to 4 carbon atoms), and R3゜R4 is hydrogen or an alkyl group having 1 to 4 carbon atoms.

For example, poly(2,6-cymethyl-1°4-72-2lene)
Ether, poly(2,6-siether-1,4-phenylene)ether, poly(2-methyl-6-ethyl-1,4
-phenylene) ether, poly(2-methyl-6-propyl-t4-phenylene) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-phenylene) ether,
-ethyl-6-broby-1,4-phenylene) ether and the like. A particularly preferred polyphenylene ether resin is PO! j(2,6-dimethyl-1,4-phenylene)etherterol.

The polyphenylene ether copolymer contains an alkyl trisubstituted phenol in the polyphenylene ether repeating unit, such as 2. Copolymers containing a portion of erotrimethylphenol can be mentioned. Alternatively, a copolymer in which a styrene compound is grafted onto these polyphenylene ethers may be used. The styrene compound grafted polyphenylene ether mentioned above may be added with a styrene compound such as styrene, α-methylstyrene, vinyltoluene,
It is a copolymer obtained by graft polymerization of chlorstyrene, etc.

The vinyl aromatic polymers used in the present invention are also known per se. Typically, the general formula (wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms, 2 represents a substituent which is a halogen or an alkyl group having 1 to 4 carbon atoms, and p is 1 to The polymer has at least 25 units of repeating structural units derived from a styrene compound represented by the integer number 5). Such styrenic polymers include, for example, homopolymers of styrene or its derivatives, as well as natural or bottom elastomers such as polybutadiene, polyimprene, butyl rubber, EFDM, ethylene-propylene copolymers, natural rubber, shrimp chlorohydrin, etc. Styrenic polymers mixed with or modified with substances, and furthermore,
Styrene-containing copolymers, such as styrene-acrylonitrile copolymer (8AM), styrene-butadiene copolymer, styrene-maleic anhydride copolymer, styrene-acrylonitrile-butadiene copolymer (AB8)
e can be mentioned.

Preferred styrenic polymers for the present invention are homopolystyrene and rubber reinforced polystyrene. The mixing ratio of the beer-based aromatic polymer to the polyphenylene ether resin is preferably within a range that does not impair the excellent properties of the polyphenylene ether resin. A ratio of parts by weight is preferred.

Examples of the inorganic filler which is component d of the composition of the present invention include glass fiber, glass peas, glass flakes, flax mica,
Examples include, but are not limited to, one or a combination of inorganic fillers such as carbon fiber, metal fiber, metal 7 lake, and talc. The amount of the inorganic filler used is 5 to 100 parts by weight based on the total of 100 parts by weight of the polyphenylene ether resin, vinyl aromatic polymer, and acid-modified petroleum resin. If it is less than 5 parts by weight, the intended improvement in elastic modulus and dimensional stability will be insufficient.
On the other hand, if it exceeds 200 parts by weight, molding becomes difficult.

As the flame retardant component e of the composition of the present invention, any conventional flame retardant can be used.

For example, a phosphoric acid ester type or a halogen type can be used.

Examples include phenylbisdotecyl phosphate, phenylbis-neopentyl phosphate, enylethylene sonnite,
Phenyl-bis(A5,5'-trimethylhexyl 7-ophosphate), ethyl diphenyl phosphate, 2-ethylhexyldi(p-tolyl) 7-o-7ate, IJ') phenyl, bis-(2- ethylhexyl)p-)ruylphos 7ate, tritolyl phosphate, bis-(2
-Ethylhexyl) phenyl phosphate, tri(nonylphenyl) 7 phosphate, dienylmethylsulfite, di(dodecyl)p-1ruyl 7 male 7 ate, tricresyl phosphate, triphenyl phosphate, dibutylphenyl phosphate, 2 -chloroethyldiphenyl phosphate, p-)ruylbis(2,s,s'-trimethylhexyl)phosphate, 2-ethylhexyldiphenyl 7 phosphate, phosphorus [ff-siphenyl, etc.]. Preferred phosphoric acid esters are - and also, for example, 2,2-bis(i5-dichlorophenyl)furopanebis(2-chlorophenyl)methanebis(2,6-dibromophenyl)methane1.1-bis(4-iodophenyl)ethane1. 2-bis(2,6-
dichlorophenyl)ethane 1,1-bis(2-chloro-
4-iodophenyl)ethane 1. 1-bis(2-chloro-4-methylphenyl)ethane 1, 1-bis(3,5-dichlorophenyl)ethane 2.
2-bis(3-phenyl-4-bromo7enyl)ethane 2.3-bis(4,6-dichlorona7tyl)furopane 2.2-bis<z, b-dichlorophenyl)pentane 2.2- Bis(55-dichlorophenyl)hexanebis(4-chlorophenyl)phenylmethanebis(55
-dichlorophenyl)cyclohexylmethane bis(3-nitro-4-bromophenyl)methane can be used.

Flame retardants are used in conventional effective amounts, depending on the type of each flame retardant and the intended degree of flame retardancy.

Generally, it is used in an amount of 2 to 30% by weight based on the total of resins a, b and C.

Now, the acid-modified petroleum resin which is component C of the composition of the present invention will be explained below.

The petroleum resin used for acid modification is an unsaturated hydrocarbon fraction obtained by cracking petroleum, such as LPG, light or heavy naphtha, kerosene or gas oil fraction, heavy oil or crude oil, etc. of petroleum [1 t, boiling point 20-28 obtained when producing ethylene, propylene, butadiene, etc. by cracking by thermal cracking methods such as so-called steam cranking, gas phase pyrolysis, sand cranking, etc. or catalytic cracking methods.
It is a resin obtained by polymerizing an unsaturated hydrocarbon fraction, which is a by-product oil fraction, with a boiling point range of 0°C. This unsaturated hydrocarbon fraction contains phthene, imbutylene, butadiene, pentene, methylpentene, isoprene, pentadiene,
It contains many monoolefins or diolefins such as styrene, methylstyrene, vinyltoluene, and indene. Depending on the properties of the unsaturated hydrocarbon fraction of the raw material,
Aliphatic petroleum resin obtained by polymerizing a fraction consisting of hydrocarbons having 4 to 5 carbon atoms with a boiling point range of 20 to 50°C, and a fraction consisting of hydrocarbons having 9 or more carbon atoms having a boiling point range of 140 to 280°C. These include aromatic petroleum resins polymerized with petroleum resins, and petroleum resins copolymerized with these petroleum resins. Preferred petroleum resins used for acid modification in the present invention are the above-mentioned aromatic petroleum resins, that is, unsaturated hydrocarbons containing unsaturated aromatic hydrocarbons such as vinyltoluene, indene, and methylstyrene with a boiling point range of 140 to 280°C. It is an aromatic petroleum resin obtained by polymerizing fractions.

The petroleum resin of the present invention is produced by using a Friedel Krach type catalyst such as aluminum chloride or boron heptadide in the above-mentioned unsaturated hydrocarbon fraction to produce a reaction mixture of -30 to +10
After incubation for 20 minutes to 15 hours at a temperature of 0°C, preferably 0 to 60°C, the catalyst is decomposed with AT or an alkali, washed with water, and further evaporated or distilled to remove unreacted oil and low molecular weight polymers. can be obtained by separating.

The softening point of the petroleum resin obtained in this way is usually 50
Medji at ~200°C, its bromine number is 10, ~60.

The acid-modified petroleum resin of the present invention has α, β
- Modified by addition of unsaturated carboxylic acids, especially α, β-unsaturated dicarboxylic acids or their anhydrides. The modification includes α,β-unsaturated dicarboxylic acids,
For example, one or more of maleic acid, citraconic acid, or anhydride thereof is used. This modification method involves heating the petroleum resin obtained above in a molten state, or in a state in which the petroleum resin is dissolved in an inert solvent such as a saturated hydrocarbon, and adding a predetermined amount of carboxylic acid to 100 parts of the resin. Or its anhydride is added, and no catalyst or a catalyst such as peroxide is added to α01-5
1 to 1 at a temperature in the range of 120 to 250 °C using vt%
This is done by reacting for 6 hours.

After the reaction is completed, unreacted components, solvent, etc. are distilled off. The amount of the added unsaturated carboxylic acid or its anhydride is determined by measuring the acid value of the obtained acid-modified petroleum resin.

The acid value of the acid-modified petroleum resin suitable for the resin composition of the present invention is 5 to 80, more preferably 10 to 60.

The acid-modified petroleum resin is 1 to 60 parts per 100 parts of the polyphenylene ether resin and the vinyl aromatic polymer.
Parts by weight, preferably 5 to 20 parts by weight. If the amount is less than 5 parts by weight, the intended effect cannot be achieved, while if the amount exceeds baM, the inherent properties of the polyphenylene ether resin and vinyl aromatic polymer, such as heat distortion temperature,
Good impact strength is lost.

The composition of the present invention may further contain flame retardant aids, processing aids, pigments, dyes, stabilizers, plasticizers, etc. in addition to the above-mentioned components a' to e, if necessary.

In the following, the invention will be further explained by examples. All resin assembly preparations were performed in the following manner.

First, the ingredients were thoroughly mixed in a Henschel mixer. Is it mixed together like this? The mixture was melt-kneaded through a twin-screw extruder with a cylinder temperature set at 280 to 300°C, and then pelletized. These pellets were injection molded at a mold temperature of 70°C using an injection molding machine set at a cylinder temperature of 250 to 300°C. Physical testing of the compositions was conducted by the following method.

The flammability test was conducted in accordance with UI, 94 V-0. The thickness of the test piece is 1/16 inch.

Flexural modulus was measured according to ASTM D 790 using sample pieces l/, # x % I x 5 #. The heat distortion temperature was determined according to ASTM D 64B using a load of 1 &6' with a load of 1 &6' of 9/
It was measured in “crs”.

Example of production of acid-modified petroleum resin: Among cracked oil fractions obtained by steam cranking of naphtha, a fraction with a boiling point range of 140 to 200°C containing vinyl toluene, indene, etc. as the main fraction is used as a raw material. After adding a boron fluoride catalyst (L 5 wt%) and polymerizing at 30° C. for 3 hours, the catalyst was decomposed with an aqueous isoda solution, washed with water, and distilled under reduced pressure to obtain a desired aromatic petroleum resin.

Softening point: 153°C 1 kg of the resin obtained above was dissolved in 1' kg of benzene, and a predetermined amount of maleic anhydride was added thereto, followed by tart.

-Butyl peroxide was added to the resin at a concentration of 1 vrt%, and the reaction was carried out at 1,400°C under autogenous pressure for 6 hours. After maleation, benzene was distilled off to obtain a desired maleated aromatic petroleum resin. Table 1 shows the softening point and acid value of each resin obtained.

Table 1 Examples 1 and 2 and Comparative Examples 1 and 2 Using the above acid-modified petroleum resin 5 and unmodified petroleum resin 1, a resin composition having the composition shown in Table 2 (numbers are parts by weight) was produced. The data obtained by measuring the performance of is shown in the lower part of Table 2.

Table 2 PPO: Poly(2,6-cymethyl-1.4-7-dinilene) ether (intrinsic viscosity α51d4/?, 30°C in chloroform solution) PS: Borysterene TPP:) Riphenyl phosphate As can be seen from the table, The resin compositions of Examples 1 and 2 according to the present invention have a smaller average burning time and a smaller standard deviation (variation) than Comparative Examples 1 and 2, respectively.

Examples 3 to 6 and Comparative Example 3 Resin compositions were prepared in the same manner as above using petroleum resins having various degrees of acid modification, and their performance was determined.

Composition and results are shown in Table 3.

Cloth 3 From Table 3, the effect of acid-modifying petroleum resin is clear.

Claims (1)

[Claims] 1. a 20 to 100 parts by weight of polyphenylene ether resin b 0 to 80 parts by weight of vinyl aromatic polymer ca 1 to 60 parts by weight of acid-modified resin based on the total of 100 parts by weight of a+b A flame-retardant polyphenylene ether resin composition that warps from petroleum resin d, 5 to 200 parts by weight of inorganic filler e, and an effective amount of flame retardant, based on a total of 100 parts by weight of a+b+c. 2. Claim 1 in which the flame retardant is a phosphoric acid ester
Compositions as described in Section.