JPS61261346A - Flame-retardant aromatic polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having excellent flame retardance, electrical properties, etc., and suitable for use as an electrical insulating material, by blending a halogenated phenoxy resin, antimony oxide, a polyfunctional epoxy compd. and a filler. CONSTITUTION:100pts.wt. arom polyester resin (e.g. polyethylene terephthalate), 3-50pts.wt. halogenated phenoxy resin contg. a skeleton of the formula (wherein X is Br, Cl; R is a 1-10C alkylene, alkylidene, carbonyl, -O-, -S-, -SO2-; n is 15-100), 1-40pts.wt. antimony oxide, 0.1-20pts.wt. polyfunctional epoxy compd. (e.g. bisphenol type epoxy compd.) and 0-200pts.wt. filler (e.g. glass fiber or silica) are mixed together to obtain the desired flame-retardant arom. polyester resin compsn.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention provides a flame-retardant aromatic polyester that has excellent flame retardancy, mechanical properties, molded product appearance, and electrical properties, and is particularly suitable for electrical insulation materials. The present invention relates to a composition.

<Prior Art> Aromatic polyesters such as polybutylene terephthalate are widely used as molding materials for mechanical parts, electrical parts, automobile parts, etc. due to their excellent moldability and mechanical properties. On the other hand, materials for these uses are required not only to have a good balance between general chemical and physical properties, but also to have strong safety against flames, that is, flame retardancy.

A known method for imparting flame retardancy to aromatic polyesters such as polybutylene terephthalate (PBT) is to add organic halogen compounds such as decabromodiphenyl ether or phosphorus compounds as flame retardants. However, with these conventional low-molecular-weight flame retardants, the flame retardant bleeds out onto the surface of the molded product, impairing its appearance and causing problems such as contact failure. For this reason, there has recently been a growing tendency to use polymeric flame retardants, and in particular, the method of adding brominated epoxy oligomers, as shown in Japanese Patent Publication No. 18068/1983, is relatively effective in preventing bleed-out. Although it is excellent, it has problems such as poor moldability and gelation.

<Problems to be Solved by the Invention> Therefore, a method of adding a high molecular weight brominated phenoxy resin with an average degree of polymerization of 11 or more has been proposed in JP-A-58-118849. Although no increase in melt viscosity was observed, it was difficult to disperse well in PBT due to the high melt viscosity of the flame retardant itself, and a molded product with good mechanical properties and molded product appearance could not be obtained.

<Means for Solving the Invention> Therefore, the present inventors conducted extensive studies in order to obtain an aromatic polyester composition with excellent flame retardance, mechanical properties, and molded product appearance in a well-balanced manner. It has been discovered that by using a halogenated phenoxy resin with a specific degree of polymerization as a flame retardant, and further using antimony oxide and a polyfunctional epoxy compound in combination, the above objects can be achieved and the electrical properties can be significantly improved, and the present invention reached.

That is, the present invention provides (A) aromatic polyester resin 10
0 parts by weight, lB) 3 to 50 parts by weight of a halogenated phenoxy resin having a skeleton represented by the following general formula, 1 to 40 parts by weight of ρ antimony oxide, ◎0.1 to 20 parts by weight of a polyfunctional epoxy compound The present invention provides a flame-retardant aromatic polyester composition containing 0 to 200 parts by weight of Filler D and Filler D.

(In the above formula, X is a bromine or chlorine atom, R is 01
~10 alkylene group, alkylidene group, carbonyl group, -〇-1-5- or -SO, -1n is 15 to 100
indicates an integer. ) The (3) component aromatic polyester used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer,
Aromatic dicarboxylic acid (or its ester-forming derivative) and diol (or its ester-forming derivative)
It is a polymer or copolymer obtained by a condensation reaction containing as main components.

The aromatic dicarboxylic acids mentioned here include terephthalic acid,
Isophthalic acid, orthophthalic acid, 1,5-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 2,6
-Naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,γ-biphenyldicarboxylic acid, 4114
'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4@4'-diphenylisopropylidene dicarboxylic acid, l e 'l -hyx(phenoxy)ethane-4. 4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4'-1)-terphenylenedicarboxylic acid,
2-5-pyridinedicarboxylic acid, etc., and terephthalic acid (preferably used).

Two or more of these aromatic dicarboxylic acids may be used in combination. In addition, in small amounts, adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid may be used along with these aromatic dicarboxylic acids.

One or more aliphatic dicarboxylic acids such as cyclohexane dicarboxylic acids and cyclohexane dicarboxylic acids can be used in combination.

The diol components include ethylene glycol, propylene glycol, butylene gelicol, hexylene glycol, neopentyl glycol, 2-methyl-1,
Aliphatic diols such as 3-prono(diol), diethylene glycol, and triethylene glycol;
Alicyclic di-JLt such as cyclohexane dimetatool
and mixtures thereof.

In addition, if it is a small amount, long-chain diols with a molecular weight of 400 to 6.000, such as polyethylene glycol, poly-1.3
-One or more types of propylene glycol, polytetramethylene glycol, etc. may be copolymerized.

Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polypropylene terephthalate,
In addition to polyethylene naphthalate, polybutylene naphthalate, polyethylene"-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, etc., polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate, polybutylene terephthalate Copolymerized polyesters such as /decanedicarboxylate, etc. Among these, mechanical properties, molded tallate and polyethylene terephthalate can be preferably used.

Aromatic polyester used in the present invention +, t, 0
．． It is preferable that the relative viscosity of a 5% O-chlorophenol solution measured at 25° C. is 115 to 2.0, particularly L3 to L85.

The halogenated phenoxy resin having the skeleton shown in the general formula of component (1) used in the present invention can be produced by a known method, for example, by polymerizing halogenated bisphenol and epichlorohydrin, or halogenated bisphenol diglycidyl ether and halogenated bisphenol under polymerization conditions. It can be obtained by condensation by adjusting.

The halogenated bisphenol compound that is a component of the halogenated phenoxy resin in the above general formula is 2.2-
Bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, bis(3,5-dibrom-4
-hydroxyphenyl)methane, bis(3,5-dibromo-4-hydroxyphenyl)phenylmethane, 1. −
1-bis(3,5-dibrom-4-hydroxyphenyl)ethane, bis(3,5-dibrom-4-hydroxyphenyl)sulfone, bis(3,5-dibrom-4-hydroxyphenyl)ether, bis(3・5-dibrome-
4-hydroxyphenyl)ketone, bis(3.5-dichloro-4-hydroxyphenyl)sulfone, bis(3.
Examples include 5-dibromo-4-hydroxyphenyl) sulfide, among which 2,2-bis(3,5-dibromo-
Most preferred is the use of 4-hydroxyphenyl)propane. Using halogenated bisphenols together with non-halogenated normal bisphenol compounds, such as 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)methane, etc. I can do it.

The halogenated phenoxy resin of the present invention generally has a glycidyl group and/or a hydroxyl group as a terminal group, but it is also possible to use a resin in which these terminal groups are blocked with carboxylic acids, phenols, amines, or alcohols. You can also use things.

The amount of halogenated phenoxy resin added in the present invention is
The amount is 3 to 50 parts by weight, preferably 5 to 25 parts by weight based on the aromatic polyester. If it is less than 3 parts by weight, the flame retardance will not be sufficient, and if it exceeds 50 parts by weight, the mechanical properties of the aromatic polyester will deteriorate. This is not preferable because it damages the

Antimony oxide used as the Ω component in the present invention is
Although there are no particular restrictions, antimony dioxide can be preferably used as long as it is normally used as a flame retardant aid for polyester. Further, zirconium oxide, zinc sulfide, barium sulfate, etc. may be used in combination with antimony oxide.

The amount of antimony oxide added in the present invention is 1 to 40 parts by weight, preferably 3 to 20 parts by weight, per 100 parts by weight of the aromatic polynitrate, and in particular, 2 to 5 parts by weight of bromine atoms in the composition.
It is preferable to add 1,000 parts of antimony per 1,000 parts.

The polyfunctional epoxy compound used in component D of the present invention is a compound that contains at least two epoxy groups and does not contain halogen. Preferred examples of polyfunctional epoxy compounds include bisphenol-type epoxy compounds obtained by reacting bisphenol A and epichlorohydrin in various proportions, novolac-type epoxy compounds obtained from novolak resin and epichlorohydrin, and novolac-type epoxy compounds obtained from polycarboxylic acid and epichlorohydrin. Polyglycidyl esters obtained from polyglycidyl esters, alicyclic compounds (e.g., dicyclopentadiene), aliphatic compounds having an alcoholic hydroxyl group (e.g., butanediol, glycerin, etc.) and epichlorohydrin. Examples include glycidyl ethers, epoxy group-containing copolymers consisting of unsaturated monomers having an oxy group, such as epoxidized polybutadiene, and glycidyl methacrylate, and other unsaturated monomers, such as ethylene.

Among these polyfunctional epoxy compounds, more preferred are the following general formulas Ql) and I O2 (wherein, bi is a cyclohexane ring, a cyclohexene ring, or a benzene ring, and n is an integer of O to 30). Glycidyl ester and bisphenol A represented by
Epoxy groups such as type epoxy compounds, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/carbon oxide/glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, etc. Among them, ethylene/glycidyl methacrylate copolymers containing 1 to 30% by weight of glycidyl methacrylate and ethylene/glycidyl methacrylate copolymers containing 1 to 30% by weight of glycidyl methacrylate.
Glycidyl methacrylate/vinyl acetate copolymer is preferred. Note that two or more of the polyfunctional epoxy compounds listed above may be used in combination.

The amount of the polyfunctional epoxy compound added in the present invention is 0.1 to 20 parts by weight, more preferably 0.5 to IO parts by weight, per 100 parts by weight of the aromatic polyester. If the amount added is less than 0.1 part by weight, the effect of improving mechanical properties will be small;
On the other hand, if it exceeds 20 parts by weight, there is a drawback that the flame retardancy of the aromatic polyester is impaired.

Fillers of component (1) that can be used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers,
Potassium titanate fiber, gypsum fiber, brass fiber, stainless steel fiber, steel fiber, ceramic fiber, boron whisker fiber, asbestos, mica, talc, silica,
Examples include fibrous, powder, granular, or plate-like inorganic fillers such as calcium carbonate, glass peas, glass flakes, clay, wollastenite, and titanium oxide.

By adding these fillers, it is possible to improve the heat distortion temperature and rigidity, and reduce the molding shrinkage rate.

Among the fillers mentioned above, glass fibers are preferably used. The type of glass fiber is not particularly limited as long as it is generally used for reinforcing resins, and can be selected from long fiber type, short fiber type chopped strand, milled fiber, etc., for example. Further, the glass fibers may be coated or bundled with a thermoplastic resin such as ethylene/vinyl acetate copolymer, a thermosetting resin such as an epoxy resin, or a coupling agent such as a silane type or titanate type, or other It may be treated with a surface treatment agent.

When adding a filler, the amount is 10% of the aromatic polyester.
The amount is up to 200 parts by weight, more preferably up to 100 parts by weight.

The composition of the present invention includes, to the extent that the object of the present invention is not impaired,
Common additives, such as UV absorbers, lubricants, mold release agents, colorants including dyes and pigments, antioxidants (e.g. hindered phenols, thiopropionate esters, phosphite compounds, etc.), other thermal It may further contain a plastic resin (eg, polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/propylene/gentar polymer, ethylene/butene-1 copolymer, ethylene/vinyl acetate copolymer), and the like. These additives may be used alone or in combination of two or more.

The method for producing the composition of the present invention is not particularly limited, but preferably aromatic polyester, halogenated phenoxy resin, antimony oxide, polyfunctional epoxy compound,
Furthermore, if necessary, a method of melt-kneading fillers and the like using an extruder may be mentioned.

The resin composition of the present invention can be easily molded by conventional methods such as injection molding and extrusion molding, and the resulting molded product exhibits excellent performance.

<Example> EXAMPLES Hereinafter, the effects of the present invention will be explained in further detail with reference to Examples.

Examples 1-5. Comparative Examples 1 to 7 100 parts by weight of polybutylene terephthalate having a relative viscosity of 165 were mixed with the following brominated phenoxy resin A, antimony dioxide, and various polyfunctional epoxy compounds shown in Table 1 in the proportions shown in Table 1 using a Henschel mixer. ,4ogg
*The mixture was melt-kneaded at 250°C using an extruder and pelletized.

The pellets were dried at 130°C for 5 hours in a hot air dryer, and then heated to 250°C using a screw in-line injection molding machine.
A combustion test piece (1/8
'X 1/2'X5', and 1/32"X
1/2' x 5''), ASTM No. 1 dumbbell and Izotz impact test specimens were molded.

The appearance of these test pieces was observed and UL-9
Vertical combustion test according to 4 standards, ASTM D-63
Tensile test according to 8 and Izot impact test according to ASTM D-256. , :ASTM D-49
Arc resistance was measured according to 5 standards. These results are shown in Table 1.

For comparison, Table 1 also shows examples in which the following brominated phenoxy resins B and C were used as flame retardants.

°Flame retardant B: @ top
. =50: Same
Top n=11
3 As is clear from the results in Table 1, the aromatic polyester blended with a halogenated phenoxy resin of a specific degree of polymerization, antimony oxide, and a polyfunctional epoxy compound of the present invention is
It can be seen that it has excellent mechanical properties such as flame retardancy, tensile properties, and Izod impact strength, as well as good molded product appearance and electrical properties.

Examples 6-8. Comparative Examples 8 to 9 20 parts by weight of the flame retardant used in Example 1 to 100 parts by weight of polybutylene terephthalate with a relative viscosity of 148,
7 parts by weight of antimony trioxide, 50 parts by weight of glass fiber (chopped strand), 1 part by weight of dilauryl thiodipropionate O, and the polyfunctional epoxy compound shown in Table 2 were mixed in a V-blender, and then extruded at 4080 mm. The mixture was melt-kneaded using a machine at 250°C and pelletized.

This pellet was molded and evaluated in the same manner as in Example 1. The results are shown in Table 2.

As is clear from Table 2, even when a filler is included, the composition of the present invention has excellent flame retardancy and mechanical properties, as well as excellent molded product appearance and electrical properties.

<Effects of the Invention> The flame-retardant aromatic polyester composition of the present invention has flame retardancy,
It has excellent mechanical properties, molded product appearance, and electrical properties, and is particularly suitable for electrical insulation materials.

Claims (1)

[Claims] (A) For 100 parts by weight of aromatic polyester resin, (
B) 3 to 50 parts by weight of a halogenated phenoxy resin having a skeleton represented by the following general formula (I), (C) 1 to 40 parts by weight of antimony oxide, (D) 0.0 parts by weight of a polyfunctional epoxy compound.
A flame-retardant aromatic polyester composition comprising 1 to 20 parts by weight of a filler (E) and 0 to 200 parts by weight of a filler (E). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (In the above formula (I), X is a bromine or chlorine atom, R
is C_1_ to_1_0 alkylene group, alkylidene group, carbonyl group, -O-, -S- or -SO_2-,
n represents an integer of 15 to 100. )