JPS60252652A - Flame-retardant polyester composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent heat-resistance and remarkably high residential stability of mechanical and electrical characteristics, by compounding an aromatic polyester with a specific halogen-containing polymer and a glycidyl-containing copolymer. CONSTITUTION:The objective composition is produced by compounding (A) 100pts.(wt.) of an aromatic polyester with (B) 3-50pts. of a halogen-containing vinyl polymer having the recurring unit of formula (R is H or 1-5C alkyl; X is Cl or Br; m is 1-5) and (C) 1-20pts. of a glycidyl-containing copolymer composed of an alpha-olefin and an alpha,beta-unsaturated acid glycidyl ester. The component A is preferably a polybutylene terephthalate or polyethylene terephthalate having a relative viscosity of 1.3-1.85 at 25 deg.C as 0.5% o-chlorophenol solution. The component B is preferably poly(pentabromobenzyl acrylate) and the component C is preferably an ethylene/glycidyl methacrylate copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a flame-retardant polyester composition having excellent retention stability and heat resistance stability in terms of mechanical properties and electrical properties.

<Prior art> Aromatic polyesters, represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, etc., are used to manufacture mechanical parts, electrical parts, automobile parts, etc. by utilizing their excellent properties. It is beginning to find uses in

On the other hand, in addition to the general balance of chemical and physical properties, these industrial materials are also strongly required to have flame safety, that is, flame retardancy, and at present, the ability to impart flame retardance is important for industrial use. It is no exaggeration to say that this will determine the possibility of expanding the use of aromatic polyester.

The use of poly(halogenated benzyl acrylate) polymers as M flammability imparting agents for aromatic polyesters such as polybutylene terephthalate is well known, as proposed in, for example, JP-A No. 52-3682. It is being In addition, when aromatic polyester is made flame retardant using this method, there is a problem that the aromatic polyester decomposes due to stagnation in a molding machine etc., resulting in a decrease in mechanical properties. 14975
A method of adding an epoxy compound such as bisphenol A-ebichlorhydrinib as shown in No. 6 has been proposed.

However, even with the above method, although the retention stability of the molding machine can be improved to some extent, there is a problem in that when the molded product is further subjected to dry heat treatment, the mechanical and electrical properties deteriorate significantly. .

<Problems to be Solved by the Invention> Therefore, the present inventors solved the above-mentioned problem in flame retardation of aromatic polyester using a poly(halogenated benzyl acrylate) flame retardant, namely, a decrease in mechanical properties during molding. As a result of intensive studies to improve the mechanical properties and electrical properties, retention stability and heat resistance stability were significantly improved by using a poly (halogenated pencil acrylate) flame retardant in combination with a specific glycidyl group-containing copolymer. The inventors have discovered that this is the case and have arrived at the present invention.

In other words, the present invention provides 100x parts of aromatic polyester, 3 to 50ffi parts of a halogen-containing vinyl polymer having repeating units as shown below, and - Provides a flame-retardant polyester composition containing 1 to 20 parts by weight of a glycidyl group-containing copolymer consisting of an olefin and a glycidyl ester of an α,β-unsaturated acid.

(However, in the formula, R is hydrogen or an alkyl group having 1 to 5 carbon atoms, X is chlorine or bromine, and m is an integer of 1 to 5.) The aromatic polyester used in the present invention refers to A polymer or copolymer that has a polyester in the chain unit of the union and is obtained by a condensation reaction containing WIF IA dicarboxylic acid (or its ester-forming derivative) and diol (or its ester-forming derivative) as the main components. It is a combination.

The aromatic dicarboxylic acids mentioned here include terephthalic acid,
Isophthalic acid, orthophthalic acid, l.

5-naphthalene dicarboxylic acid, 215-naphthalene dicarboxylic acid, 2.6-naphthalene dicarboxylic acid, 4.4'
-Biphenyldicarboxylic acid, 3.3'-biphenyldicarboxylic acid, 4.4'-diphenyl etherdicarboxylic acid, 4.4'-diphenylmethanedicarboxylic acid, 4.4'
-diphenylsulfone dicarboxylic acid, 4,4'-diphenylisopropylidene dicarboxylic acid, 1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, 2,5-
These include anthracenedicarboxylic acid, 216-anthracenedicarboxylic acid, 4,4''-1)-terphenylenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, and terephthalic acid is preferably used.

Two or more of these aromatic dicarboxylic acids may be used in combination. In addition, if the amount is small, one or more types of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used in combination with these aromatic dicarboxylic acids. be able to.

In addition, as diol components, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1
, 3-propanediol, diethylene glycol, aliphatic diols such as triethylene glycol, alicyclic diols such as 1,4-cyclohexane dimetatool, etc.
and mixtures thereof.

In addition, in small amounts, long chain diols with a molecular weight of 400 to 6.000, i.e. polyethylene glycol, poly-1
, 3-propylene glycol, polytetramethylene glycol, etc. may be copolymerized.

Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate,
In addition to polyester, ethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis(phenoxy)ethane-4゜4'-dicarboxylate, polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate, polybutylene Examples include copolymerized polyesters such as terephthalate/decanedicarboxylate. Among these, mechanical properties,
Polybutylene terephthalate and polyethylene terephthalate, which have well-balanced moldability, are preferably used.

The aromatic polyester used in the present invention is 0.5%
The relative viscosity of the 0-chlorophenol solution measured at 25° C. is preferably 115 to 2.0, particularly preferably 13 to 1.85.

The halogen-containing vinyl polymer used as a flame retardant in the present invention is a polymer essentially having a repeating unit of the following formula (1).

However, in the formula, R is hydrogen or an alkyl group having 1 to 5 carbon atoms, more preferably hydrogen, methyl, or ethyl, X is chlorine or bromine, and m is an integer of 1 to 5.

Monomers used in the production of the halogen-containing vinyl polymer of the present invention include pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tetrabromomethylbenzyl acrylate, tribromobenzyl acrylate, dibromobenzyl acrylate, bromobenzyl acrylate, and pentabromobenzyl acrylate. rombenzyl methacrylate, tetrabromobenzyl methacrylate, tetrabromomethylbenzyl methacrylate, tribromobenzyl methacrylate, pentachlorobenzyl acrylate,
Tetrachlorobenzyl methacrylate, tribromobenzyl methacrylate, pentachlorobenzyl acrylate, tetrabromobenzyl acrylate, trichlorobenzyl acrylate, pentachlorobenzyl methacrylate, tetrachlorobenzyl methacrylate, trichlorobenzyl methacrylate, pentachlorobenzyl methacrylate, tetrachlorobenzyl methacrylate, trichlorobenzyl These include methacrylate, and more than one type can be used in combination. These pentabromobenzyl acrylate, tetrabromobenzyl acrylate, tribromohensyl acrylate, pentabromobenzyl methacrylate, tetrabromobenzyl methacrylate, and tribromobenzyl methacrylate are preferable, and pentabromobenzyl acrylate is more preferable.

Further, other monomers may be copolymerized with the halogen-containing vinyl polymer of the present invention as long as the flame retardant effect of the polymer is not significantly reduced.

These include styrene, α-methylstyrene, p-methylstyrene, acrylonitrile, methacrylatetrile, acrylic esters of alcohols having 1 to 6 carbon atoms, methacrylic esters, xylylene acrylate and -
Examples include methacrylate and its chlorine-substituted products, butadiene, isoprene, fumaric acid and maleic acid or its anhydride, vinyl chloride, vinylidene chloride, and the like.

The method for producing the halogen-containing vinyl polymer is not particularly limited, but includes, for example, a method in which a peroxide or an azo compound is used in a solution.

Specific examples of the halogen-containing vinyl polymer of the present invention include poly (pentabromobenzyl acrylate), poly (
Preferred examples include poly(tetrabromobenzyl methacrylate), poly(tetrabromomethylbenzyl methacrylate), pentabromobenzyl acrylate/styrene copolymer, and pentabromobenzyl acrylate/methyl methacrylate copolymer. Among them, poly(pentabromber acrylate) is more preferred.

In the present invention, the amount of the halogen-containing vinyl polymer added is 3 to 50 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the aromatic polyester.The amount added is less than 3 parts by weight. However, if the amount exceeds 50 parts by weight, the mechanical properties of the aromatic polyester will be impaired, so both are not preferred.

The flame retardant effect of the halogen-containing vinyl polymer can be protected by the concomitant addition of a flame retardant adjuvant. Antimony dioxide is preferably used as the combustion aid. In order to obtain a sufficient effect of imparting flame retardancy and a sufficient effect of maintaining the mechanical properties of the aromatic polyester, the amount added is preferably 1 to 20 M parts, more preferably 1 to 20 M parts per 100 parts by weight of the aromatic polyester. It is 3 to 15 parts by weight.

More preferably, it is added in a ratio of 1 antimony atom in antimony trioxide to 2 to 5 halogen atoms in the 10-gen-containing vinyl polymer (added). At the same time, other flame retardant aids such as boron oxide, ruconium oxide, and iron oxide may be used in combination.

α-olefin and α used in the present invention.

The α-olefin in the glycidyl group-containing copolymer made of glycidyl ester of β-unsaturated acid includes ethylene, propylene, phthene-1, etc., and ethylene is preferably used. In addition, glycidyl esters of α,β-unsaturated acids are compounds represented by the general formula (in the formula, R is a hydrogen atom or a lower alkyl group), and specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl methacrylate, Examples include glycidyl acrylate, and glycidyl methacrylate is preferably used. α.

The amount of copolymerization of glycidyl ester of β-unsaturated acid is 0.5
A suitable range is from 1 to 50% by weight, preferably from 1 to 30% by weight, more preferably from 2 to 20% by weight. Furthermore, 40
Unsaturated monomers that can be copolymerized with the above-mentioned copolymers, ie, vinyl ethers, vinyl esters such as vinyl acetate, vinyl propionate, etc.
Acrylic acid and methacrylic acid esters such as methyl, ethyl, propyl, acrylonitrile, styrene,
- Two or more kinds of carbon oxides etc. may be copolymerized.

Preferred examples of the glycidyl group-containing copolymer in the present invention include ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, ethylene/carbon oxide/glycidyl methacrylate copolymer, and ethylene/glycidyl methacrylate copolymer. Examples thereof include glycidyl acrylate copolymer, ethylene/vinyl acetate/glycidyl acrylate copolymer, and among them, ethylene/glycidyl methacrylate copolymer is most preferred.

The amount of the glycidyl group-containing copolymer added in the present invention is 1 to 20 parts by weight, preferably 2 to 10 parts by weight, per 100 parts by weight of the aromatic polyester. If the amount added is less than 1 part by weight, the retention stability and heat resistance stability will not be improved sufficiently, and if it exceeds 20 parts by weight, the flame retardancy of the aromatic polyester will tend to be impaired, so both are not preferred.

In addition to the glycidyl group-containing copolymer used in the present invention, an ethylene copolymer consisting of ethylene and an α-olefin having 3 or more carbon atoms and/or ethylene and an α-olefin having 3 or more carbon atoms
If the terpolymer consisting of the above a-olefin and non-conjugated diene is used in combination, the impact resistance can be further improved. Specific examples of these copolymers include ethylene/
Propylene copolymer, ethylene/butene-1 copolymer,
Ethylene/pentene-1 copolymer, ethylene/propylene/butene-1 copolymer, ethylene/propylene 15-
Ethylidene-2-norbornene copolymer, ethylene/propylene/1,4-hexadiene copolymer, ethylene/
These include propylene/dicyclopentadiene copolymers, among which ethylene/propylene copolymers and ethylene/butene-1 copolymers are preferred.

The amount of the above-mentioned ethylene copolymer added is 1 to 7 parts, preferably 2 parts based on the weight of the aromatic polyester.
It is preferable that the amount is 40 parts by weight or less, and the total amount with the glycidyl group-containing copolymer is 80 parts by weight or less.

Incidentally, when a compound that promotes the reaction between the epoxy compound and the carboxylic acid is further added to the composition of the present invention, it is possible to obtain the effect that the impact resistance can be further improved. These compounds include triphenylamine, 2,4.
Tertiary amines such as 6-tris(dimethylaminomethyl)phenol, phosphite esters such as triphenyl phosphite and triisodecyl phosphite, phosphonium compounds such as triphenylallylphosphonium bromide, and tertiary phosphines such as triphenylphosphine. , carboxylic acid metal salts such as lithium stearate and calcium stearate, sulfonic acid metal salts such as sodium dodecylbenzenesulfonate and sodium 3,5-dicarbomethoxybenzenesulfonate, and sulfuric acid ester salts such as sodium lauryl sulfate. It is preferable to add 0.001 to 5 parts by weight per 100 parts by weight of polyester.

In order to improve the heat distortion temperature and rigidity of the composition of the present invention, an inorganic filler may be added. For example, as a filler,
Examples include glass fiber, carbon fiber, metal fiber, glass peas, glass flakes, mica, wollastenite, talc, clay, asbestos, sericite, calcium carbonate, magnesium carbonate, barium sulfate, and titanium oxide. Two or more of these may be used in combination.

Among the inorganic fillers, glass fiber can be preferably used.

As the glass fiber, a usual chopped strand or roving type can be used, but chopped strands with a length of 3 to 6 lengths are preferred from the viewpoint of ease of handling and surface gloss of the molded product.

In addition, it is particularly preferable to use glass m-fibers that have been treated with a conventional coupling agent such as a silane type or a titanium type, or a conventional binding agent such as an epoxy resin or vinyl acetate.

In addition, conventional additives such as a mold release agent, an ultraviolet absorber, a pigment, a dye, and a nucleating agent can also be added to the composition of the present invention.

The method for producing the composition of the present invention is not particularly limited, but preferably aromatic polyester, halogen-containing vinyl polymer, glycidyl group-containing copolymer, and other necessary additives are mixed in an extruder or kneader. A method in which the particulate materials are mixed mechanically evenly and then directly mixed and molded using an injection molding machine, A method in which additives are directly introduced into the resin polymerization pot and mixed. Examples include.

The composition of the present invention is subsequently made into molded products by extrusion molding, injection molding, compression molding, etc., and these molded products have excellent flame retardancy, heat resistance, and electrical insulation properties in addition to mechanical properties. , mechanical parts, electrical parts, etc. due to its good surface appearance.
Useful as automobile parts.

<Example> The present invention will be explained in detail below with reference to Examples.

In addition, relative viscosity refers to 0 when 0-chlorophenol is used as a solvent.
．． This is a value measured at 25°C for a 5% polymer solution.

Examples 1-6, Comparative Examples 1-8 Polybutylene terephthalate h100g with relative viscosity L71
Poly(pentabromobenzyl acrylate), 7 parts by weight of antimony trioxide, and the glycidyl group-containing copolymer shown in Table 1 were added to each part in the proportions shown in Table 1, mixed in a Hen-El Shiba mixer, and then extruded in a 40 mm diameter extruder. The mixture was melt-blended and pelletized at 250°C. Next, the obtained pellets were heated to 250°C.
Using a 2 oz screw in-line injection molding machine set to Molded, AS"14-1 dumbbell, square plate (80 silk x 80 tomo x 1 piece) and combustion test piece (1 piece)
/I Px I/2' x 5') was obtained.

Also, the molding cycle (injection time/cooling time/intermediate time)
Three types of test pieces were obtained in the same manner as above, except that the molding cycle was changed to 10 seconds/15 seconds/40 seconds (molding cycle (b)), and other conditions were kept the same.

A vertical combustion test was conducted using a combustion test piece according to the UL94 standard. In addition, using tensile test pieces, ASTM
- Tensile test according to D638 standard and dielectric breakdown test using square plate according to UL standard, 18
The half-life time of both properties when dry heat treated in a 0°C oven was determined. These results are shown in Table 1.

As shown in Table 1, the composition containing the glycidyl group-containing copolymer of the present invention has excellent heat resistance stability in mechanical properties and electrical properties, and these properties deteriorate when the molding residence time becomes long. It is clear that this can be further improved.

Examples 7-10. Comparative Examples 9-I3 Polybutylene terephthalate 100f with relative viscosity 145
-7M parts of antimony trioxide, 60 parts by weight of glass fiber (epoxy resin treated, 3-strength chopped strand) or glass peas (epoxy resin treated, average particle size 30μ), per part of fi. The poly(pentabromobenzyl acrylate) and glycidyl group-containing copolymer (α) used in Example 1 were added in the proportions shown in Table 2, triblended in a tumbler, and then melt-kneaded and pelletized.

Furthermore, as in Example 1, A
'STM's No. 1 dumbbell, a square plate, and a combustion test piece were molded, and a combustion test, a tensile test, and a dielectric breakdown test were conducted. The results are shown in Table 2.

As shown in Table 2, even when a filler is added, the composition containing the Grindyl group-containing copolymer of the present invention has excellent heat resistance stability of mechanical properties and electrical properties, and also has a molding residence time of It is clear that these properties are further improved when the length is increased.

Example 11 7 parts by weight of antimony trioxide based on 100 parts by weight of polybutylene terephthalate having a relative viscosity of 171, 2 parts of the poly(pentabromobenyl acrylate) used in Example 1
After mixing 5 parts by weight, 5 parts by weight of glycyl group-containing conjugate (α), and 5 parts by weight of ethylene/buteno-1 conjugate (90/10 molar ratio, MI-3,0) in a Hennel mixer, The mixture was melt-kneaded and pelletized in the same manner as in Example 1, and molded products were created and evaluated.

As a result, the flammability was V-0 for both molding cycles (a) and (b), and the tensile strength and dielectric breakdown voltage were also V-0 for molding cycles (a) and (b).
A) and (b) were both ◎. As can be seen by comparing these results with Example 2, it is clear that the effects of the present invention are synergistically improved by the combined use of the ethylene/buteno-1 copolymer.

Effects of the Present Invention The flame-retardant polyester composition of the present invention synergistically improves the retention stability of mechanical properties and electrical properties, and can also significantly improve heat resistance stability.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] Based on 100 parts by weight of aromatic polyester, ■ 3 to 3 halogen-containing vinyl polymers having the following repeating units:
A flame-retardant polyester composition containing 50 parts by weight and 1 to 20 parts by weight of a glycidyl group-containing copolymer comprising grindyl ester of an α-olefin and an α,β-unsaturated acid. (However, in the formula, R is hydrogen or an alkyl group having 1 to 5 carbon atoms, X is chlorine or bromine, and m is an integer of 1 to 5.)