JPH064755B2 - Flame-retardant aromatic polyester composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a flame-retardant aromatic polyester composition having improved flame retardancy, coloring during residence in molding and improved mechanical properties.

[Conventional technology]

Aromatic polyesters typified by polyethylene terephthalate and polybutylene terephthalate are being widely used for mechanical parts, electric parts, automobile parts and the like by utilizing their excellent characteristics. On the other hand, in addition to the balance of general chemical and physical properties, these industrial materials are strongly required to have flame safety, that is, flame retardancy. At present, it is necessary to impart flame retardancy to aromatic polyesters. It is no exaggeration to say that it has become an indispensable condition in order to expand the use of.

It is well known that an organic bromine compound is used as a flame retardant-imparting agent for an aromatic polyester represented by polybutylene terephthalate (PBT). However, PB
A composition obtained by adding an organic bromine compound and a flame retardant aid such as antimony trioxide to T has the advantage of excellent flame retardancy, but on the other hand, when used in a high temperature atmosphere or during molding. Some studies have been made because they have drawbacks such as coloring and large deterioration of physical properties due to retention. Among them, the method of using a phosphite compound in combination and the method of using a sulfide compound in combination as disclosed in JP-B-59-30184 are relatively excellent methods.

[Problems to be solved by the invention]

However, even when the above-mentioned method is used, there is a problem that the physical properties are deteriorated when the resin is allowed to stay in the molding machine for a long time, and the addition of these causes the molded product to be further colored and the appearance to be significantly deteriorated. .

[Means for solving problems]

Therefore, the inventors of the present invention have made extensive studies in order to improve the above-mentioned drawbacks in the flame retardation of the aromatic polyester with an organic bromine compound and antimony trioxide, and as a result, together with a specific sulfide compound and / or a trivalent organic phosphorus compound, By adding together a specific alkoxysilane compound,
The present invention was found to prevent coloring of a molded product when it is retained in the molding for a long time and to remarkably improve mechanical properties.

That is, the present invention relates to (A) 100 parts by weight of aromatic polyester, (B) 0 to 200 parts by weight of filler, (C) 1 to 60 parts by weight of organic bromine compound (D) 1 to 40 parts by weight of antimony trioxide (E) ) Sulfide compounds represented by the following general formula (I) R ¹ OOC-A ¹ -SA ² -COOR ² (I) (wherein R ¹ and R ² are each a carbon atom number of 3 to 3).
An alkyl group of 0, A ¹ and A ² each have 1 to 1 carbon atoms
0 represents an alkylene group, a substituted alkylene group) and / or a trivalent organic phosphorus compound 0.01 to 10 parts by weight,
And (F) an alkoxysilane in an amount of 0.001 to 5 parts by weight, which relates to a flame-retardant aromatic polyester composition.

The (A) aromatic polyester used in the present invention is a polyester having an aromatic ring in a polymer chain unit, and is an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative).
It is a polymer or copolymer obtained by a condensation reaction containing as a main component.

The aromatic dicarboxylic acid referred to here is terephthalic acid,
Isophthalic acid, orthophthalic acid, 1.5-naphthalenedicarboxylic acid, 2.5-naphthalenedicarboxylic acid, 2.6
-Naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4 ,.
4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenyl isopropylidene dicarboxylic acid, 1.2-bis (phenoxy) ) Ethane-4.4'-dicarboxylic acid, 2.5-anthracene dicarboxylic acid, 2.6-anthracene dicarboxylic acid, 4 *
4 ″ -p-tert-phenylenedicarboxylic acid, 2.5-pyridinedicarboxylic acid and the like, and terephthalic acid can be preferably used.

Two or more kinds of these aromatic dicarboxylic acids may be mixed and used. If it is a small amount, it is possible to mix and use one or more adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acid such as dodecanedioic acid, and alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid together with these aromatic dicarboxylic acids. it can.

As the diol component, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1.
Aliphatic diols such as 3-propanediol, diethylene glycol, and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and the like, and a mixture thereof or the like can be given. One or more long chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like may be copolymerized as long as the amount is small.

Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate,
In addition to polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / Copolymerized polyesters such as decane dicarboxylate may be mentioned. Among these, polybutylene terephthalate and polyethylene terephthalate having well-balanced mechanical properties and moldability can be preferably used.

The aromatic polyester used in the present invention is 0.5%
The o-chlorophenol solution having a relative viscosity of 1.15 to 2.0, particularly 1.3 to 1.85, measured at 25 ° C. is preferable.

As the filler of the component (B) that can be used in the present invention, glass fiber, carbon fiber, aromatic polyamide fiber, potassium titanate fiber, gypsum fiber, brass fiber, stainless fiber, steel fiber, ceramics fiber, boron Whisker fiber, asbestos, mica, talc, silica, calcium carbonate, glass beads, glass flakes,
Examples thereof include fibrous, powdery, granular or plate-like inorganic fillers such as clay, wollastonite and titanium oxide.

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

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

When the filler is added, the amount is 1
It is up to 200 parts by weight per 100 parts by weight, more preferably up to 100 parts by weight.

The organic bromine compound used as the component (C) in the present invention has a bromine atom in the molecule, and means a known organic bromine compound which is usually used as a flame retardant, and particularly has a bromine content of 20% by weight. The above is preferable.
Specifically, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl,
Hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromophenyl ether, bis (pentabromophenoxy) ethane, ethylene bis- (tetrabromophthalimide),
A low molecular weight organic bromine compound such as tetrabromobisphenol A, a brominated polycarbonate (for example, a polycarbonate oligomer produced by using brominated bisphenol A as a raw material), a brominated epoxy compound (for example, a reaction between brominated bisphenol A and epichlorohydrin) Monoepoxy compound obtained by reaction of produced diepoxy compound or brominated phenol with epichlorohydrin), poly (brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, cyanuric chloride and brominated phenol And a halogenated polymer or oligomer such as brominated polystyrene, or a mixture thereof, and brominated polycarbonate is particularly preferably used.

The amount of the organic bromine compound (C) added is 100 parts by weight of the aromatic polyester, and 1 to 60 parts by weight, preferably 5 to 30 parts by weight. If the addition amount is less than 1 part by weight,
The flame retardance is not sufficient, and when it exceeds 60 parts by weight, the physical properties of the composition are deteriorated, which is not preferable.

The antimony trioxide used as the component (D) in the present invention is not particularly limited as long as it is usually used as a flame retardant aid for polyester. Further, zirconium oxide, zinc sulfide, barium sulfate or the like may be used together with antimony trioxide.

The amount of antimony trioxide added in the present invention is 1 to 40 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the aromatic polyester.
It is preferable to add one antimony atom per five.

The sulfide compound as the component (E) used in the present invention is represented by the following general formula (I).

R ¹ OOC-A ¹ -SA ² -COOR ² (I) (In the formula, R ¹ and R ² each have 3 to 30 carbon atoms.
Is an alkyl group, A ¹ and A ² each have 1 to 10 carbon atoms.
The alkylene group and the substituted alkylene group of) are shown as preferred specific examples of the above-mentioned sulfidic compound: dilaurylthiodipropionate, ditridecylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, laurylstearyl Examples include thiodipropionate, dilauryl-β / β'-thiodibutyrate, dimyristyl-β / β'-thiodibutyrate, distearyl-β / β'-thiodibutyrate, among which distearyl thiodipropionate. Most preferred.

Further, the trivalent organic phosphorus compound which is another component constituting the component (E) is represented by the following formula (II).

PR ³ , R ⁴ , R ⁵ (II) where R ³ , R ⁴ , and R ⁵ represent an aliphatic group, an aromatic group, an alicyclic group, an alkoxy group, an alkylthio group, an amino group, or a derivative thereof. , May be the same or different. Also, two or more of R ³ , R ⁴ and R ⁵ may be linked by an arbitrary chemical bond. Further, R ³ , R ⁴ and R ⁵ may contain a trivalent or pentavalent phosphorus atom. That is, two or more phosphorus atoms may be contained in the organic phosphorus compound.
R ³ , R ⁴ and R ⁵ are, for example, methyl, ethyl, propyl, butyl, octyl, decyl, penzyl, phenyl, tolyl,
Naphthyl, cyclohexyl, ethoxy, isodecoxy,
It is a phenoxy or dimethylamino group and may be substituted with a halogen atom such as chlorine or bromine. Preferred examples of the trivalent organic phosphorus compound include triphenylphosphite, triisodecylphosphite, tris (nonylphenyl) phosphite, and the like, and compounds represented by the following formulae.

The addition amount of the sulfide compound represented by the general formula (I) and / or the trivalent organic phosphorus compound is 0.01 to 10 parts by weight with respect to 100 parts by weight of the aromatic polyester,
It is preferably 0.1 to 5 parts by weight. If the amount added is less than 0.01 parts by weight, the retention stability will not be sufficiently improved, while if it exceeds 10 parts by weight, the flame retardant effect will decrease and the physical properties will tend to deteriorate, such being undesirable.

The component (F) used in the present invention has the following general formula (X)
Is an alkoxysilane.

(Here, R ⁶ is an organic group having 1 to 30 carbon atoms, and sulfur,
It may contain oxygen, nitrogen atoms and the like. R ⁷ is a hydrocarbon group having 1 to 15 carbon atoms. n is an integer of 0 to 3) Preferred examples of R ⁶ are methyl group, glycidyl group, amino group and the like. Specific preferred examples of the alkoxysilane of the formula (X) include, for example, dimethyldimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methylsec-octyloxysilane, and methyltriphenoxy. Sisilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane,
Vinyltributoxysilane, tetra-2-ethylhexylsilicate, tetranonylsilicate, tetratridecylsilicate, γ-glycidoxypropyltrimethoxysilane, β- (3.4-epoxycyclohexyl) ethyltrimethoxysilane, γ-methacrylopropyl Trimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, N-β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxy Examples thereof include silane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane and the like. Particularly preferable examples include γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane and the like.

The amount of alkoxysilane added is 10
0.001 to 5 parts by weight, preferably 0.05 to 1 part by weight, based on 0 parts by weight. If the addition amount is less than 0.001 part by weight, the effect of preventing coloration of the molded product is small, while if it exceeds 5 parts by weight, mechanical properties tend to be deteriorated, which is not preferable.

Further, when (G) a glycidyl group-containing copolymer composed of α-olefin and a glycidyl ester of an α-β-unsaturated acid is further added to the composition of the present invention, impact resistance is improved, and further, at the time of residence. It is preferable because it has a feature that the mechanical properties of are further improved.

The α-olefin in the glycidyl group-containing copolymer composed of the α-olefin and a glycidyl ester of an α / β-unsaturated acid is ethylene, propylene, butene-1 or the like, and ethylene is preferably used. Also, α ・ β-
The glycidyl ester of unsaturated acid has the following general formula (In the formula, R ⁸ is a hydrogen atom, a lower alkyl group or a lower alkyl group substituted with a lower alkyl group or a glycidyl ester group), and specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylic acid, Glycidyl itaconate and the like, and glycidyl methacrylate can be preferably used. The copolymerization amount of the α / β-unsaturated glycidyl ester in the glycidyl group-containing copolymer is appropriately in the range of 1 to 50% by weight, particularly 2 to 30% by weight. Further, if it is 40% by weight or less, unsaturated monomers copolymerizable with the above-mentioned copolymers, that is, vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate, acrylic acids such as methyl, ethyl, propyl and butyl. Further, one or more of methacrylic acid ester acid, acrylonitrile, styrene, carbon monoxide and the like 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 monoxide / glycidyl methacrylate copolymer, ethylene. / Glycidyl acrylate copolymer, ethylene / glycidyl acrylate / vinyl acetate copolymer, and the like. Among them, ethylene /
Glycidyl methacrylate copolymer is preferred.

The addition amount of the (G) glycidyl group-containing copolymer in the present invention is 1 to 30 with respect to 100 parts by weight of the aromatic polyester.
Parts by weight, preferably 2 to 10 parts by weight. Addition amount is 1
If the amount is less than parts by weight, the impact properties are not sufficiently improved, and if the amount exceeds 30 parts by weight, the flame retardancy tends to be impaired, and thus neither is preferable.

The composition of the present invention, within the range which does not impair the object of the present invention, includes conventional additives such as an ultraviolet absorber, a lubricant, a release agent, a coloring agent containing a dye and a pigment, an antioxidant, and other thermoplastics. Resin (eg polyethylene, polypropylene, ethylene /
Further, a propylene copolymer, an ethylene / propylene / diene-terpolymer, an ethylene / butene-1 copolymer, an ethylene / vinyl acetate copolymer) and the like can be further contained. 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 an aromatic polyester, an organic bromine compound,
Antimony trioxide, sulfide compound and / or 3
A method of melt-kneading a valent organophosphorus compound and an alkoxysilane and, if necessary, a filler and the like using an extruder.

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

〔Example〕

 Hereinafter, the effects of the present invention will be described in more detail with reference to examples.

Examples 1 to 5 and Comparative Examples 1 to 3 With respect to 100 parts by weight of polybutylene terephthalate having a relative viscosity of 1.48, brominated polycarbonate (produced by Teijin Chemicals Ltd.)
FG-7500) 20 parts by weight, antimony trioxide 7 parts by weight,
30 parts by weight of glass fiber (chop strands), 0.3 parts by weight of dilauryl thiodipropionate, 0.3 parts by weight of triphenyl phosphite and γ-methacryloxypropyltrimethoxysilane (MPTS) were added at the ratios shown in Table 1. After mixing with a ribbon blender, it was melt-kneaded and pelletized at 250 ° C. using a 40 mmφ extruder. Next, the pellets obtained were molded using a 2 ounce screw in-line type injection molding machine set at 250 ° C, the mold temperature was 80 ° C, and the molding cycle (injection time / cooling time / intermediate time) was 10 seconds / 1.
Molded in 5 seconds / 10 seconds (molding cycle (a)), ASTM-1
Dumbbells, 1/2 ″ wide Izod impact test pieces and combustion test pieces (1/16 ″ × 1/2 ″ × 5 ″) were obtained.

Also, molding cycle (injection time / cooling time / intermediate time)
Was changed to 10 seconds / 15 seconds / 40 seconds (molding cycle (b), and other conditions were the same, and two kinds of test pieces were obtained in the same manner as above.

Appearance observation and UL
A vertical burning test according to 94 standard, a tensile test according to ASTM-D638 standard, and an Izod impact test according to ASTM-D256 were performed. The results are shown in Table 1.

From the results shown in Table 1, it is apparent that the composition of the present invention containing the alkoxysilane is significantly improved in coloring and mechanical properties during molding retention.

Examples 6 to 13 and Comparative Example 4 100 parts by weight of polybutylene terephthalate having a relative viscosity of 1.58 was added to brominated polycarbonate (manufactured by Teijin Chemicals Ltd.).
FG-7500) 20 parts by weight, antimony trioxide 7 parts by weight, distearyl thiodipropionate 0.3 parts by weight, the following formula (III)
0.3 parts by weight of the trivalent phosphorus compound and 0.05 parts by weight of the alkoxysilanes shown in Table 2 were added and extruded in the same manner as in Example 1 to evaluate after molding. The results are shown in Table 2.

Trivalent phosphorus compound: From the results shown in Table 2, it is clear that the composition of the present invention containing the alkoxysilane is greatly improved in coloring and mechanical properties during molding retention.

Example 14 100 parts by weight of polybutylene terephthalate having a relative viscosity of 1.48 was added to brominated polycarbonate (produced by Teijin Chemicals Ltd.).
FG-7500) 20 parts by weight, antimony trioxide 7 parts by weight,
30 parts by weight of glass fiber (chop strand), 0.3 part by weight of dilauryl thiodipropionate, 0.3 part by weight of triphenyl phosphite, 0.05 part by weight of γ-methacryloxypropyltrimethoxysilane, and ethylene / glycidyl methacrylate copolymer ( 90/10 weight ratio, melt index = 3) 10 parts by weight were kneaded with a ribbon blender, extruded in the same manner as in Example 1, and evaluated after molding. The appearance is good with no coloration in both molding cycles (a) and (b), and there is no difference in flammability between molding cycles (a) and (b).
It was -0. Also, the tensile strength is 1320k in the molding cycle (a).
g / cm ² , molding cycle (b) 1300 kg / cm ² , Izod impact strength is molding cycle (a) 13 kg cm / cm, molding cycle
(B) It was 12 kgcm / cm.

From the above results, it is clear that the composition of the present invention containing the glycidyl group-containing copolymer has further improved impact resistance and improved molding retention stability.

〔The invention's effect〕

The flame-retardant aromatic polyester composition of the present invention can prevent the coloration of a molded product when it has been molded and retained for a long time, and can also remarkably improve the mechanical properties.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area // (C08L 67/02 69:00)

Claims (1)

[Claims] 1. (A) 100 parts by weight of aromatic polyester (B) 0 to 200 parts by weight of filler (C) 1 to 60 parts by weight of organic bromine compound (D) 1 to 40 parts by weight of antimony trioxide (E) Sulfide compound represented by the following general formula (I): R ¹ OOC-A ¹ -SA ² -COOR ² (I) (wherein R ¹ and R ² are each a carbon atom number of 3 to 30).
Is an alkyl group, A ¹ and A ² each have 1 to 10 carbon atoms.
Of alkylene group, substituted alkylene group) and / or trivalent organic phosphorus compound 0.01 to 10 parts by weight,
And (F) 0.001 to 5 parts by weight of alkoxysilane, which is a flame-retardant aromatic polyester composition.