JPS61203164A - Flame-retardant aromatic polyester composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. having excellent flame retardance and mechanical properties and being hardly colored during residence in a molding machine, containing an arom. polyester, a filler, an organobromine compd., Sb2O3, a sulfide compd. and an alkoxysilane. CONSTITUTION:100pts. (by weight; the same applies hereinbelow) arom. polyester (e.g. polybutylene terephthalate) having a relative viscosity of 1.15-2.0 (in 0.5% o-chlorophenol soln. at 25 deg.C), 0-200pts. fibrous, powdered, particulate or lamellar inorg. filler (e.g. glass fiber), 1-60pts. organobromine compd. having a bromine content of 20wt% or above, 1-40pts. Sb2O3, 0.01-10pts. sulfide compd. of the formula [wherein R<1>, R<2> are each a 3-30C alkyl; A<1>, A<2> are each a 1-10C (substd.)alkylene] and/or trivalent organophosphorous compd. (e.g. triphenyl phosphite), 0.001-5pts. alkoxysilane (e.g. methyltrimethoxysilane) and optionally 1-30pts. glycidyl group-contg. copolymer are blended together. The mixture is melt-kneaded.

Description

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

[Conventional technology]

Aromatic polyesters such as polyethylene terephthalate, polybutylene terephthalate, and phthalate have excellent properties. Applications are being expanded to include mechanical parts, electrical parts, and automobile parts. 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. It is no exaggeration to say that this is an essential condition for expanding the uses of polyester.

It is well known that an organic bromine compound is used as a flame retardant imparting agent to aromatic polyesters represented by polybutylene terephthalate (PBT). However, a composition prepared by adding an organic bromine compound and a flame retardant aid such as antimony trioxide to PBT has the advantage of excellent flame retardancy, but when used in a high temperature atmosphere, Several studies have been made because they have drawbacks such as coloring and significant deterioration of physical properties due to retention during molding.

Among these, the method of using a phosphite compound in combination and the method of using a sulfide compound in combination as shown in Japanese Patent Publication No. 59-40184 are relatively excellent methods.

[Problem that the invention seeks to solve]

However, even if the above method is used, physical properties will deteriorate if left in the molding machine for a long time. There was a problem in that the addition of this compound increased the coloring of the molded product, significantly degrading its appearance.

, [Means for Solving the Problems] The present inventors have conducted intensive studies to improve the above-mentioned drawbacks in making aromatic polyester flame retardant using organic bromine compounds and antimony trioxide. and/or by adding a specific alkoxysilane compound together with a trivalent organic phosphorus compound,
The present invention has been accomplished by discovering that it is possible to prevent coloring of a molded product due to long retention in molding, and to significantly improve mechanical properties.

That is, the present invention provides (A) per 100 parts by weight of aromatic polyester (B)
Filler 0 to 200 parts by weight (C) Organobromine compound 1 to 60 parts by weight (D) Antimony trioxide 1 to 40 parts by weight (E) The following general formula (
I) Sulfide compound R1OOC-A'-8-A2-00OR"
(I) (in the formula, R1 and R2 each represent an alkyl group having 3 to 30 carbon atoms, and AI and A2 each represent an alkylene group or substituted alkylene group having 1 to 10 carbon atoms) and/or relates to a flame-retardant aromatic polyester composition characterized by containing 0.01 to 10 parts by weight of a trivalent organic phosphorus compound and 0.001 to 11 parts by weight of (F) an alkoxysilane.

The aromatic polyester (A) used in the present invention has an aromatic ring? A polymeric copolymer having a polyester in the chain unit of the polymer obtained by a condensation reaction containing an aromatic dicarboxylic acid (or its ester-forming derivative) and a 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, 1,5-naphthalene dicarboxylic acid, 2-5-naphthalene dicarboxylic acid, 2,6
-naphthalene dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,8-biphenyldicarboxylic acid, 4,4'
-Diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 4,4'-diphenylisopropylidene dicarboxylic acid, 1,2-bis(phenoxy)ethane-
4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4-
These include p-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 it is a small amount, one or more types of aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, and ring group dicarboxylic acids such as cyclohexanedicarboxylic acid can be used in combination with these aromatic dicarboxylic acids. .

In addition, diol components include ethylene glycol, propylene glycol, butylene gelicol, hexylene glycol, neopentyl glycol, 2-methyl-1.
Examples include aliphatic diols such as 3-propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexane dimetatool, t-k, 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, polyhexylene terephthalate,
Polyethylene naphthalate, polybutylene naphthalate, polyethylene-1-2-bis(phenoxy)ethane-
In addition to 4,4'-dicarboxylate, copolymerized polyesters such as polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate, polybutylene terephthalate/decanedicarboxylate, etc. can be mentioned. Among these, mechanical properties,
Polybutylene terephthalate and polyethylene terephthalate, which have well-balanced moldability, are preferably used.

Aromatic atomizer used in the present invention, 0.5
% 0-chlorophenol solution t Those having a relative viscosity of 1.15 to 2.0, particularly preferably 1.3 to 1.85, as measured at 25°C.

The fillers of component (B) that can be used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, potassium titanate fibers, gypsum fibers, brass fibers,
Fibrous, powder, granular or plate-like materials such as stainless fiber, steel fiber, ceramic fiber, poron whisker fiber, asbestos, mica, talc, silica, calcium carbonate, glass peas, glass flakes, clay, wollastenite, titanium oxide, etc. Examples include inorganic fillers.

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

Among the photonic agents 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; for example, it can be selected from long fiber types, short fiber types, chopped strands, milled fibers, etc. Furthermore, the glass fibers may be coated or bundled with a thermoplastic resin such as ethylene/vinyl acetate copolymer, a thermosetting resin such as an egoxy resin, or may be coated with 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 1% of the aromatic polyester
The amount is up to 200 parts by weight, more preferably up to 100 parts by weight, per 00 parts by weight. The organic bromine compound used as component (C) in the present invention has a bromine atom in the molecule, and usually has a bromine atom in the molecule. It refers to a known organic bromine compound used as a fuel, and those having a bromine content of 20% by weight or more are particularly preferred.

Specifically, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl
Hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)
Ethane, ethylene bis-(tetrabromophthalimide)
, low molecular weight organic bromine compounds such as tetrabromobisphenol A, brominated polycarbonates (e.g. polycarbonate oligomers produced from brominated bisphenol A), brominated epoxy compounds (e.g. produced by the reaction of brominated bisphenol A and epichlorohydrin), Jepoxy compounds and brominated phenols.

monoepoxy compound obtained by reaction with chlorohydrin), poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A1
Examples include condensates of cyanuric chloride and brominated phenol, halogenated polymers and oligomers such as brominated polystyrene, and mixtures thereof, with brominated polycarbonate being particularly preferred.

The amount of these organic bromine compounds (C) added is 1 to 60 parts by weight, preferably 5 to 30 parts by weight, per 100 parts by weight of the aromatic polyester. If the amount added is less than 1 part by weight,
Flame retardancy is not sufficient, and if it exceeds 60 parts by weight, the physical properties of the composition deteriorate, which is not preferable.

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

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

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

R'ooamA'-3-A"-000R2(I) (In the formula, R1 and R2 are each an alkyl group having 3 to 30 carbon atoms. AI and A2 are each an alkyl group having 1 to 1 carbon atoms.
0 alkylene group, substituted alkylene group) Preferred specific examples of the above sulfide compounds include dilaurylthiodipropionate, ditridecylthiodipropionate, simyristylthiodipropionate, distearylthiodipropionate, and lauryl. These include stearyl thiodipropionate, dilauryl-β-β′-thiodibutyrate, cimilistyl-β・β′-thiodibutyrate, and distearyl-β・β′-thiodibutyrate, among which distearyl thiodipropionate is most preferred.

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

PR', R4, R' (II) where R3
, R4, and R5 are aliphatic groups, aromatic groups, aliphatic group 11 groups, alkoxy groups, alkylthio groups, amide groups, etc., or derivatives thereof? may be the same or different.

Two or more of R3, R4, and HM may be connected by any chemical bond. Furthermore, are R3, R4, and R's trivalent or pentavalent phosphorus atoms? May contain. That is, two or more phosphorus atoms may be contained in the organic phosphorus compound. R3, R4, R5 are, for example, methyl, ethyl,
Propyl, butyl, octyl, decyl, benzyl, phenyl, tolyl, naptyl, cyclohexyl, ethoxy,
It is an isodekoxy, phenoxy, dimethylamino group, etc., and may be substituted with a halogen atom such as chlorine or bromine.

Preferred examples of trivalent organic phosphorus compounds include triphenyl phosphite, triisodecyl phosphite, tris(nonylphenyl) phosphite, and compounds represented by the following formulas.

Oh.

Oh.

irises Oh.

OH3 The amount of the sulfide compound and/or octavalent organic phosphorus compound represented by the above general formula (I) is 0.01 to 10 parts by weight, preferably 0.01 to 10 parts by weight, per 100 parts by weight of the aromatic polyester. .1 to 5 parts by weight. Addition! If i is less than 0.01 part by weight, the improvement in retention stability will not be sufficient, while if it exceeds 10 parts by weight, the flame retardant effect will decrease and the physical properties will tend to deteriorate, which is not preferred.

As the component (F) used in the present invention, the following general formula (X)
This is an alkoxysilane represented by

R'11L-8:L+OR')4-:n
(X) (Here, R6 is an organic group having 1 to 80 carbon atoms, and may contain sulfur, oxygen, nitrogen atoms, etc. R? is a hydrocarbon group having 1 to 15 carbon atoms. (n is an integer of θ to 8) Preferred examples of R6 include a methyl group,
These include glycidyl groups and amine groups. Preferred specific examples of the alkoxysilane of formula (X) include dimethyldimethoxysilane, -methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyl 5ea-octyloxysilane, and methyltrifoxysilane. enoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
Vinyltriethoxysilane, vinyltriptoxysilane, tetra2-ethylhexylsilicate, tetranonylsilicate, tetratridecylsilicate, γ-glycidoxyprobyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrisilicate Methoxysilane, γ
-methacrylobrovir trimethoxysilane, γ-(2-
aminoethyl)aminopropyltrimethoxysilane, γ
-(2-aminoethyl)aminopropylmethyldimethoxysilane, N-β(N-vinylbenzylaminoethyl)
-γ-aminopropyltrimethoxysilane and γ-anilinopropyltrimethoxysilane. Particularly preferred examples include γ-methacryloxypropyltrimethoxysilane, r-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, and dimethyldimethoxysilane.

The amount of alkoxysilane added is 10% of the aromatic polyester.
The amount is 0.001 to 5 parts by weight, preferably 0.05 to 1 part by weight. The amount added is Q. 0
If the amount is less than 1 part by weight, the effect of preventing coloring of the molded product will be small, while if it exceeds 5 parts by weight, the mechanical properties will tend to deteriorate, which is not preferable.

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

The α-olefin in the glycidyl group-containing copolymer composed of the α-olefin and the glycidyl ester of an α/β-unsaturated acid is ethylene, propylene, butene-1, etc., and ethylene is preferably used. Also, α・β−
A glycidyl ester of an unsaturated acid is a compound represented by the following general formula (wherein R8 is a hydrogen atom, a lower alkyl group, or a lower alkyl group substituted with a glycidyl ester group), and specifically: These include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate, among which glycidyl methacrylate is preferably used. The copolymerized amount of glycidyl ester of α/β-unsaturated acid in the glycidyl group-containing copolymer is suitably in the range of 1 to 50% by weight, particularly 2 to 30% by weight. Furthermore, if it is 40% by weight or less, unsaturated monomers copolymerizable with the above copolymers, such as vinyl ethers, vinyl esters such as vinyl acetate and vinyl propionate, and acrylic acids such as methyl, ethyl, propyl, butyl, etc. Also, one or more types of methacrylic esters, acrylonitrile, styrene, carbon oxide, 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. /glycidyl acrylate copolymer,
Examples include ethylene/glycidyl acrylate/vinyl acetate copolymer, among which ethylene/glycidyl methacrylate copolymer is preferred from the viewpoint of heat resistance.

In the present invention, the amount of the glycidyl group-containing copolymer (G) added is 1 to 30 parts by weight per 100 parts by weight of the aromatic polyester.
Parts by weight, preferably 2 to 10 parts by weight. Addition amount is 1
If it is less than 30 parts by weight, the impact properties will not be improved enough. Exceeding this value tends to impair flame retardancy, so both are unfavorable.

The compositions of the present invention may contain conventional additives such as ultraviolet absorbers, lubricants, mold release agents, colorants including dyes and pigments, antioxidants, other thermoplastics, etc., to the extent that the objects of the present invention are not impaired. Resin (e.g. polyethylene, polypropylene, ethylene/
It may further contain a propylene copolymer, ethylene/propylene/genter 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 uses an aromatic polyester, an organic bromine compound, antimony trioxide, a sulfide compound and/or a trivalent organic phosphorous compound, and an alkoxysilane, and optionally Depending on the method, a method of melting and 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 properties.

〔Example〕

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

・Examples 1 to 5, Comparative Examples 1 to 8 Polybutylene lentiphthalate with a relative viscosity of 1.48) 100
Based on parts by weight, brominated polycarbonate (Teijin Kasei)
Co., Ltd. pa-75ffO) 20 parts by weight, antimony trioxide 7 parts by weight, glass fiber (chopped strand) a
o weight W, dilauryl thiodipropionate o, a weight f
i part, 0.3 part by weight of triphenylphosphite and γ
-Methacryloxypropyltrimethoxysilane (MPT
S) i Add the ingredients shown in Table 1 in the proportions shown in Table 1, mix with a ribbon blender, and then mix using a 40 mm diameter extruder. melt-kneaded and pelletized at 250°C. Next, the obtained pellets ft250
2oz screw in-line injection molding machine set at ℃? Using a mold temperature of 80 ° C, molding cycle (injection time / cooling time / intermediate time) 10 seconds / 15 seconds / 10 seconds (molding cycle (a)), ASTM-1 dumbbell, 1/2' Width Izot impact test piece and combustion test piece (
I/16' x 1/2' x 5') were obtained.

Also, molding cycle (injection time/cooling time/intermediate time)
Two 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.

The appearance of these test pieces was observed, and the UL
Vertical combustion test according to 94 standard, ASTM-D
Tensile test according to 618 standard, ASTM-D25
An Izot impact test was conducted in accordance with 6. These results are shown in Table 1.

From the results in Table 1, it is clear that compositions of the invention containing alkoxysilanes have significantly improved coloration and mechanical properties during mold retention.

・Examples 6 to 18, Comparative Example 4 Polybutylene lentiphthalate with a relative viscosity of 1.58) 100
Based on parts by weight, brominated polycarbonate (Kijin Kasei)
Co., Ltd. ya-7500) 20 parts by weight, tertiary antimony 7 parts by weight, distearyl thiodipropionate 0.3
Parts by weight, 0.8 parts by weight of an octavalent phosphorus compound of the formula below and 0.05 parts by weight of each alkoxysilane shown in Table 2 were added, extruded in the same manner as in Example 1, and evaluated after molding. I did this. These results are shown in Table 2.

Trivalent phosphorus compound: From the results in Table 2, it is clear that the compositions of the present invention containing alkoxysilanes have significantly improved coloration and mechanical properties during molding retention.

・Example 14 Polybutylene lenticule (relative viscosity 1.48) 100
Based on parts by weight, brominated polycarbonate (Kijin Kasei)
Co., Ltd. F, o-75oO) 2 .

Heavy parts, 7 parts by weight of antimony trioxide, 30 parts by weight of glass fiber (chopped strand), 11 g by weight of 0.8 parts (dilaurylthiodiprobione), 0 parts by weight of triphenyl phosphite.
．． After kneading 8 parts by weight, 0.05 weight [1 part of γ-methacryloxypropyltrimethoxysilane], and 10 parts of ethylene/glycidyl methacrylate copolymer (90/1G weight ratio, melt index -8) in a ribbon blender, It was extruded and evaluated after molding in the same manner as in Example 1. The appearance is good with no coloring in both molding cycles (a) and (b), and the flammability is also good as in molding cycles (a) and (b).
There is no difference and it is v-0. Also, the tensile strength is 1820pc9/'' at molding cycle (A), 13 o o kg/a' at molding cycle (B), and the Izot impact strength is 18≠φm1 at molding cycle (A), 12 kgcm at molding cycle (C). /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 molding retention stability.

C Effects of the Invention The flame-retardant aromatic polyester composition of the present invention can prevent coloring of molded products when molded for a long time and can also significantly improve mechanical properties.

Claims (1)

Scope of Claims (A) Per 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 ) A sulfide compound R^1OOC-A^1-S-A^2-COOR^2 (
I) (However, in the formula, R^1 and R^2 are each an alkyl group having 3 to 30 carbon atoms, and A^1 and A^2 are each an alkylene group or substituted alkylene group having 1 to 10 carbon atoms. ) and/or 0.01 to 10 parts by weight of a trivalent organic phosphorus compound, and 0.001 to 5 parts by weight of (F) an alkoxysilane. thing.