JPH0562141B2 - - Google Patents

Description

[Detailed description of the invention]

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. Thermoplastic polyesters, represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, etc., are being used for mechanical parts, electrical parts, automobile parts, etc. by taking advantage of their excellent properties. be. On the other hand, these industrial materials are strongly required to have safety against flames, that is, flame retardancy, in addition to the balance of general compounds and physical properties. It is no exaggeration to say that this will determine the possibility of expanding the uses of plastic polyester. The use of cyanuric acid ester compounds of halogenated bisphenols as a flame retardant imparting agent to aromatic polyesters such as polybutylene terephthalate is disclosed, for example, in JP-A-54-11158;
This is well known as proposed in Japanese Patent Application Laid-Open No. 55-65250, Japanese Patent Application Laid-Open No. 57-96040, etc.
However, when aromatic polyester is made flame-retardant using this method, there is a problem in that the mechanical and electrical properties deteriorate significantly when the aromatic polyester remains in the molding machine. It also had the disadvantage of being significant when treated. Therefore, the present inventors have conducted intensive studies to improve the above-mentioned drawbacks in flame retardant aromatic polyesters using cyanuric acid ester compound flame retardants of halogenated bisphenols. The inventors have discovered that by using a compound flame retardant and a specific sulfide compound in combination, the retention stability and heat stability of mechanical properties and electrical properties can be significantly improved, and the present invention has been achieved. That is, the present invention provides 100 parts by weight of aromatic polyester, (A) 3 to 50 parts by weight of a cyanuric acid ester compound of halogenated bisphenols, (B) 1 to 20 parts by weight of antimony trioxide, and (C) the following: A flame-retardant polyester composition containing 0.01 to 3 parts by weight of a sulfide compound represented by the general formula (), and a flame-retardant polyester composition further containing 0.1 to 3 parts by weight of a polyepoxy compound.
The present invention provides a composition containing 10 parts by weight. R ¹ OOC−Al ¹ −S−Al ² −COOR ² ...() (In the formula, R ¹ and R ² are each an alkyl group having 3 to 30 carbon atoms, and Al ¹ and Al ² are each a carbon (Indicates an alkylene group or substituted alkylene group having 1 to 10 atoms.) The aromatic polyester used in the present invention is a polyester having an aromatic ring in the chain unit of the polymer, and is a polyester having an aromatic dicarboxylic acid (or its ester forming property) derivative) A polymer or copolymer obtained by a condensation reaction containing diol (or its ester-forming derivative) as a main component. 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'-biphenyl dicarboxylic acid, 3,3'-biphenyl dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl sulfone 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″-p-terphenylenedicarboxylic acid,
These include 2,5-pyridinedicarboxylic acid, and terephthalic acid is preferably used. Two or more of these aromatic dicarboxylic acids may be used in combination. If the amount is small, one or more 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. can. In addition, diol components include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol,
Examples include aliphatic diols such as diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and mixtures thereof. In addition, one or more types of long-chain diols having a molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1,3-propylene glycol, and polytetramethylene glycol, may be copolymerized in a small amount. Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polyethylene terephthalate.
In addition to 1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, copolymerized polyesters such as polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate, polybutylene terephthalate/decanedicarboxylate, etc. can be mentioned. Among these, polybutylene terephthalate and polyethylene terephthalate, which have well-balanced mechanical properties and moldability, can be preferably used. The aromatic polyester used in the present invention is
It is preferable that the relative viscosity of a 0.5% o-chlorophenol solution measured at 25° C. is 1.15 to 2.0, particularly 1.3 to 1.85. The cyanuric acid ester compound of halogenated bisphenols used as a flame retardant in the present invention is:
Usually, it is a compound obtained by reacting a halogenated cyanuric acid, preferably cyanuric chloride, with a halogenated bisphenol, and is represented by the following general formula. (In the above formula (), Ar ¹ to ^{Ar 4} are each a monovalent aromatic group, and include a halogen, a lower alkyl group,
It may be substituted with a halogenated lower alkyl group or the like. Ar is a divalent aromatic group substituted with halogen, and may be further substituted with a lower alkyl group, a halogenated lower alkyl group, or the like. n
indicates the degree of polymerization. ) Preferred examples of Ar ¹ to ^{Ar 4} include substituents of formula (). (In the above formula (), R ³ represents a lower alkyl group or a halogenated lower alkyl group, and X represents bromine or chlorine. k and l are each an integer from 0 to 5, and k+l≦5.) Ar Specific examples of ¹ to Ar ⁴ include phenyl, monobromo phenyl, tribromo phenyl, pentabromo phenyl, monochloro phenyl, trichloro phenyl, pentachloro phenyl, mono bromo tolyl, tribromo tolyl, mono chloro tolyl, and tribromo phenyl. Bromotolyl, dibromopropylphenyl and the like are preferred, and tribromophenyl, pentabromophenyl, trichlorophenyl, pentachlorophenyl and the like are particularly preferred. Preferred examples of Ar include substituents of formula (). (In the above formula (), R ⁴ and R ⁵ each represent a lower alkyl group or a halogenated lower alkyl group, and Y
is a lower alkylene group, a halogenated lower alkylene group, an alkylidene group, -SO ₂ -, -SO-, -S-,
-O-, -CO-, a chemical bond, and Z ¹ and Z ² each represent bromine or chlorine. p, q, r, s are each 0
is an integer of ~4, p+q+r+s≦8 and r+
It satisfies s≧2. ) Ar is a residue of halogenated bisphenol used during flame retardant synthesis. A preferred example of such bisphenol is 2,2-bis(3
-chloro-4-hydroxyphenyl)propane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2
-bis(3,5-dibromo-4-hydroxyphenyl)propane, bis(3-chloro-4-hydroxyphenyl)sulfone, bis(3,5-dichloro-4-hydroxyphenyl)sulfone, bis(3-dichloro-4-hydroxyphenyl)sulfone, -bromo-4-hydroxyphenyl) sulfone, bis(3,5-dibromo-4-hydroxyphenyl) sulfone, bis(3,5-dichloro-4
-hydroxyphenyl)methane, bis(3,5-
dibrom-4-hydroxyphenyl)methane, among others 2,2-bis(3,5-dibrom-4-hydroxyphenyl)propane and bis(3,5-dibrom-4-hydroxyphenyl)
Sulfones are particularly preferably used. The degree of polymerization n is preferably in the range of 1 to 50, more preferably in the range of 3 to 20. Further, the halogen content in the cyanuric acid ester compound of halogenated bisphenols is preferably 30% by weight, especially 50% by weight or more when the halogen is bromine, and 20% by weight, especially when the halogen is chlorine.
40% by weight or more is preferred. Furthermore, when both bromine and chlorine are included as halogens, the amount thereof is preferably at least a value approximately intermediate between the above-mentioned bromine and chlorine contents. The amount of the cyanuric acid ester compound of halogenated bisphenols added is 3 to 50 parts by weight, preferably 5 to 20 parts by weight. If the amount added is less than 3 parts by weight, imparting flame retardance will not be sufficient, and if it exceeds 50 parts by weight, the mechanical properties of the aromatic polyester will be impaired, which is not preferable. The flame retardant effect of cyanuric acid ester compounds of halogenated bisphenols is significantly enhanced by the combined addition of antimony trioxide. The amount added is 1 to 20 parts by weight per 100 parts by weight of aromatic polyester.
The amount is preferably 3 to 15 parts by weight; less than 1 part by weight will not provide sufficient flame retardancy, and more than 20 parts by weight will impair the mechanical properties of the aromatic polyester. More preferably, the halogenated bisphenols are added in a ratio of 1 to 5 halogen atoms in the cyanuric acid ester compound in the antimony trioxide. At the same time, other flame retardant aids such as boron oxide, zirconium oxide, iron oxide, etc. may be used in combination. A composition comprising an aromatic polyester containing a cyanuric acid ester compound of a halogenated bisphenol and antimony trioxide has excellent flame retardancy. Addition of the compound further improves the mechanical properties and electrical properties, and further improves the retention stability and thermal stability of the mechanical properties and electrical properties. The sulfide compound used in the present invention is represented by the following general formula (). R ¹ OOC−Al ¹ −S−Al ² −COOR ² ...() (In the formula, R ¹ and R ² are each an alkyl group having 3 to 30 carbon atoms, and Al ¹ and Al ² are each a carbon (Indicates an alkylene group or substituted alkylene group having 1 to 10 atoms.) Preferred specific examples of the above sulfide compounds include dilaurylthiodipropionate, ditridecylthiodipropionate, dimyristylthiodipropionate, and distearyl. Thiodipropionate, laurylstearylthiodipropionate, dilauryl-β,β′-thiodibutyrate, dimyristyl-β,β′-thiodibutyrate, distearyl-β,β′-thiodibutyrate, etc.
Among them, distearyl thiodipropionate is most preferred. The amount of the sulfide compound used in the present invention is selected from the range of 0.01 to 3 parts by weight, particularly 0.05 to 0.5 parts by weight, based on 100 parts by weight of the aromatic polyester. If the amount of the sulfide compound added is less than 0.01 part by weight, the retention stability and heat resistance stability of mechanical properties and electrical properties will not be sufficiently improved, and if the amount is 3 parts by weight or more, the mechanical properties of the composition will deteriorate. On the contrary, it decreases, which is not desirable. In the present invention, if a polyvalent epoxy compound is used in combination, retention stability of mechanical properties and electrical properties can be improved.
Heat resistance stability can be improved. Such polyvalent epoxy compounds are compounds having at least two epoxy groups in the molecule, and include, for example, bisphenol-type epoxy compounds obtained by reacting bisphenol A and epichlorohydrin in various ratios, novolak resins, and Novolac type epoxy compounds obtained from epichlorohydrin, polyglycidyl esters obtained from polycarboxylic acids and epichlorohydrin, alicyclic epoxy compounds obtained from alicyclic compounds (e.g. dicyclopentadiene), aliphatic compounds having an alcoholic hydroxyl group compounds (e.g. butanediol,
Examples include glycidyl ethers obtained from glycerin, polyalkylene glycol, etc.) and epichlorohydrin, and epoxidized polybutadiene. Suitable examples of these epoxy compounds include polyethylene glycol diglycidyl ether,
Examples include polypropylene glycol diglycidyl ether, polyglycidyl ester represented by the following general formula (), and bisphenol type epoxy compounds represented by the following general formula (). (However, in the formula, R ⁶ represents an alkylene group having 4 to 40 carbon atoms, a phenylene group, a partially hydrogenated phenylene group, or a cyclohexylene group.) (However, in the formula, m is a number from 0 to 20.) Specific examples of the polyvalent epoxy compound of formula () include hexahydrophthalic acid diglycidyl ester,
Examples include tetrahydrophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, and terephthalic acid diglycidyl ester. When a polyvalent epoxy compound is used in the present invention, the amount added is preferably 0.1 parts by weight or more and 10 parts by weight or less per 100 parts by weight of aromatic polyester. Furthermore, the inorganic filler that can be added in the present invention may be in any form such as fibrous, plate-like, or granular. Examples include glass fiber, carbon fiber, metal fiber, glass beads, glass flakes, mica, wollastenite, talc, and clay. , asbestos, sericite, calcium carbonate, magnesium carbonate, barium sulfate, titanium oxide, etc. Two or more of these may be used in combination. Among the inorganic fillers, glass fiber can be preferably used. As the glass fiber, ordinary tipped strands or roving types are used, but tipped strands with a length of 3 to 6 mm are preferred from the viewpoint of ease of handling and surface gloss of the molded product. In addition, glass fiber is silane-based,
Particularly preferably used are those treated with ordinary coupling agents such as titanium-based coupling agents, epoxy resins, ordinary binding agents such as vinyl acetate, etc. The amount of inorganic filler added is 100% of the aromatic polyester.
It is 0 to 100 parts by weight. The heat stability of the composition of the present invention is further improved by the addition of a stabilizer. These stabilizers include phosphorus compounds such as phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonic acid, and polyphosphonates;
A hindered phenol compound or the like can be used. The amount of these stabilizers added is generally preferably 0.01 to 3 parts by weight per 100 parts by weight of the aromatic polyester. The compositions of the present invention may contain conventional additives such as ultraviolet absorbers, lubricants, mold release agents, colorants including dyes and pigments, other thermoplastic resins (e.g. polyethylene , polypropylene, ethylene/propylene copolymer, ethylene/propylene/diene terpolymer, ethylene/butene-1 copolymer, ethylene/vinyl acetate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate/methacrylate acid glycidyl copolymer, etc.). 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,
Examples include a method in which four components, a cyanurate ester compound of halogenated bisphenols, antimony trioxide, and a sulfide compound, are melt-kneaded using an extruder. When adding inorganic fillers,
It is preferable to melt and knead the above four components simultaneously using an extruder. 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. The effects of the present invention will be explained in further detail with reference to Examples below. Examples 1 to 9, Comparative Examples 1 to 9 Polybutylene terephthalate with a relative viscosity of 1.67
Add the following flame retardant (α), (β) or (γ), 7 parts by weight of antimony trioxide and the following sulfide compounds (A) to (C) to 100 parts by weight in the proportions shown in Table 1, After mixing with a Henschel mixer, the mixture was melt-kneaded and pelletized at 250°C using a 40 mmΦ extruder. Next, the obtained pellets were heated to 250°C.
Using a screw-in-line injection molding machine with a mold temperature of 80°C and a molding cycle (injection time/
Cooling time/intermediate time) 10 seconds/15 seconds/10 seconds (molding cycle (a)), ASTM-1 dumbbell,
A square plate (80 mm x 80 mm x 1 mm) and a combustion test piece (1/16" x 1/2" x 5") were obtained. Also, the molding cycle (injection time / cooling time / intermediate time) was changed to 10 seconds / 15 seconds/40 seconds (molding cycle (b))
Three types of test pieces were obtained in the same manner as above, except that the other conditions were the same. Vertical combustion tests were conducted using combustion test pieces in accordance with the UL94 standard. In addition, we conducted a tensile test using a tensile test piece according to the ASTM-D638 standard, and a dielectric breakdown test using a square plate according to the UL standard. I asked for it. These results are shown in Table 1. Flame retardant α: A flame retardant having the following structure obtained by reacting cyanuric chloride, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, and tribromophere. n is about 7 β: A flame retardant having the following structure obtained from cyanuric chloride, bis(4-hydroxyphenyl) sulfone and tribromophenol. n is about 5 γ: flame retardant having the following structure (n is about 4) Sulfide compound A: distearylthiodipropionate S (CH ₂ CH ₂ COOC ₁₈ H ₃₇ ) ₂ B: dilauryl thiodipropionate S (CH ₂ CH ₂ COOC ₁₂ H ₂₅ ) ₂ C : Distearyl-β,β′-thiodibutyrate

[Table] As shown in Table 1, compositions containing the sulfide compound of the present invention have better mechanical and electrical properties than compositions containing no sulfide compound and compositions containing other sulfide compounds. It is clear that it has excellent heat resistance stability and that these properties are further improved when the molding residence time is increased. Examples 10-15, Comparative Examples 10-13 Polybutylene terephthalate with relative viscosity 1.49
7 parts by weight of antimony trioxide per 100 parts by weight,
50 parts by weight of glass fiber (epoxy resin binder, 3 mm long chopped strand), the flame retardant (α) used in Example 1 and the sulfide compound were added in the proportions shown in Table 2, and after dry blending in a tumbler, The mixture was melt-kneaded and pelletized. Furthermore, as in Example 1, ASTM
A No. 1 dumbbell, a square plate, and a combustion test piece were molded and subjected to a vertical combustion test, a tensile test, and a dielectric breakdown test. The results are shown in Table 2.

[Table] As shown in Table 2, the compound containing the phosphite compound of the present invention has excellent heat resistance stability in mechanical properties and electrical properties even when glass fiber is added, and when the molding residence time is long, It is clear that the characteristics of Examples 16-18, Comparative Examples 14-19 Polyethylene terephthalate (PET) with relative viscosity 1.35 as aromatic polyester, relative viscosity 1.65
polybutylene terephthalate/dodecanedioic acid (90/10 molar ratio) copolymer (PBT/D), polybutylene terephthalate/isophthalate (90/10 molar ratio) copolymer (PBT/I) with a relative viscosity of 1.77.
20 parts by weight of the flame retardant (α) used in Example 1, 7 parts by weight of antimony trioxide, 0.3 parts by weight of sulfide compound (A) and glass fiber (epoxy resin binder, 3 mm
50 parts by weight of long, chopped strands) were dry blended, melt-kneaded and pelletized in the same manner as in Example 1, and then injection molded to produce ASTM No. 1 dumbbells, square plates, and combustion test pieces. However, in the case of PET, the melt-kneading and molding temperatures were set at 290°C, and the mold temperature was set at 130°C. Table 3 shows the evaluation results for the molded products.

[Table] Based on the results in Table 3, as aromatic polyester
PBT also applies when using PET, PBT/D, and PBT/I.
It can be seen that the same effect is produced. Examples 19-22, Comparative Examples 20-22 Polybutylene terephthalate with a relative viscosity of 1.61
To 100 parts by weight, 20 parts by weight of the flame retardant (α) used in Example 1, 7 parts by weight of antimony trioxide, 0.05 parts by weight of sulfide compound (A), and the polyvalent epoxy compound shown in Table 4 were dried. After blending, the mixture was melt-kneaded and pelletized in the same manner as in Example 1, and then injection molded to produce ASTM-1 dumbbells, square plates, and combustion test pieces. The evaluation results of the molded product are shown in the fourth
Shown in the table.

【table】

[Table] From the results in Table 4, it is clear that when the composition of the present invention contains a polyvalent epoxy compound, the heat resistance stability and retention stability of mechanical properties and electrical properties are further improved.

Claims (1)

[Claims] 1. Based on 100 parts by weight of aromatic polyester, (A) 3 to 50 parts by weight of a cyanuric acid ester compound of halogenated bisphenols, (B) 1 to 20 parts by weight of antimony trioxide, and (C) A flame-retardant polyester composition containing 0.01 to 3 parts by weight of a sulfide compound represented by the following general formula (). R ¹ OOC−Al ¹ −S−Al ² −COOR ² ...() (In the formula, R ¹ and R ² are each an alkyl group having 3 to 30 carbon atoms, and Al ¹ and Al ² are each a carbon 2. The composition according to claim 1, which contains 0.1 to 10 parts by weight of a polyvalent epoxy compound to 100 parts by weight of aromatic polyester. thing.