JPS60202149A - Flame-retardant polyester composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant polyester composition having excellent mechanical properties, electrical properties, retention stability, and heat resistance stability.

Thermoplastic polyesters, represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polychlorohexane dimethylene terephthalate, etc., are used in mechanical parts, electrical parts, automobile parts, etc. by taking advantage of their excellent properties. It's coming. 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 thermoplastic polyester.

Polybutylene lentil reflex clay! The use of cyanuric acid ester compounds of halogenated bisphenols as a flame retardant imparting agent to aromatic polyesters represented by - is disclosed, for example, in JP-A-54-11158 and JP-A-55-65.
This is well known as proposed in Japanese Patent Application Laid-open No. 250, Japanese Patent Application Laid-open No. 57-96040, and the like. 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 it remains in a molding machine. It also had the disadvantage of being significant in some cases.

Therefore, the present inventors have conducted intensive studies to improve the above-mentioned drawbacks in flame retardant aromatic polyester using a flame retardant based on a noanuric acid ester compound of halogenated bisphenols. The inventors have discovered that by using a flame retardant and a specific sulfide yarn compound in combination, the retention stability and heat resistance stability of mechanical properties and electrical properties are significantly improved, and the present invention has been achieved.

That is, the present invention provides 100 parts by weight of aromatic polyester, 3 to 50 parts by weight of a halogenated bisphenol cyanuric acid ester compound, 1 to 20 parts by weight of antimony trioxide, and 0 the following general formula (1). ) 0.0
The present invention provides a flame-retardant polyester composition containing 1 to 3 parts by weight, and a composition containing 0.1 to 10 parts by weight of a polyvalent engineered polyester compound.

R'00C-Ad'-5-Afi2-COOR2--,
(1) (In the formula, R and R2 each represent an alkyl group having 3 to 30 carbon atoms, and AR' and Al1 each represent an alkylene group or substituted alkylene group having 1 to 10 carbon atoms.) This invention The aromatic polyester used in is a polyester that has an aromatic ring in the chain unit of the polymer, and is a condensed polyester whose main components are 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 reaction.

Here, the aromatic dicarboxylic acids include terephthalic acid,
Isophthalic acid, orthophthalic acid, '1.5-naphthalenedicarbonoic acid, 2.5-naphthalenedicarbonoic 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'-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'-p-terphenylenedicarboxylic acid, 2,5-
Examples include 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 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. I can do it.

In addition, rheol components include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopenotyl glycol, 2--'thi, t,
-1・3 "P0"nodiono'・-'1 Aliphatic diols such as ethylene glycol and triethylene glycol, 1
Examples include alicyclic diols such as 14-cyclohexane dimetatool, and mixtures thereof. In addition, if it is a small amount, the molecular weight is 400 to 6.0. OO long chain diol i.e. polyethylene glycol, poly-1,3
- Flopylene gelylcol, polytetramethylene glycol, etc.

One or more types may be copolymerized.

Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate,
In addition to polyethylene naphthalate-1, polybutylene naphthalate, polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate, polyethylene isophthalate/terephthalate, polybutylene terephthalate-h/iso Examples include copolymerized polyesters such as phthalate, polybutylene terephthalate/dikanjikarme chiyushihito, and the like. Among these, polybutylene lentil clay 1- and polyethylene terephthalate, which have well-balanced mechanical properties and moldability, can be preferably used.

The aromatic polyester used in the present invention preferably has a relative viscosity of 1.15 to 2.0, particularly 1.3 to 185, as measured in a 0.5% O-chlorophenol solution at 25°C.

The cyanuric acid ester compound of halogenated hisphenols used as a flame retardant in the present invention is usually a compound obtained by reacting a halogenated cyanuric acid, preferably cyanuric chloride, with a halogenated bisphenol, and is represented by the following general formula. It will be done.

(In the above formula (It), Ar' to Ar' are each a monovalent aromatic group, and may be substituted with a halogen, a lower alkyl group, a halogenated lower alkyl group, etc.).

Ar is a divalent aromatic group substituted with halogen,
Furthermore, it may be substituted with a lower alkyl group, a halogenated lower alkyl group, or the like. n indicates the degree of polymerization. ) Preferred examples of Ar' to Ar' include substituents of formula (llll).

In the formula (all) above, R3 represents a lower alkyl group or a halogenated lower alkyl group, and X represents bromine or chlorine. kll is each an integer of θ~5, and k-l-l≦
It is 5. ) Specific examples of Ar' to Ar4 include phenyl, monobromphenyl, tribromo phenyl, benotar f rom phenyl, monochloro phenyl, trichlorfer, monochlorotolyl, tribromo tolyl', ^ dibromopropylphenyl, etc., and tribromo phenyl , pentabromphenyl, trichlorophenyl, pentachlorophenyl and the like are particularly preferred.

Further, preferable examples of Ar include substituents of formula (1').

(In the above formula (IV), R4 and R5 each represent a lower alkyl group or a halogenated lower alkyl group, and Y represents a lower alkyref group, a halogenated lower alkylene group, an alkylideno group, -5O2-1-SO, -5- 1-0-1-CO
-1 chemical bond, Zl and Z2 each represent bromine or chlorine. p, q, , r, and s are each integers from 0 to 4, and satisfy p+q+r→-8≦8 or 1') r +s≧2. ) Ar is a residue of halogenated bisphenol used during flame retardant synthesis. Preferred specific examples of such bisphenols include 2,2-bis(3-chloro-4-hydroxyphenyl)fluoro, 2°2-bis(3,5-
dichloro-4-hydroxyphenyl)propane, 2,2
-bis(3-bromo-4-hydroxyphenyl)furopane, 2,2-his(3゜5-dibromo-4-hydroxyphenyl)bronoman, bis(3-chloro-4-hydroxyphenyl)sulfone, bis(3, 5-dichlor-4
-Hydroxyphenyl)sulfone, bis(3-bromo-
4-hydroxyphenyl)sulfone, bis(3,5-sibromo-4-hydroxyphenyl)sulfo7, his(3
, 5-dichloro-4-hydroxyphenyl)methane, bis(3,5-dibromo-4-hydroxyphenyl)methane, among which mo-2,2-his(3,5-'; from-4-hydroxyphenyl) ) propane and bis(3,5
Particular preference is given to using Salel -'; bromo-4-hydroxyphenyl)sulfone.

The degree of polymerization n preferably ranges from 1 to 50, more preferably from 3 to 20.

Further, the halogen content in the cyanuric acid ester compound of halogenated bisphenols is preferably 30% by weight or more, especially 50% by weight or more when the halogen is bromine, and 20% by weight, especially 40% by weight when the halogen is chlorine. % or more is preferable. Furthermore, when both bromine and chlorine are included as the chlorogen, the amount thereof is preferably at least a value approximately intermediate between the above-mentioned bromine and chlorine contents.

The amount of the noanuric 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, so both are not preferred.

The flame retardant effect of the noanurate ester compound of halogenated bisphenols is significantly enhanced by the combined addition of anotymone trioxide. The amount added is 100% aromatic polyester
The amount is 1 to 20 parts by weight, preferably 3 to 15 parts by weight, and if it is less than 1 part by weight, it will not provide sufficient flame retardancy, and if it exceeds 20 parts by weight, the mechanical properties of the aromatic polyester will deteriorate. is damaged. More preferably, the halogenated bisphenol is added in a ratio of 2 to 5 halogen atoms in the cyanuric acid ester compound to 1 antimony atom in the antimony dioxide.

At the same time, other flame retardant adjuvants such as boron oxide, zirconium oxide, iron oxide, etc. may be used in combination.

A composition comprising an aromatic polyester containing the above-mentioned noanuric acid ester compound of a halogenated bisphenol and anotymone trioxide has excellent flame retardancy. However, when a specific sulfide compound is further added to this composition, the mechanical properties and electrical properties are further improved, and the retention stability and thermal stability of the mechanical properties and electrical properties are also improved. can get.

The Nurphyto compound used in the present invention has the following general formula (1
).

R100C-Afil-5-Ad2-COOR2,,,
(1) (wherein R+ and R2 are each an alkyl group having 3 to 30 carbon atoms, A11 and A12 are each,
It represents an alkylene group or substituted alkylene group having 1 to 10 carbon atoms. ) Preferable specific examples of the sulfide compounds described in 1. Among them, distearylthione propionate is the most preferred.

The amount of the sulfide compound used in the present invention is from 0.01 to 100 parts by weight of aromatic polyester.
3 parts by weight, especially from 0.05 to 0.5 parts by weight. If the amount of the sulfide compound added is less than 0.01 parts by weight, the retention stability and heat resistance stability of the mechanical 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. The properties are rather deteriorated, which is not preferable.

In the present invention, if a polyvalent epoxy compound is used in combination, the retention stability and heat resistance stability of mechanical properties and electrical properties can be further improved. Such a polyvalent epoxy compound is a compound having at least two epoxy groups in the molecule, and includes, for example, bisphenol-type epoxy compounds obtained by reacting bisphenol A and epichlorohydrin in various proportions, and compounds obtained from novolak resin and epichlorohydrin. Novolac type epoxy compounds obtained, polyglycyl esters obtained from polycarboxylic acids and epichlorohydrin, alicyclic epoxy compounds obtained from alicyclic compounds (e.g. dinoclopentalenine), fats having alcoholic hydroxyl groups. Examples include grindyl ethers obtained from group compounds (for example, butanediol, glycerin, polyalkylene glycol, etc.) and epichlorohydrin, and epoxidized polybutadiene.

Suitable examples of these epoxy compounds include polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyglycyl ester represented by the following general formula (V), and bisphenol type epoxy compounds represented by the following general formula (B). can be mentioned.

(However, in the formula, R6 is an alkylene group having 4 to 40 carbon atoms,
Shows phenylene group, partially hydrogenated phenylene group, and nocrohequinoleno group. ) (However, in the formula, m is a number from O to 20.) Specific examples of the polyvalent epoxy compound of formula (V) include hexahydrophthalic acid diglycyler ester, tetrahydrophthalic acid diglycyler ester, and fucuric acid. Examples include diglycidyl ester and diglycidyl terephthalate.

When a polyvalent epoxy compound is used in the present invention, the amount added is preferably 01 parts by weight or more and 10 parts by weight or less per 100 parts by weight of the aromatic polyester.

Furthermore, the inorganic filler that can be added in the present invention is fibrous,
It may be in any form such as plate or granule, such as glass fiber, carbon fiber, metal fiber, glass peas, glass flakes, mica, wollastenite, talc, 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. Normally chopped strands and roving types are used as glass fibers, but from the viewpoint of ease of handling and surface gloss of molded products,
Chopped strands of 6 fight length are preferred. Furthermore, glass fibers treated with a conventional coupling agent such as a furano group or a techno group, or a conventional binding agent such as an epoxy resin or vinyl acetate are particularly preferably used.

The amount of the inorganic filler added is 0 to 100 parts by weight per 100 parts by weight of the aromatic polyester.

The heat stability of the composition of the present invention is further improved by the addition of a stabilizer. These stabilizers include phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, phenylphosphinic acid, diphenylphosphonoic acid, and polyester-1.
It can be made using phosphorus compounds such as ・, hinodado phenol compounds, etc. The amount of these stabilizers added is generally preferably 0.001 to 3 parts by weight per 100 parts by weight of the aromatic polyester.

The composition of the present invention may contain conventional additives such as ultraviolet absorbers, lubricants, mold release agents, colorants including dyes and pigments, other thermoplastic resins ( For example, polyethylene, polypropylene, ethylene/propylene copolymer, ethylene/propylene/geno terpolymer, ethylene/Latin-1 copolymer, ethylene/vinyl acetate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/vinyl acetate /glycidyl methacrylate copolymer, etc.).

These additives may be used alone or in combination of two or more.

Although the method for producing the composition of the present invention is not particularly limited, it is preferable to use an extruder to prepare four components: an aromatic polyester, a cyanuric acid ester compound of halogenated hisphenols, antimony trioxide, and a sulfide compound. An example of this method is to melt and knead the mixture. When adding an inorganic filler, it is preferable to melt-knead it simultaneously with the above four fillers 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 6 Polybutylene terephthalate 100 with a relative viscosity of 1.67
The following flame retardant (α) or ■, 7 parts by weight of antimony trioxide and the following sulfide compound (c) to parts by weight
◎ was added in the proportions shown in Table 1, mixed with a heno shell mixer, and then mixed using a 4 Q mm cl) extruder.
Melt and knead at ℃ to form pellets. Next, the obtained Beretsu 1- was molded using a 2-ounce screw Innoline injection molding machine set at 250°C, with a mold temperature of 80°C and a molding cycle (injection time/cooling time/intermediate time) of 10 seconds/15.
sec/10 seconds (molding cycle (a)), ASTM
-, No. 1 dumbbell, square plate (80y x 80 III
X 1 ww ) and combustion test piece (1/16' XI
/2'x5') were obtained.

Also, 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 measured. These results are shown in Table 1.

Flame retardant a: cyanuric chloride, 2,2-bis(3,5-dibrom-
A flame retardant having the following structure obtained by reacting 4-hydroxyphenyl)propane and tribromophenol.

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 Sulfide compound A distearyl thiodipropionate i 5 (CH2
CH2COOC18H37) 2B: dilauryl thiolepropionate 5 (CH2CH2COOC22H2 Are the compositions containing the sulfide compounds without the addition of sulfide compounds or with the addition of other sulfide compounds? , Z composition, it is clear that the thermal stability of mechanical properties and electrical properties is excellent, and these properties are further improved when the molding residence time is increased.

Examples 10 to 15, Comparative Examples 7 to 10 Polybutylene terres clay 1-100 with a relative viscosity of 149
Based on the weight parts, 7 parts by weight of antimono trioxide, 50 parts by weight of glass fiber (epoxy resin binder, 3 tomocho chopped strands), UJI refueling agent used in Example 1 (α
) and a sulfide compound were added in the proportions shown in Table 2, and after tri-blending with a Tanoblar, the mixture was melt-kneaded and formed into pellets. Further, ASTM-1 dumbbells, square plates, and combustion test pieces were molded using the molding cycle under two conditions in the same manner as in Example 1, and a vertical combustion test, a tensile test, and a dielectric breakdown test were conducted. The results are shown in Table 2.

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 these properties deteriorate when the molding residence time is long. It is clear that this has been further improved.

Examples 16 to 18, Comparative Examples 11 to 16 Polyethylene terephthalate (PET) with a relative viscosity of 1.35 as aromatic polyester, relative viscosity 1, 1i
l+ no, l? Reno No 1:・Nol Sota 1,1・,V No' Tsuno Shidionoic acid (90
/10 molar ratio) copolymer (PBT/D), relative viscosity 1
．． 77 polybutylene terephthalate/inophthalate 1-(90/10 molar ratio) copolymer (PBT/I
), 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 the sulfide compound (A), and glass fiber (epoxy resin Tri-blend 13 pieces of Beitzter 13, Long, Chiyo, and Human Butto strands), melt-knead and pelletize in the same manner as in Example 1, and then use injection molding, ASTM No. 1 dumbbells, square plates, and combustion tests. I created a piece.

However, in the case of PET, the melt-kneading and molding temperature is 29
Set the mold temperature to 0°C and 130'C.

Table 3 shows the evaluation results of the molded products.

(Blank below on this page) From the results in Table 3, PET1P is an aromatic polyester.
It can be seen that the use of BT/D and PBT/I also produces the same effects as PBT.

Examples 19-22, Comparative Examples 17-19 Polybutylene terephthalate 100 with a relative viscosity of 1.61
Flame retardant (a) used in Example 1 based on parts by weight 20
Parts by weight, 7 parts by weight of anotimono trioxide, 0.05 parts by weight of the sulfide compound formula, and the polyvalent epoxy compound shown in Table 4 were triblended, melt-kneaded and pelletized in the same manner as in Example 1, and then injection molded. ASTM-1 dumbbells, square plates, and combustion test pieces were prepared. Table 4 shows the evaluation results of the molded products.

(Blank below on this page) From the results in Table 4, it is clear that when the composition of the present invention contains a polyvalent epoxy compound, the heat stability and retention stability of mechanical properties and electrical properties are further improved. It is.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (2)

[Claims] (1) Aromatic polyester 100! 3 to 50 parts by weight of a cyanuric acid ester compound of halogenated bisphenols, 1 to 20 parts by weight of antimono trioxide, and 0.01 to 0.01 to 0.01 to 0.01 of a sulfide compound represented by the following general formula (1), based on the weight of each part.
A flame-retardant polyester composition containing 3 parts by weight. RI 0OC-A6'-5-A12-COOR2,,
, (1) (wherein R and R2 are each an alkyl group having 3 to 30 carbon atoms, A41 and A12 are each,
It represents an alkylene group or substituted alkylene group having 1 to 10 carbon atoms. ) (2) The composition according to claim 1, which contains 0.1 to 1 part of a polyvalent epoxy compound based on 100 parts by weight of the aromatic polyester.