JPH01201357A - Flame-retarding aromatic polyester resin composition - Google Patents

Abstract

PURPOSE:To provide the title resin composition excellent in flow during molding, and stability during residence, and giving a molding excellent in flame retardancy, tensile strength, etc., by mixing an aromatic polyester resin with a specified epoxy compound and an organobromine compound in a specified ratio. CONSTITUTION:100pts.wt. aromatic polyester resin composition (A) (e.g., polyethylene terephthalate) is mixed with 0.01-10pts.wt. epoxy compound (B) of formula I (wherein Ar is a 6-20C aromatic group or an alicyclic group, and n is 0 or 1-20), e.g., formula II or III, and 1n50pts.wt. organobromine compound (C) (e.g., hexabromobenzene or brominated polycarbonate) to produce a flame- retarding aromatic polyester resin composition. The obtained resin composition can be easily molded by a process such as injection molding or extrusion molding, and it is excellent in hydrolysis resistance, etc., and can be desirably used as, e.g., the parts of automobile electric equipment.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention provides a flame retardant material having hydrolysis resistance, retention stability during molding, collapse in fluidity, and good heat cycle resistance. The present invention relates to aromatic polyester resin compositions.

<Prior Art> Aromatic polyester resins, represented by polybutylene terephthalate and polyethylene terephthalate, are being used in a wide range of applications, including electronic and electrical parts and automobile parts, by taking advantage of their excellent properties.

When used as a material for these industrial applications, it has become extremely important to have safety against flames, that is, flame retardancy, in addition to chemical and physical properties.
Since aromatic polyester resins do not have sufficient flame retardancy by themselves, various techniques for reducing the number of flame retardants are being considered. Among the weight and weight methods, from the point of view of cost performance, a method of using a cara organic bromine compound in combination with antimony oxide has been extensively studied. However, when these methods are applied, the aromatic polyester deteriorates due to the effects of halogen radicals, water, antimony oxide, etc. generated during melt processing, resulting in a decrease in mechanical strength and coloring. In addition, when used in automobile electrical components such as distributor caps, hydrolysis resistance is increasingly required, but organic bromine compounds and antimony oxide are added. It has been pointed out that in some cases, the hydrolysis resistance of aromatic polyesters, which are originally poor, becomes even worse.

In order to suppress the deterioration and improve the hydrolysis resistance of such flame-retardant aromatic polyester resins, there is a method of adding epoxy compounds such as bisphenol A diglycidyl ether, for example, to suppress the deterioration of aromatic polyester resins. Many methods of adding epoxy compounds have been proposed, such as in the corresponding Japanese Patent Application Laid-open No. 54-149756 and Japanese Patent Application Laid-Open No. 161452-1985, which purports to improve hydrolysis resistance.

<Problems to be Solved by the Invention> However, the effect of improving the water decomposition properties and deterioration of the 5R flammable aromatic polyester by the above method is not very great, and not only does it significantly reduce the flowability of the resin during molding. There are problems such as these, and a method for improving these functions of flame-retardant aromatic polyester resins has not yet been found.

Means for Solving the Problems The inventors of the present invention have developed a four-combustible aromatic polyester resin that has excellent thermal deterioration properties and satisfies all of the following: composition;@'! As a result of intensive studies, we found that when a specific epoxy compound is added to aromatic polyester and an organic bromine compound, not only the above objective is achieved, but surprisingly, the heat cycle resistance is also significantly improved. We have found that this can be improved and have arrived at the present invention.

``That is, the present invention is directed to aromatic polyester 100** section (B)
Epoxy compound represented by the following general formula (1) 0.0
1-10 parts by weight (wherein Ar is an aromatic group or alicyclic group having 6 to 20 carbon atoms, and n is 0 or an integer of 1 to 20.) (C) Organic backbone compound 1~ The present invention provides a flame-retardant aromatic polyester resin composition tube containing a polyester resin bottle.

The aromatic polyester used in the present invention is a polyester that has an aromatic ring in the superstition unit of the polymer, and is composed of an aromatic dicarboxylic acid (or its ester-forming derivative) and a diol (or its ester-forming derivative). It is a polymer or copolymerization obtained by a violet-polymerization reaction in which the main component is violet.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, ortho-7thalic acid, 1.5-naphthalene/
dicarboxylic acid, 2.5-naphthalene dicarboxylic acid, 2,
6-naphthalenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,
4'-biphenyl dicarboxylic acid, 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-pyridinedicarboxylic acid, and terephthalic acid is preferably used.

Two or more of these aromatic dicarboxylic acids may be used in combination. If you are using pocket money, you can mix one or more of these aromatic dicarboxylic acids with aliphatic dicarboxylic acids such as adipic acid, azelaic acid, dodecanedioic acid, and sebacic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. can be used.

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

In addition, if it is pocket money, Min-P! One or more long-chain diols having a molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc., may be copolymerized.

Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate (L/-), yt'jJ engineering f'l/-1,2-bis(phenoxy)ethane-4 , 4'-dicarboxylate, and copolymerized polyesters such as polyethylene isophthalate/terephthalate, polybutylene terephthalate/isophthalate, and polybutylene terephthalate/decanedicarboxylate. 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 0.5
96 O-chlorophenol HH has a relative viscosity of 115 to 2.01, particularly preferably 1.3 to 185, as measured at 25°C.

The epoxy compound (6) used in the present invention is represented by the general formula (1) above.

Specific examples of Ar include l,4-phenylene, 1,3-
Phenylene, 1,2-phenylene, 2-methyl-1,4
-phenylene, 4,4'-biphenylene, 3,3'-biphenylene, 2,2'-biphenylene, 3,4'-biphenylene, l,4-naphthylene, l,5-naphthylene,
2,6-naphthylene, 2,7-naphthylene, 1,4-cyclohexylene, 1,3-cyclo5-xylene, 1.

Preferred examples include 2-cyclohexylene, 4,4'-bicyclohexylene, 2,6-zocahydronaphthylene, and especially 1,4-phenylene, 1,3-phenylene, and 2,6-naphthylene. preferable.

The value of the degree of polymerization n of the compound of formula (1) is 0 or 1 to 20
is an integer of , preferably an integer of 0 or l −10,
It may also be a mixture of compounds having various degrees of polymerization.

It is preferable that the average degree of fidelity is in the range of 0 to 2,
Ratio M of weight average molecular m (MW) and number average molecular structure (Mn)
w/Mn is in the range of 1.0 to 3.0. The method for producing the epoxy compound shown in intermediate formation is not particularly limited, but for example, hydroxycarboxylic acid and shrimp halohydrin are heated at 40°C to 150°C in the presence of a catalyst such as a quaternary ammonium salt, a tertiary amine, or a tertiary phosphine. ℃
An example of this method is to perform a reaction with a helohydrin ester to etherify the helohydrin ester, and then add an alkali metal salt to remove halogen.

A product with a high electric power can be obtained by further reacting a hydroxycarboxylic acid in the presence of a catalyst while changing the ratio.

The amount of the epoxy compound added in the intermediate composition in the present invention is 0.000 m/100 m parts of the aromatic polyester. O1
~1031! It is desirable that the imaginary part is preferably 0.05 to 5 N11 parts, more preferably 0.2 to 3N11 parts. Addition amount is 0. In the case where the O1 area is not exposed, the effect of improving the hydrolysis resistance of the aromatic polyester is not sufficient;
If it exceeds the w-kite part, the mechanical properties of the aromatic polyester will be impaired, so it is not preferable.

The (O organic bromine compound) used in the present invention refers to a known organic bromine compound that has a bromine atom in its molecule and is usually used as a flame retardant.
Preferably, the content is 20 MN% or more. Specifically, hexabromobenzene, pentabromotoluene, hexabromo piphenyl, thecapromo biphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis(pentabromophenoxy)ethane, ethylene bis- (tetodipromophthalimide), low molecular weight I organic bromine compounds such as tetrabromobisphenol A, brominated polycarbonates (e.g. polycarbonate oligomers produced from brominated bisphenol A), brominated epoxy or brominated phenoxy compounds (e.g. brominated phenoxy compounds) Jepoxy compounds, brominated epoxy oligomers, brominated epoxy polymers, brominated phenoxy polymers), poly (brominated benzyl acrylate), brominated polyphenylene ethers, brominated bisphenol A produced by the reaction of brominated bisphenol A and epichlorohydrin
/cyanuric chloride/Jl-phenol condensates, halogenated polymers and oligomers such as brominated polystyrene, and mixtures thereof, among which brominated epoxy oligomers and polymers (with an average degree of polymerization of 4 to 1
00), brominated polystyrene (average degree of polymerization 20-200
), deep-X polyphenylene ether (average degree of polymerization lO ~
200), brominated polycarbonate (average degree of polymerization 3-3
0) and cyanuric chloride/brominated bisphenol/brominated phenol condensates (average degree of polymerization 3 to 30) are preferred, particularly tetrabromo end-capped with a monovalent 7 enol such as p-tert-butylphenol and tribromophenol. Average degree of polymerization using bisphenol A as raw material: 3
-30 brominated polycarbonate or its co-combination with bisphenol A polycarbonate can be preferably used.

The amount of these organic bromine compounds (C) added is 1 to 50 pages, preferably 5 to 30 pages, per 100 M imaginary parts of the aromatic polyester. If the amount of Addition 1 is less than lfim parts, the flammability will not be sufficient, and if it exceeds 50 parts by weight, the physical properties of the composition will deteriorate, which is not preferable.

Antimony oxide that can be used in the present invention is
There are no particular restrictions as long as it is normally used as a flame retardant aid for polyester, but antimony trioxide is preferred. Furthermore, zirconium oxide, zinc sulfide, barium sulfate, acetate/sodium acid, triphenylstibine, etc. may be used in combination with antimony dioxide.

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

The composition of the present invention exhibits sufficient performance without a filler, but by adding a filler, it is possible to improve the heat distortion temperature and rigidity, and reduce the molding shrinkage rate, and the performance is further improved.

The fillers used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, potassium titanate fibers, gypsum fibers, brass fibers, stainless steel fibers, steel m fibers, seven-mix fibers, poronquisker fibers, mica, Examples include fibrous, granular, powder, or plate-like inorganic fillers such as talc, silica, calcium carbonate, glass peas, glass flakes, clay, wollastenite, and titanium oxide. Also in (I), fibrous inorganic fillers are preferred, and glass fibers are particularly preferably used.

The type of glass fiber is generally not particularly limited as long as it can be used for reinforcing the resin, and can be selected from, for example, long fiber type, short fiber type, chipped strand, milled fiber, etc. Furthermore, the glass fibers may be coated or bundled with a thermoplastic resin such as an ethylene/vinyl acetate copolymer, a thermoplastic resin such as an epoxy resin, a coupling agent such as a silane type or a titanate type, or other surface treatment. It may be treated with a processing agent.

When adding a filler, aromatic polyester 10
The amount is 1 to 200 parts, more preferably 5 to 100 parts per 0 mKm part.

The composition of the present invention can be prepared by:
Customary additives such as UV absorbers, lubricants, molding agents, colorants including dyes and pigments, antioxidants, other thermoplastics (e.g. polyethylene, polypropylene, ethylene/propylene co-i, ethylene/propylene) /genter polymer, ethylene/butene-1 coelectrolyte, ethylene/glycidyl methacrylate copolymer, ethylene/
It is possible to further contain a vinyl acid/glycidyl methacrylate copolymer) or the like. These additives may be used in one volume 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, a specific epoxy compound, an organic bromine compound, and if necessary, antimony oxide or a filler are added using an extruder. Examples include a method of melt-kneading.

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.

In addition, the part in the example means the eastern amount part.

Examples 1-5, Ratio Examples 1-3 Polybutylene terephthalate 100 with relative viscosity 1.65
1, the following epoxy compound, 24 parts of brominated polycarbonate (Kijin Kasei (Copper FG-7500)) and 8 parts of antimony trioxide were blended in the combinations and proportions shown in Table 1, and after kneading with a blender. The mixture was melted and mixed into pellets at 250° C. using a 40 Wφ extruder.

After drying the pellets, use a 5-ounce screw-in-line 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/15 seconds/10. seconds (molding cycle (a))
, 10 seconds/15 seconds/185 seconds (molding cycle (b)) to obtain an ASTM-1 dumbbell and the minimum pressure necessary to fill the resin into the mold (lower limit pressure for molding).
was measured. In addition, L/8' impact test piece, combustion test piece (1
/16'X 1/2' X 5') were obtained.

These test pieces were subjected to a combustion test in accordance with the UL-94 standard, a tensile test in accordance with ASTM D638, and AS'
Izod impact tests were carried out according to rlVI D 256. For the tensile test pieces of molding cycle 0), high slag (
2 hours at -40℃ using a thermal cycle tester made by Co., Ltd.
After conducting a heat cycle test with 2 hours at 150°C for 30 days (test subject) and hot water treatment at 100°C for 15 days (test)), the treated specimens were subjected to a tensile test. . The results are shown in Table-1.

[Epoxy compounds a to e]

\/ As is clear from the results in Table 1, when the specific epoxy compound of the present invention is used in addition to both the aromatic polyester and the organic bromine compound, the molding fluidity, mechanical properties, especially impact strength are improved. It can be seen that an Mm-based aromatic polyester resin composition can be obtained which not only has excellent properties but also extremely excellent heat cycle properties and hydrolysis resistance. 1 - When something other than the specific epoxy compound of the strength wood invention was added (Comparative Examples 2 and 3), not only the retention stability and mechanical properties during molding were inferior, but also the fluidity during molding was significantly reduced. descend.

Examples 6 to 8, Comparative Examples 5 to 7 100 parts of polybutylene terephthalate with relative viscosity L47, glass m fiber (3 lengths, tricyclic strand type)
50 parts, 24 parts of brominated polycarbonate (FG-7000 manufactured by Kijin Kasei (Ten) Co., Ltd.), 8 parts of antimony trioxide, and the gc positions listed in Table 2 of epoxy compounds a to e were triblended in a tumbler, and then mixed with Example 1. In the same way,
Injection molding (molding temperature was 260°C) and characteristic evaluation were performed. These results are shown in Table-2.

As is clear from the results in Table 2, even when glass fiber is used in combination, the composition of the present invention not only significantly improves mechanical properties such as fluidity during molding, tensile strength, and impact resistance, but also improves resistance. It can be seen that a flame-retardant aromatic polyester resin composition having excellent hydrolyzability and heat cycle resistance can be obtained.

The brominated polycarbonate of Example 119-13, Specific Yield Examples 8-12, and Practical Example-2 was converted into the following specific bromine compound f-
All the ponds changed to i have the same composition, and condition V of Actual Example 2 is applied.
Accordingly, melt mixing, injection molding and property evaluation were performed (Examples 9 to 13). Further, specific epoxy-free compositions were similarly evaluated (Ratio 4!2 Examples 8-12).
).

These results are shown in Table 3.

[Special bromine compounds]

r (S is approximately 10) BrOUBr It is clear from the results in Table 3 that the present invention was effective even when organic bromine compounds other than aromatic polyester and brominated polycarbonate were used together with a specific epoxy compound. The composition not only has excellent fluidity during molding, but also exhibits excellent hydrolysis resistance, mechanical properties, and heat cycle resistance. On the other hand, compositions that do not contain a specific epoxy not only have significantly reduced silk fixing stability, but also have poor oral decomposition resistance and heat cycle resistance.

<Effects of the Invention> The flammable aromatic polyester resin composition of the present invention has good fluidity and WtI retention stability during molding, and the molded products obtained have good Ia mechanical properties such as flame retardancy and tensile strength. Since it not only has excellent hydrolysis resistance but also extremely heat cycle resistance, it can be used not only for gas/electronic applications but also for a wide range of automotive electrical equipment applications.

Patent application Daitoshi Co., Ltd.

Claims (1)

[Claims] (A) Based on 100 parts by weight of aromatic polyester resin, (B) 0 epoxy compound represented by the following general formula (I)
．． 01 to 10 parts by weight ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼... (I) (However, in the formula, Ar is an aromatic group or alicyclic group having 6 to 20 carbon atoms, and n is 0 or 1 to 1. (Indicates an integer of 20.) (C) A flame-retardant aromatic polyester resin composition containing 1 to 50 parts by weight of an organic bromine compound.