JPS59155454A - Flame-retardant polyethylene terephthalate resin composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. which has excellent melt stability and does not cause the bleed out of flame retarder, consisting of a specified modified polyethylene terephthalate, a reinforcing filler, an aliph. polyester, a brominated polystyrene and a modified brominated epoxy resin. CONSTITUTION:35-85wt% polyethylene terephthalate resin (A) modified by adding 0.1-5wt% compd. of formula I or II (wherein M, M' are each an alkali metal; n, m are each 1 or 2) before the completion of polymn., 1-10wt% aliph. polyester (B) having an acid value of 0.1 or below and an MW of 4,000 or above obtd. by reacting an aliph. dibasic acid with a 2-8C glycol, 5-30wt% brominated polystyrene (C) having a bromine content of 40wt% or above and a weight- average MW of 20,000 or above and of formula III (wherein X is Br; n is 58 or greater; m is 1-3), 0.1-30wt% modified brominated epoxy resin (D) obtd. by adding a compd. of formula V to a compd. of formula IV (wherein X is Br; n is a degree of polymn. and 0 or greater) and 5-60wt% reinforcing filler (E) such as glass fiber are blended together.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flammable resin composition made of polyethylene terephthalate.More specifically, it has improved crystallinity, excellent melt thermal stability, thermal properties, and mechanical properties, and The present invention relates to a flame-retardant reinforced polyethylene terephthalate resin composition in which a flame agent does not become cylindrical.

Reinforced thermoplastic polyester resins are widely used as industrial materials because of their excellent thermal, mechanical, and electrical properties.

For flame retardant materials for electrical parts, please contact Underwriters.
Passed Lazeratories UL94 ■-0 to V-2,
Moreover, there is a demand for the development of a material that does not bleed into the fuel.

For example, compared to glass fiber reinforced polyethylene terephthalate resin, glass fiber reinforced polyethylene terephthalate resin has a lower crystallization rate at an injection mold temperature of 100°C or less, so it has sufficient thermal properties, mechanical properties, and dimensional stability. Since a satisfactory product cannot be obtained, the mold temperature is usually set at 140° C. or higher for injection molding.

Furthermore, polyethylene terephthalate resin has a high melting point and is molded at a very high temperature of 270 to 290°C. Therefore, in polyethylene terephthalate resin with added flame retardant, the flame retardant decomposes and the resin foams. The flame retardant must have high heat resistance because the flame retardant may bleed out or bleed out onto the surface of the injection mold. However, even if the flame retardant has high heat resistance, if plasticized resin is allowed to remain in the cylinder, the molten resin may flow out from the nozzle tip (causing dripping). For example, Tokushu 48-52834
No., JP 55-3375, JP 57-53505
When the flame retardant found in the publication was applied to polyethylene terephthalate resin, it was found that the melt viscosity decreased and caused sagging.

In addition, electrical parts are used at high temperatures for long periods of time, so
Flame retardants must not be allowed to form on the surface of the product and impair flame retardancy and electrical properties.

Conventionally, the most effective flame retardant imparting agent for thermoplastic polyester resins is a combination type of decabromodiphenyl oxy-P and antimony trioxide. 83% odor cord content
When a performance test was conducted using a combination of decabromodiphenyl oxy-P and antimony trioxide and added to glass fiber reinforced polyethylene terephthalate resin, it showed excellent heat resistance and initial flame retardancy, and the rate of decrease in mechanical properties was also low. Although it is small, decazolomodiphenyl oxide is solvated onto the surface of the product over time, resulting in a decrease in gloss and a very large decrease in arc resistance.

A method of making polyethylene terephthalate resin flame retardant using brominated polystyrene is found in JP-A-57-53505. Although this blended composition has excellent flame retardancy and bleed resistance, the crystallinity of the polyethylene terephthalate resin has not been improved, and the injection mold temperature can be increased to 90°C.
If molded at temperatures below 0.degree. C., it is impossible to obtain a material with sufficiently satisfactory thermal and mechanical properties. Also, is there a bromination technology for polyethylene terephthalate resin? A method of making flame retardant using xy resin can be found in JP-A-54-103458. This blended composition has excellent flame retardancy and bleed resistance, but when molded at an injection mold temperature of 90°C or lower, it has poor crystallinity, a low heat distortion temperature, and a short molding cycle. It turned out to be a long time.

In general, unmodified flame-retardant reinforced polyethylene terephthalate resin does not crystallize much even when injection molded within the hot water mold temperature range, so its thermal and mechanical properties are practically satisfactory. The disadvantage is that you cannot get what you want.

Even in the UL94 flame retardant vertical combustion test, there is a lot of dripping and cotton ignition is more likely to occur.

In the present invention, the crystallinity of polyethylene terephthalate resin itself is improved using a compound of the following general formula [■] or [■] and an aliphatic polyester, and brominated polystyrene and modified brominated chemical compound H? It is made flame retardant by adding xylene resin. As a result, injection molding was possible using a mold cooled by muddy water.
We have discovered the flame-retardant reinforced polyethylene terephthalate resin composition of the present invention, which has excellent melting thermal stability, thermal properties, and sexual properties, and also has the feature that the flame retardant does not bleed.

The polyethylene terephthalate resin used in the present invention is a resin modifier represented by the general formula (in the formula, M and M' are the same or different alkali metals, and n and m are 1 or 2). This is a modified polyethylene terephthalate in which a compound is added in an amount of 0.1 to 5% by weight based on the weight of polyethylene terephthalate before completion of polymerization.

Even if it is added after the polymerization is completed, almost no modification effect can be exerted.

The compounds represented by the general formula [1)'t or CI+) used in the present invention include disodium P-phenolmalphonate, disodium 2-naphthol-6-sulfonate, and disodium 2-naphthol-8-sulfonic acid. disodium, 2
．． Examples include trisodium 3-naphthalenediol-6-sulfonate.

Regarding a method for completely promoting crystallization of polyethylene terephthalate resin, JP-A-54-158452 niha,
A composition is shown in which a polyethylene terephthalate resin is blended with glass fibers, an ionomer, and neobentyl glycol dibendoate. In addition, % Kaisho 53-65
No. 354 discloses that a highly crystalline composition can be obtained by blending an esterified product having a molecular weight of about 135 to 2,000 with a polymer capping polyalkylene terephthalate resin.

When these compositions were molded at a polyethylene terephthalate resin injection molding temperature of 270 to 290°C and a mold temperature of 90°C, a large amount of gas was generated from the nozzle of the molding machine, and the heat distortion temperature h Bit mechanical properties It turns out that the characteristics are not necessarily satisfactory.

As the aliphatic polyester used in the present invention, one or more polyesters having an acid value of 1.0 or less and a molecular weight of 4,000 or more, consisting of an aliphatic dibasic acid and a glycol having 2 to 8 carbon atoms, are used in an amount of 1 to 10% by weight. %, the volatile gas during molding process is small and crystallization can be carried out over a wide range of mold temperature expansion.

Examples of the dibasic acids constituting the polyester used in the present invention include chloride acid, glutaric acid, adipic acid, pimeline acid, cepacic acid, and F-decanoic acid. Glycols include ethylene glycol,
1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, etc. can be used. Particularly suitable polyesters include polyzotylene adipate, polybutylene quinocate, and polyvinylene sepacate.

The brominated polystyrene used in the present invention is tribromo polystyrene obtained from polystyrene and bromine chloride. The bromine content is 40% or more, and the weight average molecular weight as measured by gel permeation chromatography is 2o, oo
It is a polymer with a weight average molecular weight of 100,000 to 200, since the flame retardant effect decreases as the weight average molecular weight increases.
000 is good. The modified brominated epoxy resin used in the present invention is a product obtained by adding brominated bisphenol to a polymer of tetrabromobisphenol A and epichlorohydrin. The higher the bromine content, the greater the flame retardant effect, and the smaller the amount added, the more economical it is.

The ratio of the brominated polystyrene to the modified brominated epoxy resin used in the present invention is preferably 171 to 29.910.1, and the total amount added is preferably 5 to 30% by weight based on the total amount of the composition. When the amount of modified brominated epoxy resin added increases, the melting thermal stability becomes very good and no sagging occurs, but on the other hand, the setting property is inhibited and the dimensional stability deteriorates.

In order to further improve the flame retardancy of the composition according to claim (1) of the present invention, an antimony compound such as antimono trioxide or sodium antimonate can be added as a flame retardant auxiliary agent.

Examples of reinforcing fillers used in the present invention include fibrous inorganic substances such as glass fibers, carbon fibers, and potassium titanate fibers, non-fibrous substances such as mica, talc, and kaolin, and fibrous organic substances such as polyphenylene terephthalamide. can do.

If the reinforcing filler is less than 5% by weight, the mechanical strength and heat resistance will be insufficient, but the surface appearance of the molded product will be excellent. 6
At 0 parts % or more, the mechanical strength reaches saturation strength.

The composition of the present invention may contain various additives such as antioxidants, mold release agents, lubricants, antistatic agents, ultraviolet absorbers, colorants, etc. depending on the use and purpose.

The present invention will be explained below with reference to Examples.

■ Production of modified polyethylene terephthalate 2,000 parts of dimethyl terephthalate, 1,4 parts of ethylene glycol
20 parts, disodium p-phenolsulfonate (or disodium 2-naphthol-6-sulfonate)
20 parts, manganese acetate 1.0 part, antimony trioxide 1.
0 part was charged into a reactor and transesterification was carried out at 190°C for 3 hours under a nitrogen stream to distill off most of the methanol.Then, the temperature was raised to 250°C and the pressure was reduced, and the vacuum was 0.5 parts mnHg. A polycondensation reaction was carried out at 270° C. for 4 hours. The obtained polymer was white, had a melting point 1 of 253 to 258°C, and an intrinsic viscosity of 0.62 (or 0.67).

■ Molding of test piece To the modified polyethylene terephthalate resin obtained by the method of ■, tribromopolystyrene, modified brominated epoxy resin, antimony trioxide, aliphatic polyester, and reinforcing filler were added as shown in Tables 1 and 2. The proportions shown in the table were weighed and mixed in a rotating P-ram blender. This mixture was put into a hollow chamber of a 30 yn twin screw extruder, and melted and kneaded at a cylinder temperature of 270-275 to 275°C to form pellets to obtain the flame-retardant resin composition of the present invention. The obtained pellets were sufficiently dried in a hot air dryer at 130°C.
The specimens were molded in an injection molding machine. Molding flexibility is cylinder temperature 275-275-270℃, mold temperature 90℃
℃, molding cycle 45 seconds, injection pressure 300 ~ qsoKt
Molded with p/c7n2.

■ Performance test method for molded products Crystallinity was measured using a differential thermometer (heating and cooling rate 2°/min)
The melting point and crystallization onset temperature were measured using Heat K type r
7M 181 is AsTMD648 (thickness%〃, stress 18
．． 5 to 7 parts cm2), tensile breaking strength HASTMI) 6
38, Izotsu 1i! FJ Ning strength is AS'rMD25
6 (V-/ff) K, +7, measured respectively. Aging resistance was determined by bending strength (ASTMD 790
) was measured. Zolead resistance was determined by leaving a 3M thick extensible test piece in an oven at 130° C. for 96 hours, and then determining the rate of decrease in gloss and visual appearance of the surface. The flame retardance was measured based on the UL9'4 vertical combustion test method, and the size of the test piece was 5" length x % width x 1/16" thickness.

Examples 1 to 12 Disodium p-phenolsulfonate (still, 2-
Polyethylene terephthalate resin modified with disodium naphthol-6-sulfonate), chopped glass strand (1'-03MA429'' manufactured by Asahi Fiberglass Co., Ltd.) with a length of 6 m, tribromopolystyrene (molecular weight 1
35,000, bromine content 68%), modified epoxy resin (polymer of tetranobisphenol A and shrimp chlorohydrin with brominated bisphenol added, molecular weight 7,000).

(bromine content: 52%), antimony trioxide, and polyzotylene adibate (acid value: 0.3, molecular i: 7,000) in the proportions shown in Tables 1 and 2 and subjected to molding.

Tables 1 and 2 show the results of evaluating the melt thermal stability (presence or absence of sagging), crystallinity, thermal properties, mechanical properties, aging resistance, and flame retardancy during injection molding.

The tribromopolystyrene compositions of Comparative Examples 1 to 3 are as follows:
Although it has excellent crystallinity and thermal properties, it has insufficient melt thermal stability and aging resistance.

The modified brominated shrimp 9x compositions of Comparative Examples 4 to 6 have excellent melt thermal stability, mechanical properties, and aging resistance, but have insufficient crystallinity. Comparative Example 70 The decaglomodiphenyl oxide composition had a very large pull-out.

Examples ~5 and 8~12 have melt thermal stability, crystallinity,
A fully satisfactory flame-retardant polyethylene terephthalate resin composition having thermal properties, mechanical properties, severe aging resistance, and flame retardance properties that are well balanced can be obtained.

The following is a margin procedural amendment (voluntary): October-7, 1980 Director General of the Patent Office Kazuo Wakasugi 1 Indication of the case Patent Application No. 2854, 1988
4 No. 2 Name of the invention Flame-retardant polyethylene terephthalate resin composition a Relationship with the case of the person making the amendment Patent applicant 1-2-6-4 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture, subject of amendment” 53.1o, 2 5. Contents of the amendment (1) In the second line of page 14 of the specification, "Examples 1-12" is amended to "Examples 1-ra'J."

(2) In the specification, page 14, lines 12-13, [-antimony trioxide and polybutylene adipate] is amended to "antimony trioxide or sodium antimonate and polybutylene adipate."

(3) In the specification, page 15, line 7, [Examples 1-5 and 8-12°, I is corrected as [Examples 1-5 and 8-13J].

(4) Page 17 (Table 1) of the specification is amended as shown in the attached sheet.

that's all

Claims (4)

[Claims] (1) Modified polyethylene terephthalate 3 modified with a compound represented by the following general formula (1) [■]
5-85% by weight, reinforcing filler 5-60% by weight, aliphatic polyester 1-10% by weight, brominated folystyrene 5-3
A flame-retardant polyethylene terephthalate resin composition consisting of 0% by weight and 0.1 to 30% by weight of a modified brominated epoxy resin, where M and M' are the same or different alkali metals, and n and m are 1 or 2) (2) The aliphatic polyester is composed of an aliphatic dibasic acid and glycosylation having 2 to 8 carbon atoms, has an acid value of 1 or less, and has a molecular weight of 4.
,000 or more polyester (
Composition described in section 1) (3) Brominated polystyrene is represented by the general formula (wherein X is a bromine atom, n is an integer of 58 or more, and m is 1 to 3).
) The composition described in item (4) The general formula n of the modified brominated epoxy resin is 0 in the degree of polymerization.
The composition according to claim (1), which is obtained by adding the above)