JPS61246249A - Flame-retardant polyester composition - Google Patents

Abstract

PURPOSE:To obtain a compsn. which has excellent flame retardance and flow characteristics during molding and gives moldings having good appearances and mechanical properties, by blending an organobromine compd., antimony trioxide and sepiolite with an arom. polyester. CONSTITUTION:A compsn. is obtd. by blending 0-200pts.wt. glass fiber (A), 1-60pts.wt. organobromine compd. (B), 1-40pts.wt. antimony trioxide (C) and 0.5-100pts.wt. sepiolite (D) with 100pts.wt. arom. polyester (E). As the arom. polyester, polybutylene terephthalate and polyethylene terephthalate are preferred from the viewpoints of good mechanical properties and moldability. As the organobromine compd., brominated polycarbonates prepd. from tetrabromo bisphenol A whose terminals are blocked with a monohydric phenol such as tribromophenol or copolymers of bisphenol A polycarbonate are preferred.

Description

[Detailed description of the invention] <Industrial application field> The present invention has excellent fluidity during molding, flame retardancy, especially resistance to large particles falling during combustion, and has good mechanical properties and molded product appearance. The present invention relates to a flame-retardant polyester composition.

<Prior Art> Aromatic polyesters, represented by polyethylene terephthalate, polybutylene terephthalate, etc., are being used increasingly in mechanical parts, electrical parts, automobile parts, etc., due to their excellent properties. On the other hand, in addition to the general chemical and physical property balance, these industrial materials also have
There is a strong demand for safety against flames, that is, flame retardancy, and it is no exaggeration to say that at present, imparting flame retardance is an essential condition for expanding the use of aromatic polyesters.

It is well known that an aromatic polyester represented by polybutylene terephthalate (PBT) is used in combination with an organic bromine compound as a flame retardant imparting agent and antimony trioxide as a flame retardant imparting aid. However, although the combustion rate can be suppressed by blending these organic bromine compounds with antimony trioxide, the issue of large particles falling during combustion remains unsolved, and several studies have been conducted. Ta. Among them, JP-A-50-493
The method of using asbestos in combination, as shown in Publication No. 61, is a relatively excellent method.

<Problems to be solved by the invention> However, when the above method is used, there are problems in handling as asbestos itself is a toxic substance, as well as problems such as poor movement during molding and poor appearance of the molded product. There were problems such as inferiority.

As a result of intensive studies to improve the above-mentioned problems in flame retardant aromatic polyester, the inventors of the present invention decided to use sepiolite together with an organic bromine compound flame retardant and antimony trioxide. It has been discovered that this method causes no handling problems, has excellent fluidity during molding, flame retardancy, and especially resistance to large droplets during combustion, and has good mechanical properties and molded product appearance. invention has been achieved.

That is, the present invention comprises: (1) 0 to 200 parts by weight of glass fiber (C) 1 to 60 parts by weight of an organic bromine compound (C) 1 to 40 parts by weight of arthium trioxide/timone, and (2) 0. It relates to a flame-retardant polyester composition characterized in that it contains 5 to 100 parts by weight.

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 containing an aromatic dicarboxylic acid (or its ester-forming derivative).
It is a polymer or copolymer obtained by a condensation reaction mainly consisting of diol and diol (or its ester-forming derivative).

The aromatic dicarboxylic acids mentioned here include terephthalic acid,
Isophthalic acid, orthophthalic acid, 1,5-7thalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,7
-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-pyridinedicarboxylic acid, etc. Terephthalic acid is preferable. Can be 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.
Examples include aliphatic diols such as 3-propanediol, diethylene glycol, and triethylene glycol, alicyclic diols such as 1,4-cyclohexane dimetatool, 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, polytetramethylene glycol, etc., may be copolymerized in a small amount.

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, and polybutylene terephthalate/decanedicarboxylate may be mentioned. Among these, mechanical properties,
Polybutylene terephthalate and polyethylene terephthalate, which have well-balanced moldability, are preferably used.

The aromatic polyester used in the present invention is 0.5
Chi's. - Chlorphenol solution having a relative viscosity of 1.15 to 2.0, particularly preferably 1.3 to 1.85, measured at 25°C.

The glass fiber of component (1) that can be used in the present invention is not particularly limited as long as it is generally used for reinforcing resins, and for example, it can be selected from long fiber type or short fiber type chopped strands, milled fibers, etc. I can do it. 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 epoxy resin, or a coupling agent such as a silane type or titanate type, or other It may be treated with a surface treatment agent.

The amount of glass fiber added is 1 to 200 parts by weight, preferably 5 to 100 parts by weight, per 100 parts by weight of the aromatic polyester.

The organic bromine compound used as component (C) in the present invention has a bromine atom in its molecule, and means a known organic bromine compound that is usually used as a flame retardant. % or more is preferable.

Specifically, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromopyphenyl,
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 or brominated phenoxy compounds (e.g. brominated bisphenol A and Jepoxy compounds, brominated epoxy oligomers, brominated epoxy polymers, brominated phenoxy polymers), poly(brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A1 cyanuric chloride and brominated bisphenol produced by reaction with epichlorohydrin brominated epoxy oligomers and polymers, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate and cyanuric chloride/ Polycondensates of brominated bisphenols are preferred, especially p
A brominated polycarbonate made from tetrabromobisphenol A end-capped with a monohydric phenol such as -tert-butylphenol or trifluorochloride phenol, or a copolymer thereof with bisphenol A polycarbonate can be preferably used.

The amount of these organic bromine compounds Ω added is 1 to 60 parts by weight, preferably 5 parts by weight, per 100 parts by weight of aromatic polyester.
~30 parts by weight. If the amount added is less than 1 part by weight, the flame retardance will be insufficient, but if it exceeds 60 parts by weight, the physical properties of the composition will deteriorate, which is not preferable.

Antimony trioxide used as component (2) 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 1 to 40 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the aromatic polyester.
It is preferable to add one antimony atom per five antimony atoms.

Seviolite, component (2), used in the present invention is a hydrous magnesium silicate whose main component is represented by the following formula (I).

(OH2)4 (OH)4Mg6 St 12030
・6-8 H2O (1) Also, the crystal structure is composed of a porous structure consisting of plate-shaped microcrystals and alternating pores, and is essentially different from asbestos, talc, etc. be.

Seviolite used in the present invention each contains 13 to 33% by weight of magnesium as magnesium oxide and silicon oxide.
, those containing 43 to 63% by weight of silicon are preferable,
Magnesium 18-28% by weight, silicon 48-58%
Those containing % by weight are more preferable. Further, the loss on ignition is preferably 5 to 15%, and each of iron, calcium, potassium, sodium, titanium, etc. may be contained in the form of oxides of several titers or less.

The sepiolite used in the present invention has an average fiber length of 1 to 1
00μ, preferably 3 to 30μ, average fiber diameter 0.01
It is a fibrous material with a diameter of ~0.5μ, preferably 0.05-0.3μ, and an aspect ratio of 10 or more.

The amount of sepiolite used in the present invention is from 0.5 to 100 parts by weight, preferably from 2 to 60 parts by weight, based on 100 parts by weight of the aromatic polyester.

If the amount added is less than 0.5 parts by weight, the resistance to falling of large particles during combustion of the flame-retardant aromatic polyester is insufficient;
If it exceeds 100 parts by weight, the mechanical properties tend to be impaired, and both are not preferred.

Even though sepiolite is fibrous, it has a different composition and crystal structure, so it is not as toxic to the human body as asbestos, and it also has better drop-off resistance and molding fluidity than asbestos.

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/genterpolymer, ethylene/butene-1 copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/glycidyl methacrylate/vinyl acetate copolymer), etc. . Torera has one or two types of additives.
More than one species can be used in combination.

The method for producing the composition of the present invention is not particularly limited, but preferably aromatic polyester, organic bromine compound, antimony trioxide, sepiolite, and if necessary, glass fiber etc. are melt-kneaded using an extruder. One method is to do so.

The polyester 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 more detail below.

Examples 1-4, Comparative Examples 1-3 Polybutylene terephthalate 100 with relative viscosity 1.47
Based on parts by weight, brominated polycarbonate (Kinjin Kasei ■
FG-7500) 20 parts by weight, antimony trioxide 7 parts by weight, glass fiber (chopped strand) 50 parts by weight,
Add 0.3 parts by weight of dilauryl thiopropionate and sepiolite (4 Nido Plus' Takeda Pharmaceutical ■) in the proportions shown in Table 1, mix with a ribbon pre/goo, and then add 40 m
Using an extruder with a φ vent, the mixture was melt-kneaded and pelletized at 250°C. The resulting pellets were then molded using a 2 oz screw in-line injection molding machine set at 250"C at a mold temperature of 80"C, and subjected to ASTM-1 dumbbell, 1/2' wide Izot impact test. A specimen and a combustion test specimen (1/16' x 1/2' x 5') were obtained, respectively. At this time, as a measure of fluidity during molding, the minimum pressure required to completely fill the mold with resin (lower limit molding pressure) was determined.

The appearance of the obtained test piece was observed and UL
Vertical combustion test according to 94 standard, ASTM-D
Tensile test according to 368 standard, ASTM-D25
An Izot impact test was conducted in accordance with 6. The results are shown in Table 1.

For comparison, asbestos (U) is used as a substitute for sepiolite.
An example using Calidria Asbestos RG-144-) manufactured by CC Corporation is also shown.

From the results in Table 1, it is clear that the composition containing sepiolite of the present invention does not cause large particles to fall during the combustion test, has excellent mechanical properties, and has good molded product appearance and fluidity during molding. be.

<Effects of the Invention> The flame-retardant polyester composition of the present invention has excellent fluidity and flame retardancy during molding, particularly resistance to falling branches during combustion, and can produce molded products with good mechanical properties and appearance. can be given.

Claims (1)

Scope of Claims (A) Based on 100 parts by weight of aromatic polyester (B) 0 to 200 parts by weight of glass fiber (C) 1 to 60 parts by weight of organic bromine compound (D) 1 to 40 parts by weight of antimony trioxide and (E) a flame-retardant polyester composition containing 0.5 to 100 parts by weight of Seviolite.