JPH064756B2 - Flame-retardant polyester composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention has excellent fluidity at the time of molding, flame retardancy, particularly resistance to falling of fire particles at the time of combustion, and good mechanical properties and appearance of molded articles. The present invention also relates to a flame-retardant polyester composition having both properties.

<Prior Art> Aromatic polyesters typified by polyethylene terephthalate and polybutylene terephthalate are being widely used for mechanical parts, electric parts, automobile parts and the like by utilizing their excellent properties. On the other hand, in addition to the balance of general chemical and physical properties of these industrial materials,
There is a strong demand for flame safety, that is, flame retardancy, and it is no exaggeration to say that at present, imparting flame retardancy is an essential condition for expanding the applications of aromatic polyesters.

It is well known that an aromatic bromine 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 it is possible to suppress the burning rate by blending these organic bromine compounds and antimony trioxide, it is still unsolved that the dropping of fire particles occurs during burning, and some studies have been made. Came. Above all, JP-A-50-49
The method of using asbestos shown in Japanese Patent No. 361 or the like is a relatively excellent method.

<Problems to be Solved by the Invention> However, when the above method is used, there is a problem in handling because asbestos itself is a toxic substance, and the immobility during molding becomes poor. There were problems such as being inferior.

<Means for Solving Problems> Therefore, the inventors of the present invention have made diligent studies to improve the above problems in flame retarding an aromatic polyester, and as a result, have found that an organic bromine compound-based flame retardant and antimony trioxide have a specific water content. By using magnesium silicate, there are no problems in handling, it has excellent fluidity at the time of molding, flame retardancy, especially resistance to dropping of fire particles at the time of combustion, and has good mechanical properties and the appearance of molded products. The present invention has been discovered and the present invention has been reached.

That is, the present invention relates to (A) 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) (OH ₂ ) ₄ (OH) ₄ Mg ₈ Si ₁₂ O ₃₀ 6 to 8H ₂ O 0.5 to 100 parts by weight of hydrous magnesium silicate It relates to a polyester composition.

The (A) aromatic polyester used in the present invention is a polyester having an aromatic ring in a polymer chain unit, and is 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 a condensation reaction containing as a main component.

The aromatic dicarboxylic acid referred to here is terephthalic acid,
Isophthalic acid, orthophthalic acid, 1.5-naphthalenedicarboxylic acid, 2.6-naphthalenedicarboxylic acid, 2.7
-Naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4 ,.
4'-diphenyletherdicarboxylic acid, 4.4'-diphenylmethanedicarboxylic acid, 4.4'-diphenylsulfonedicarboxylic acid, 4.4'-diphenylisopropylidenedicarboxylic acid, 1.2-bis (phenoxy) ethane-4.4 ′ -Dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4 ·
4 ″ -p-phenylenedicarboxylic acid, 2.5-pyridinedicarboxylic acid and the like, and terephthalic acid can be preferably used.

You may use these aromatic dicarboxylic acid in mixture of 2 or more types. If it is a small amount, it is possible to mix and use one or more adipic acid, azelaic acid, sebacic acid, aliphatic dicarboxylic acid such as dodecanedioic acid, and alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid together with these aromatic dicarboxylic acids. it can.

As the diol component, ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1.
Aliphatic diols such as 3-propanediol, diethylene glycol, and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and the like, and a mixture thereof or the like can be given. One or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like may be copolymerized as long as the amount is small.

Specific aromatic polyesters include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexylene terephthalate,
In addition to polyethylene naphthalate, polybutylene naphthalate, polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate, polybutylene terephthalate / Copolymerized polyesters such as decane dicarboxylate may be mentioned. Among these, polybutylene terephthalate and polyethylene terephthalate having well-balanced mechanical properties and moldability can be preferably used.

The aromatic polyester used in the present invention is 0.5%
The o-chlorophenol solution having a relative viscosity of 1.15 to 2.0, particularly 1.3 to 1.85, is preferable.

The glass fiber of the component (B) that can be used in the present invention is not particularly limited as long as it is generally used for reinforcing a resin, for example, long fiber type or short fiber type chopped strand, selected from milled fiber, etc. Can be used. Further, the glass fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, a silane-based or titanate-based coupling agent, or other It may be treated with a surface treatment agent.

When glass fiber is added, the amount is 1 to 200 parts by weight, and more preferably 5 to 100 parts by weight, based on 100 parts by weight of the aromatic polyester.

The organic bromine compound used as the component (C) in the present invention has a bromine atom in the molecule, and means a known organic bromine compound which is usually used as a flame retardant, and particularly has a bromine content of 20% by weight. The above is preferable.
Specifically, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl,
Hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy)
Low molecular weight organic bromine compounds such as ethane, ethylene bis- (tetrabromophthalimide), tetrabromobisphenol A, brominated polycarbonate (for example, a polycarbonate oligomer produced from brominated bisphenol A as a raw material), brominated epoxy or brominated phenoxy compound (For example, a diepoxy compound produced by the reaction of brominated bisphenol A and epichlorohydrin, a brominated epoxy oligomer, a brominated epoxy polymer, a brominated phenoxy polymer), poly (brominated benzyl acrylate), brominated polyphenylene ether, bromine Bisphenol A, cyanuric chloride, brominated bisphenol condensate, halogenated polymers and oligomers such as brominated polystyrene, and mixtures thereof. Among them, bromine Epoxy oligomers and polymers, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate and polycondensate of cyanuric chloride / brominated bisphenol are preferable, p-te
A brominated polycarbonate obtained by using tetrabromobisphenol A end-capped with a monovalent phenol such as rt-butylphenol or tribromophenol as a raw material or a copolymer with the bisphenol A polycarbonate can be preferably used.

The amount of the organic bromine compound (C) added is 1 to 60 parts by weight, preferably 5 parts by weight, per 100 parts by weight of the aromatic polyester.
~ 30 parts by weight. If the amount added is less than 1 part by weight, the flame retardancy is not sufficient, and if it exceeds 60 parts by weight, the physical properties of the composition deteriorate, which is not preferable.

The antimony trioxide used as the component (D) in the present invention is not particularly limited as long as it is usually used as a flame retardant aid for polyester. Further, zirconium oxide, zinc sulfide, barium sulfate or the like may be used together 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.

The hydrous magnesium silicate used as the component (E) in the present invention is hydrous magnesium silicate whose main component is represented by the following formula (I).

(OH ₂ ) ₄ (OH) ₄ Mg ₈ Si ₁₂ O ₃₀ 6-8H ₂ O (I) In addition, the crystal structure is composed of a plate-like fine crystal part and a porous structure composed of alternating repeating pores. Cage,
It is essentially different from asbestos and talc.

The hydrous magnesium silicate used in the present invention contains magnesium oxide as magnesium oxide and magnesium as silicon oxide of 13 to 13%, respectively.
Those containing 33% by weight and 43 to 63% by weight of silicon are preferable, and those containing 18 to 28% by weight of magnesium and 48 to 58% by weight of silicon are more preferable. Also,
The reinforcing weight loss is preferably 5 to 15%, and iron, calcium, potassium, sodium, titanium and the like may each be contained as oxides of several% or less.

The hydrous magnesium silicate used in the present invention is a fibrous material having an average fiber length of 1 to 100 µ, preferably 3 to 30 µ, and an average fiber diameter of 0.01 to 0.5 µ, preferably 0.05 to 0.3 µ, and an aspect ratio. Is preferably 10 or more.

The amount of hydrous magnesium silicate used in the present invention is 0.5 to 1 with respect to 100 parts by weight of the aromatic polyester.
The amount is 00 parts by weight, preferably 2 to 60 parts by weight. If the amount added is less than 0.5 parts by weight, the drop resistance of the fire particles during combustion of the flame-retardant aromatic polyester is insufficient, and if it exceeds 100 parts by weight, the mechanical properties tend to be impaired. ,
Neither is preferable.

Since hydrous magnesium silicate has a different composition and crystal structure even if it is fibrous, it does not show toxicity to human body like asbestos, and has more resistance to drop of fire particles and molding fluidity than asbestos.

The composition of the present invention, to the extent that the object of the present invention is not impaired,
Conventional additives such as UV absorbers, lubricants, mold release agents, colorants including dyes and pigments, antioxidants, other thermoplastics (eg polyethylene, polypropylene, ethylene / propylene copolymers, ethylene / propylene / A diene terpolymer, an ethylene / butene-1 copolymer, an ethylene / glycidyl methacrylate copolymer, an ethylene / glycidyl methacrylate / vinyl acetate copolymer) and the like can be further contained. 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 it is preferable to use an aromatic polyester, an organic bromine compound, antimony trioxide, hydrous magnesium silicate and, if necessary, an extruder such as glass fiber. A method of melting and kneading is exemplified.

The polyester composition of the present invention can be easily molded by a usual method such as injection molding or extrusion molding, and the obtained molded product exhibits excellent properties.

<Example> Hereinafter, the effect of the present invention will be described in more detail with reference to examples.

Examples 1-4, Comparative Examples 1 to 4 100 parts by weight of polybutylene terephthalate having a relative viscosity of 1.47 was added to brominated polycarbonate (Teijin Chemicals Ltd.).
FG-7500) 20 parts by weight, antimony trioxide 7 parts by weight, glass fiber (chop strand) 50 parts by weight,
0.3 parts by weight of dilauryl thiopropionate and hydrous magnesium silicate (“Adeplus” Takeda Pharmaceutical Co., Ltd.)
Was added at a ratio shown in Table 1, mixed with a ribbon blender, and melt-kneaded-pelletized at 250 ° C. using a 40 ^mmφ vented extruder. 25 of the pellets obtained
Molded at a mold temperature of 80 ° C using a 2 ounce screw in-line type injection molding machine set at 0 ° C, and
No. 1 dumbbells, 1/2 ″ wide Izod impact test pieces and combustion test pieces (1 × 16 ″ × 1/2 ″ × 5 ″) were obtained. At this time, as a measure of fluidity during molding, the minimum pressure (molding lower limit pressure) required to completely fill the resin in the mold was determined.

Appearance observation and UL
Vertical combustion test according to 94 standard, ASTM-D
A tensile test according to 368 standard, ASTM-D25
An Izod impact test was conducted according to No. 6. The results are shown in Table-1.

For comparison, instead of hydrous magnesium silicate, asbestos (made by UCC, Calidria Asbestos RG-14
An example using 4) is also shown.

For further comparison, also combined example using hydrous magnesium silicate (sepiolite) present in serpentinite rocks represented by _{Mg 8 H 2 Si 12 O 33} · 3H 2 O.

From the results shown in Table-1, the composition containing the hydrous magnesium silicate of the present invention has no drop of fire particles at the time of the combustion test, has excellent mechanical properties, and has good appearance of molded articles and good fluidity at the time of molding. It is clear.

Further, Comparative Example 4 is not preferable because the resistance to drop of fire particles at the time of combustion, the mechanical characteristics, and the molding fluidity are poor.

<Effects of the Invention> The flame-retardant polyester composition of the present invention is a molded article having excellent fluidity at the time of molding, flame retardancy, particularly resistance to dropping of fire particles during combustion, and good mechanical properties and appearance. Can be given.

Claims (1)

[Claims] 1. (A) 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) (OH ₂ ) ₄ (OH) ₄ Mg ₈ Si ₁₂ O ₃₀ · 6 to 8H ₂ O 0.5 to 100 parts by weight of hydrous magnesium silicate Polyester composition.