JPH03296560A - Flame-retarding aromatic polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which does not drip even when burnt and prevents fire propagation by mixing an aromatic polyester with a bromine compound, an antimony compound and a fibrous basic magnesium sulfate compound. CONSTITUTION:100 pts.wt. aromatic polyester (e.g. polybutylene terephthalate) is mixed with 5-40 pts.wt. bromine compound (e.g. brominated polycarbonate), 1-20 pts.wt. antimony compound (e.g. antimony trioxide) and 1-100 pts.wt. fibrous basic magnesium sulfate compound (MgSO4.5MgO.8H2O). The title composition improved in combustibility)especially the prevention of dripping on burning and fire propagation by drips without detriment to the appearance and mechanical properties of a molding can be obtained.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention is a flame retardant material that improves flammability, particularly the falling of large particles during combustion and the combustibility caused by large particles, without impairing the appearance and mechanical properties of molded products. The present invention relates to aromatic polyester resin compositions.

<Prior Art> Aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate are used in electrical and electronic parts, automobile parts, etc., taking advantage of their various excellent properties, and their usage and applications are expanding. However, as the environments in which each component is used become more diverse and harsh, the required characteristics of the industrial materials used in these components are also changing year by year.

One of its properties is flame retardancy, and it is becoming essential to impart flame retardancy to aromatic polyesters as well. Moreover, it has become important not only to simply suppress combustibility, but also to prevent large particles from falling due to combustion and the resulting combustion of combustible materials such as cotton dust inside the device.

Various studies have been conducted to impart flame retardancy to aromatic polyesters such as polybutylene terephthalate and polyethylene terephthalate. A technique is known in which an antimony compound typified by antimony trioxide is used in combination as a flame retardant additive (Japanese Patent Application Laid-open Nos. 49-14563 and 1986-865).
50, JP-A-51-73555, etc.).

However, by blending these bromine compounds and antimony compound 7, it is possible to suppress the burning speed of the composition, but it is also possible to suppress and prevent the falling of large particles due to combustion, and prevent the spread of fire due to large particles. It is difficult to do so, and several studies have been made.

As a method for preventing and suppressing the falling of large particles, Japanese Patent Laid-Open No. 5
Methods of using asbestos as shown in JP-A No. 0-49361, JP-A No. 61-246248 and JP-A-6
There are methods that utilize specific active particles as shown in Japanese Patent No. 1-246249, and methods that utilize reactive compounds and compounds that have the effect of suppressing the decomposition of polyester due to combustion.

<Problems to be Solved by the Invention> However, when the above method is used, there are various practical problems as follows. First, the use of asbestos
Asbestos itself is a toxic substance, which poses problems in handling, and because it is in the form of fibers, there are problems such as poor fluidity during molding and poor appearance of molded products.

In addition, although methods using specific active particles are effective with a certain degree of mixing, the particles themselves have an almost spherical shape, and depending on the composition, there is a risk of losing mechanical strength. These techniques are effective for glass fiber-reinforced compositions, as seen in the examples in these patent publications, but compositions that do not contain fibrous reinforcing agents such as glass fibers have a poor effect on preventing large particles from falling, and There was a problem in that the large grains caused the burning. Furthermore, when the molecular weight of the aromatic polyester used is low, the effect of preventing large particles from falling tends to be poor.

Furthermore, when using reactive compounds or decomposition inhibitors, the properties of the composition may change depending on the production conditions and special storage conditions during use, making it impossible to obtain uniform properties and, in some cases, causing molding. There was a problem that the stability and fluidity of the product were significantly impaired.

<Method for solving the problem> As a result of intensive studies to improve the above-mentioned problems in making aromatic polyester flame retardant, the present inventors have developed an organic bromine compound-based flame retardant or a polymeric bromine compound-based flame retardant. Along with antimony compounds such as fuel and antimony dioxide,
By using a fibrous basic magnesium sulfate compound, there are no handling problems, and while maintaining and improving the fluidity, mechanical properties, and appearance of the molded product during molding, it also has flame retardancy, especially preventing and suppressing large particles from falling during combustion. The present inventors have discovered that the large grains can provide the effect of preventing the spread of fire, and have arrived at the present invention.

That is, the present invention comprises: (^) 100 parts by weight of an aromatic polyester, (B) 5 to 40 parts by weight of a bromine compound, (C) 1 to 20 parts by weight of an antimony compound, and (D) 1 part by weight of a fibrous basic magnesium sulfate compound. The present invention relates to a flame-retardant aromatic polyester resin composition, characterized in that it contains up 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 that undergoes a condensation reaction mainly consisting of 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.

The aromatic dicarboxylic acids used here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
2,7-naphthalenedicarboxylic acid, 4,4°-biphenidicarboxylic acid, 3゜3゛-biphenyldicarboxylic acid, 4
, 4゛-diphenyl ether dicarboxylic acid, 4,4°-
Diphenylmethanedicarboxylic acid, 4,4''-diphenylsulfonedicarboxylic acid, 4,4°-diphenylsulfidedicarboxylic acid, 4,4゛-diphenylisopropylidenedicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid etc., and their ester-forming derivatives, among which terephthalic acid or its dialkyl ester can be preferably used.

Two or more of these aromatic dicarboxylic acids may be used in combination. Further, a part of the aromatic dicarboxylic acids can be replaced with aromatic tricarboxylic acids such as trimellitic acid, aromatic tetracarboxylic acids such as pyromellitic acid, and biphenyltetracarboxylic acid.

If the amount is small, one or more types of aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and dodecanedioic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used in combination with these aromatic dicarboxylic acids. You can also do it.

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-cyclohexanedimetatool, and mixtures and ester-forming derivatives thereof.

In addition, if it is a small amount, long chain diols with a molecular weight of 400 to 6000 (polyethylene glycol, poly 1,3-propylene glycol, polytetramethylene glycol, etc.)
You may copolymerize one or more types.

Specific examples of aromatic polyesters include polybutylene terephthalate, polyethylene terephthalate, polyhexylene terephthalate, polypropylene terephthalate, poly-14-cyclohexylene dimethylene terephthalate, as well as polyethylene terephthalate/isophthalate, polybutylene terephthalate/ Examples include copolymerized polyesters such as isophthalate. Among these, polybutylene terephthalate, polyethylene terephthalate, and derivatives thereof, which have well-balanced mechanical properties and moldability, are most preferably used.

The aromatic polyester used in the present invention is not particularly limited in its properties, but has an intrinsic viscosity of 0.6 to 2.0 when measured at 30°C using a mixed solvent of equal amounts of phenol and tetrachloroethane. It is preferable to use

The bromine compound used as a flame retardant in the present invention has a bromine atom in its molecule, and means a known organic or polymeric bromine compound that is usually used as a flame retardant. is preferably 20% by weight or more. If the bromine content is less than 20% by weight, the flame retardant effect will be small, and not only will the amount of flame retardant itself be increased, but also the amount of flame retardant aid will be required, which will have an adverse effect on mechanical properties, etc. There is a fear.

Specific examples of bromine compounds include hexabromobenzene,
Low molecular weight organic bromine compounds such as pentabromotoluene, hexabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, ethylene bis-(tetrabromophthalimide), tetrabromobisphenol A, brominated bisphenol A Brominated polycarbonate compounds such as polycarbonate oligomers produced using polycarbonate oligomers as raw materials and their copolymers with bisphenol A, jepoxy compounds produced from brominated bisphenol A and epichlorohydrin, and monomers produced from brominated phenols and epichlorohydrin. Examples include brominated epoxy compounds such as epoxy compounds, brominated acrylic compounds such as poly(brominated benzyl acrylate), brominated polymer compounds such as brominated polyphenylene ether, brominated polystyrene, and mixtures thereof. Among them, brominated epoxy oligomers, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated acrylic compounds, etc. are preferred, and brominated polycarbonate terminal-capped with bulk tert-butylphenol, tribromophenol, etc. is particularly preferred.

The amount of these bromine compounds added is
00 parts by weight, 5 to 40 parts by weight, preferably 10 to 3 parts by weight
0 parts by weight, more preferably 15 to 25 parts by weight.

If the amount added is less than 5 parts by weight, the flame retardance, especially the combustion time, will not be sufficiently short, and if it exceeds 40 parts by weight, the physical properties of the composition will deteriorate, which is not preferable.

The antimony compound used as a flame retardant aid in the present invention is not particularly limited as long as it is a compound commonly used as a flame retardant aid for aromatic polyesters. Specific examples of antimony compounds include antimony dioxide, antimony tetroxide, and antimony pentoxide, with antimony trioxide being particularly preferred. Further, zirconium oxide, zinc sulfide, barium sulfate, etc. may be used in combination with these antimony compounds.

The antimony compound used in the present invention preferably has an average particle size in the range of 0.1 to 10 nm. When the average particle size is less than 0.1n, it is difficult to sufficiently disperse it in the polymer using normal mixing methods.
This is not preferable because it causes deterioration of mechanical properties and non-uniformity of flame retardancy. Further, those having an average particle size exceeding 1 On are not preferable because they exist as foreign matter in the composition, leading to a decrease in impact strength and a decrease in the flame retardant effect.

The amount of the antimony compound added in the present invention is 1 to 20 parts by weight, preferably 5 to 15 parts by weight, per 100 parts by weight of the aromatic polyester, particularly with respect to 100 parts by weight of bromine atoms in the brominated flame retardant used at the same time. It is preferable to use it in a range of 40 to 100 parts by weight. If the antimony compound is less than 1 part by weight, a sufficient flame retardant effect cannot be exhibited;
If the antimony compound exceeds 20 parts by weight, the mechanical strength, especially the impact strength, of the composition decreases, which is not preferable.

The fibrous basic magnesium sulfate compound used in the present invention is a white inorganic high-strength single crystal fiber (whisker) produced using magnesium hydroxide as a raw material.
It is a compound represented by the molecular formula of SOa.5Mg0.8H20.

This fibrous basic magnesium sulfate compound has a reinforcing effect because it has a fibrous shape, and has a flame retardant effect because it has water of crystallization in its molecules, and also has a fine fiber diameter that makes it difficult to use in compositions. It also has the effect of improving the surface of molded products.

The amount of the fibrous basic magnesium sulfate compound added in the present invention is 1 to 1 per 100 parts by weight of the aromatic polyester.
00 parts by weight, preferably 1 to 50 parts by weight, particularly preferably 2 to 20 parts by weight.

If the amount of the fibrous basic magnesium sulfate compound added is less than 1 part by weight, no flame retardant improvement effect will be observed, and if it exceeds 100 parts by weight, fluidity will be markedly deteriorated and molding will become difficult.

The fibrous basic magnesium sulfate compound is a fibrous compound with water of crystallization, but the temperature is 350°C1, especially 400°C.
If it exceeds C, it has the property of releasing crystal water and irreversibly losing its fibrous form and losing its reinforcing properties and flame retardant effect.
When the temperature exceeds ℃, the fibrous form is preserved, but water is partially released. Therefore, when adding this fibrous basic magnesium sulfate compound for the purpose of the present invention, 300'
It is necessary to use the temperature below 280°C, preferably below 280°C.

Various commonly used fillers can be used in the composition of the present invention as long as the purpose of the present invention is not impaired. Examples of materials that can be used include glass fibers, carbon fibers, aluminum fibers, stainless steel fibers, metal fibers such as brass fibers, inorganic fibrous compounds such as silicon nitride whiskers, potassium titanate whiskers, and aluminum silicate whiskers, glass flakes, mica, talc, kaolin,
Examples include inorganic fillers such as wollastonite, calcium carbonate, and titanium oxide, and organic fillers such as aramid fibers and powdered epoxy compounds, with glass fibers being particularly preferred.

The amount of filler that can be used in the present invention varies depending on its type, but for example, in the case of glass fiber, it is 0 to 200 parts by weight, preferably 0 to 150 parts by weight, and more preferably 0 to 150 parts by weight, based on 100 parts by weight of aromatic polyester. It is 0 to 120 parts by weight.

Furthermore, various commonly used additives can be used in the composition of the present invention as long as they do not impair the purpose of the present invention. Examples of what can be used include: ultraviolet absorbing side;
Examples include lubricants, mold release agents, heat stabilizers, colored sides containing dyes and pigments, and the like.

Furthermore, other thermoplastic resins can be used in the composition of the present invention as long as they do not impair the purpose of the present invention. Examples of things that can be used include polyolefins such as polyethylene and polypropylene, polyolefin copolymers,
Examples include styrene copolymers, polycarbonates, and polyphenylene ethers. Furthermore, two or more of these fillers, additives, and thermoplastic resins may be used in combination.

The method for producing the composition of the present invention is not particularly limited, but aromatic polyesters, organic bromine compounds or organic polymeric bromine compounds, antimony compounds, fibrous basic magnesium sulfate compounds, and various Examples include a method of melt-kneading additives and fillers using an extruder. In this case, it is desirable to keep the temperature during kneading at 280°C or less, and furthermore, feed a fibrous basic magnesium sulfate compound from the middle of the kneader together with a fibrous filler such as glass fiber to prevent the fibers from breaking. It is desirable to reduce the

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 are given below to explain the effects of the invention in detail.

The fibrous basic magnesium sulfate compound used in this experiment was manufactured by Ube Industries, Ltd. (trade name: Moss-Hide, average fiber length 10 to 100 n, average fiber diameter 1 p or less) (hereinafter abbreviated as Moss-Hide).

In evaluating the Examples and Comparative Examples, the following method was used.

(1) Kneading Kneading was performed using a 35 sφ vented twin-screw extruder. As for raw materials, unless otherwise specified, a bromine compound, an antimony compound, a fibrous basic magnesium sulfate compound, and other additives were stirred and mixed in a Henschel mixer, and the mixture was supplied separately from the aromatic polyester in the same mouth. Moreover, the glass fiber was supplied from the middle of the extruder. The temperature, rotation speed, and throughput of the kneader are such that the extruder outlet temperature of the resin composition is 260°C.
I set it so that it was below 'C.

(2) Next, pre-mix the obtained resin composition pellets 2
The required specimens were molded in an injection molding machine set at 50°C. The temperature of the mold used for molding was 80°C.

(3) Evaluation The evaluation was based on the following items.

(3)-1, according to flammability UL-94 standard, 127Iax12.7mmX0
．． A vertical combustion test was conducted on a 78 mm strip specimen.

(3) -2. Appearance of molded product The surface of each test piece was visually observed, and the presence or absence of surface roughness and patterns was relatively evaluated.

(3) -3. Tensile Test A tensile test was conducted using an ASTM I dumbbell according to ASTM D63 B, and the strength at break and elongation were measured.

(3) -4, Bending test according to ASTM D790, 127m+X 12°7peng×
A three-point bending test was conducted using a strip-shaped test piece of 6.311II11 at a distance between fulcrums of 100Illfll and a test speed of 2.5 m+/min, and the bending strength and bending elastic modulus were measured.

(3)-5. Impact Test According to ASTM D256, the impact strength with a notch was measured using a 3.2 m thick Izot impact test piece.

Examples are shown below.

Examples 1-5 Polybutylene terephthalate 100 with intrinsic viscosity 1.13
Based on parts by weight, 23 parts by weight of brominated polycarbonate (BC-58 manufactured by Great Lake Chemicals), 7 parts by weight of antimony trioxide with an average particle diameter of IIFM, Moshyge 2
A composition consisting of ~20 parts by weight and 50 parts by weight of glass fiber was evaluated.

Comparative Example 1 Comparative Example 1 except that the amount of Moshyge added was 0.5 parts by weight
- Evaluation was made in the same manner as in 5.

Comparative Examples 2 to 6 Asbestos, powdered phenol resin (manufactured by Kanebo ■, product name: Bell Pearl R-800), aluminum silicate whiskers (manufactured by Shikoku Kasei ■, product name: Arborex), potassium titanate whiskers instead of Moiheidi (manufactured by Titan Kogyo ■), talc (manufactured by Fuji Talc ■), average particle size 5-6
Evaluations were made in the same manner as in Examples 1 to 5, except that 5 parts by weight of each of n) were used based on 100 parts by weight of polybutylene terephthalate.

Example 6 Evaluation was carried out in the same manner as in Example 3, except that Moshyge was fed from the middle of the extruder in the same way as the glass fibers.

Example 7 Evaluation was carried out in the same manner as in Example 3 except that polybutylene terephthalate having an intrinsic viscosity of 0.85 was used in place of the polybutylene terephthalate used in Examples 1 to 5.

Comparative Example 7 Evaluation was carried out in the same manner as in Comparative Example 3 except that polybutylene terephthalate having an intrinsic viscosity of 0.85 was used instead of the polybutylene terephthalate used in Comparative Example 3.

Examples 8 to 11 Evaluations were made in the same manner as in Example 3, except that the amount of glass fiber added was 15 to 120 parts by weight per 100 parts by weight of polybutylene terephthalate.

Example 12.13 Evaluation was carried out in the same manner as in Example 3.4 except that the glass fibers were omitted.

Comparative Example 8.9 In Example 12, asbestos and powdered phenol resin (manufactured by Kanebo ■, trade name: Belbar R-
Evaluation was conducted in the same manner as in Example 2 except that 800) was used.

These results are shown in Table 1.

From the results in Table 1, it is clear that the composition containing the fibrous basic magnesium sulfate compound of the present invention has the effect of preventing or suppressing the falling of large particles during combustion, or preventing the spread of fire due to large particles. It is clear that the material has excellent physical properties and molded product appearance.

<Effects of the Invention> The flame-retardant polyester resin composition of the present invention has the effect of preventing and suppressing the falling of large particles during combustion, or preventing the occurrence of secondary fire due to large particles, and has excellent mechanical properties and molded products. It is possible to give a molded article with an appearance.

Claims (1)

Scope of Claims: (A) 100 parts by weight of aromatic polyester, (B) 5 to 40 parts by weight of bromine compound, (C) 1 to 20 parts by weight of antimony compound, and (D) 1 part by weight of fibrous basic magnesium sulfate compound. A flame-retardant aromatic polyester resin composition, characterized in that it contains ~100 parts by weight.