JP3301496B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame-retardant resin composition. Molded articles and fiber products obtained from the composition of the present invention are excellent in flame retardancy, low smoke emission, coloring property and the like, and can be widely used for electric parts, automobile parts, machine parts, building materials, clothing and the like.

[0002]

2. Description of the Related Art Synthetic resin molded products and textile products are widely used in industrial parts and materials such as the electronic and electrical industries, the automobile industry, the housing construction industry, the machinery and equipment industry, and the textile and textile industry. From the viewpoint, the demand for flame-retardant and low-smoke emission of these parts and materials is increasing.

[0003] Synthetic resins such as polyethylene, polypropylene, polystyrene, ABS resin, polycarbonate and polyester have the disadvantage that they are easily combustible. Halogen-containing resins such as vinyl chloride are less likely to burn than the above-mentioned synthetic resins. In this case, there is a drawback that smoke is high. Therefore, there are already various additives for making these synthetic resins flame-retardant or flame-retardant with low smoke emission, and various flame-retardant resin compositions have been proposed. Generally, a flame-retardant resin composition is used in which an organic halogen compound and a phosphorus compound or antimony trioxide, antimony pentoxide, antimony pentoxide, and sodium antimonate are mixed with a synthetic resin. Further, a flame-retardant low-smoke-resin composition in which a halogen-containing resin is blended with a zinc compound such as antimony trioxide and zinc borate is employed. For example, JP
JP-A-2-172050 discloses a flame-retardant resin composition in which an organic halogen compound and sodium antimonate anhydride are blended in a polyester resin, and JP-B-50-33904 discloses an organic halogen compound and an antimonic acid in a thermosetting resin. A flame retardant resin composition containing soda is disclosed, and JP-A-60-11543 discloses that polyvinyl chloride resin is selected from antimony trioxide and zinc oxide, zinc sulfide, zinc carbonate and zinc silicate. A flame-retardant low-smoke resin composition comprising at least one zinc compound is disclosed.

[0004]

For resins such as polyethylene, polypropylene, polystyrene, and ABS, a resin composition having good flame retardancy can be obtained by blending an organic halogen compound and antimony trioxide. Is ineffective, and antimony trioxide has the drawback of being strong in whiteness due to its high concealing property and difficult to be colored.

[0005] On the other hand, a resin composition in which an organic halogen compound and antimony pentoxide are blended with the above resin has good coloring properties, but has insufficient flame retardancy and has no effect on low smoke emission. ing. In a resin composition in which an organic halogen compound and antimony trioxide are blended with a thermoplastic polyester, the depolymerization of the polyester is promoted at a normal molding temperature, the thermal stability is significantly reduced, and the mechanical properties of the obtained molded article are reduced. It has the disadvantage of being significantly reduced. Also,
When antimony pentoxide or sodium antimonate anhydride is used in place of antimony trioxide, the depolymerization during molding is suppressed and the thermal stability is good, but the disadvantage that sufficient flame retardancy is difficult to obtain is obtained. Have. In addition, none of the above compositions has an effect on low smoke emission.

A resin composition containing a halogen-containing resin and antimony trioxide or antimony pentoxide has good flame retardancy but does not provide low smoke emission. An object of the present invention is to provide a flame-retardant resin composition in which the above disadvantages are improved.

[0007]

The flame-retardant resin composition of the present invention is used in an amount of from 0.8 to 1.0 based on 100 parts by weight of a synthetic resin containing a halogen-containing synthetic resin or an organic halogen compound.
2, characterized in that 0.5 to 30 parts by weight of anhydrous zinc antimonate having a ZnO / Sb2O5 molar ratio of ₂ and a primary particle diameter of _{5 to} 500 nm is blended. In the present invention, the synthetic resin is a synthetic resin such as a thermoplastic resin, a thermosetting resin or a thermoplastic elastomer, and it is one or two selected from the group consisting of a thermoplastic resin, a thermosetting resin, and a thermoplastic elastomer. The above mixture or alloy is used. These are appropriately selected according to various functions possessed by the synthetic resin depending on the use. Typical examples include thermoplastic resins such as polyethylene, polypropylene, polyvinyl acetate, polystyrene, polybutene, polycarbonate, polyvinyl chloride, polyester, and polysulfone. A copolymer with a monomer or a mixture thereof may be used.

As the thermosetting resin, an epoxy resin,
There are phenolic resins, melamine resins, unsaturated polyester resins, vinyl ester resins, allyl resins, diallyl phthalate resins, and silicone resins. These resins can be used alone or in the form of a copolymer or a mixture. It is possible. As the organic halogen compound used in the present invention, hexabromobenzene, hexachlorobenzene, pentabromobenzene, pentachlorobenzene, pentabromophenol, pentachlorophenol, hexabromobiphenyl, decabromobiphenyl, chlorotetrabromobutane, tetrabromobutane,
Hexabromocyclododecane, perchloropentacyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, ethylenebis-tetrabromophthalimide, tetrachlorobisphenol A, tetrabromobisphenol A, brominated polystyrene, Examples thereof include halogenated polycarbonate, halogenated epoxy compound, brominated polyphenylene oxide, polychlorostyrene, chlorinated paraffin, tetrabromophthalic anhydride, and tetrachlorophthalic anhydride.

In the present invention, properties and uses of the synthetic resin
In consideration of the above, one or two kinds of the organic halogen compounds are used.
The above can be selected and used. None in the present invention
Water zinc antimonate is ZnSb_TwoO₆Or Zn₇Sb
_TwoO ₁₂Do not use structural materials alone or in combination.
But ZnSb _TwoO₆With the structure of
Is preferred.

Anhydrous zinc antimonate is obtained by calcining a mixture of zinc oxide and antimony trioxide at 800 ° C. or higher, zinc oxide, zinc hydroxide or a salt of zinc and antimony pentoxide,
It can be produced by a method of firing a mixture of colloidal antimony oxides such as antimony hexaoxide at 500 to 1100 ° C, a method of firing zinc antimonate hydrate at 500 to 1100 ° C, and the like.

In the present invention, Z of 0.8 to 1.2 is particularly preferred.
After mixing the zinc compound and colloidal antimony oxide nO / Sb ₂ O ₅ molar ratio, preferably anhydrous zinc antimonate primary particle size created is 5~500nm by firing at 500 to 1100 ° C.. Here, the zinc compound is at least one zinc compound selected from the group consisting of zinc hydroxide, zinc oxide, an inorganic acid salt of zinc, and an organic acid salt of zinc. As inorganic acid salts of zinc, zinc carbonate,
Basic zinc carbonate, zinc nitrate and the like can be mentioned. Examples of the organic acid salt of zinc include zinc formate, zinc acetate, zinc oxalate and the like. Anhydrous zinc antimonate obtained by this method can be used as a zinc antimonate ZnSb ₂ O ₆ (ASTM No.
3-0455) and the diffraction peak. In addition, as a result of differential thermal analysis (DTA-TG), no weight loss of this anhydrous zinc antimonate was observed at room temperature to 1000 ° C. Further, as a result of observation with a transmission electron microscope, it was confirmed that the anhydrous zinc antimonate had a primary particle size of 5 to 500 nm and was fine particles of a colloid level.

In the present invention, anhydrous zinc antimonate is generally used as a white to off-white powder, and the particle size is not particularly limited. Anhydrous zinc antimonate produced by the above-mentioned method can be used in a ball mill, a jet-omizer, a pin disk mill, and the like. The average particle diameter of the aggregate obtained by pulverizing by means of 10 μm or less is preferred.

In the flame-retardant resin composition of the present invention, the amount of the organic halogen compound is from 0 to 30 parts by weight based on 100 parts by weight of the synthetic resin. When the synthetic resin is a halogen-containing resin, it is not necessary to add an organic halogen compound.
The organic halogen compound can be added within 30 parts by weight based on parts by weight. In the case of a halogen-free resin, the amount of the organic halogen compound is 2 to 30 parts by weight.

On the other hand, in the flame-retardant resin composition of the present invention, the amount of anhydrous zinc antimonate is 0.5 to 30 parts by weight, preferably 2 to 100 parts by weight of the synthetic resin.
-20 parts by weight. In some cases, the flame-retardant resin composition of the present invention may further contain additives in addition to the above-mentioned components in order to further impart required properties. Examples of these additives include glass fiber, carbon fiber, potassium titanate fiber, wollastonite, glass flake, talc, mica, aluminum hydroxide, magnesium hydroxide, feldspar, calcium carbonate, synthetic mica, silica and the like. Fillers. The amount of addition is synthetic resin 1
It is preferably 50 parts by weight or less based on 00 parts by weight. Other additives include a heat stabilizer, an antioxidant, a crystal nucleating agent, a release agent, a colorant, a processing aid, a lubricant, a surface treatment agent, an ultraviolet absorber, and an antistatic agent.

[0015]

The anhydrous zinc antimonate used in the present invention is a compound of zinc oxide and antimony pentoxide, which functions as a flame retardant aid derived from antimony pentoxide and zinc oxide and as a low smoke generating agent derived from zinc oxide. Has both features. In particular, anhydrous zinc antimonate having a primary particle size of 5 to 500 nm has excellent reactivity with an organic halogen compound at the time of combustion, and therefore exhibits very good flame retardancy and low smoke emission. In particular, it is excellent in the effect of reducing the smoke emission of resins such as vinyl chloride and polystyrene, which have remarkable smoke emission properties.

The zinc antimonate used in the present invention is anhydrous, thermally stable, and neutral because it is a compound of an acidic oxide and a basic oxide. The composition does not cause depolymerization of the resin even when molded at a high temperature, and is excellent in mechanical properties of a molded article or a fiber product of the obtained composition. Further, since anhydrous zinc antimonate used in the present invention has good dispersibility in resin,
The molded article has excellent surface smoothness, and the refractive index of anhydrous zinc antimonate is 1.8 to 1.9, which is larger than the refractive index of antimony pentoxide 1.72, but the refractive index of antimony trioxide is 2.1. Since it is considerably smaller than 2.3, the concealing property is small, and the molded article and the fiber product are excellent in coloring property.

In the flame-retardant resin composition of the present invention, when the synthetic resin is a halogen-free resin, if the compounding amount of the organic halogen compound is less than 2 parts by weight per 100 parts by weight of the resin, sufficient flame retardancy is obtained. On the other hand, if the amount is more than 30 parts by weight, flame retardancy can be obtained, but the mechanical properties of resin molded products and textile products are significantly reduced. If the amount of anhydrous zinc antimonate in the flame retardant resin composition of the present invention is less than 0.5 part by weight per 100 parts by weight of the resin, it is difficult to obtain sufficient flame retardancy and low smoke emission. If the amount is more than the weight part, the mechanical properties and the like of the resin molded product and the fiber product are deteriorated.

[0018]

【Example】

Example 1 (Preparation of anhydrous zinc antimonate) 1300 g of antimony trioxide (manufactured by Sangoku Smelting Co., Ltd.) was dispersed in 5587 g of water, and 953.7 g of 35% hydrogen peroxide solution (reagent) was added. The mixture was heated to 100 ° C. and reacted for 2 hours to obtain an antimony pentoxide sol. The obtained sol has a specific gravity of 1.1.
98, pH 1.80, viscosity 19.5 c. p. , Sb ₂ O
₅ is 18.4% by weight, the particle size of which is 20 to
30 nm, specific surface area by BET method is 55.0 m ² / g
Met. This sol is spray-dried to give a colloidal antimony pentoxide powder (Sb ₂ O ₅ content of 9
0% by weight and an average particle diameter of 3.0 μm).

The above colloidal antimony pentoxide powder 38
A V-type mixer comprising 5.6 g (containing 347 g as Sb ₂ O ₅ ) and 125.2 g (containing 87.6 g as ZnO) of basic zinc carbonate (ZnO content 70% by weight manufactured by Sakai Chemical Industry Co., Ltd.) For 0.5 hour. This mixture had a ZnO / Sb ₂ O ₅ molar ratio of 1.0. Next, this mixture was baked at 700 ° C. for 8 hours in an electric furnace to obtain a white powder. As a result of X-ray diffraction,
The peak coincided with the peak of anhydrous zinc antimonate ZnSb ₂ O ₆ . The obtained anhydrous zinc antimonate powder was pulverized with a pin disc mill to obtain a fine powder having an average particle diameter of 1.2 μm (measured by a centrifugal sedimentation method). This anhydrous zinc antimonate had a primary particle size of 2
0-100 nm, specific surface area by BET method is 25 m ²
/ G.

(Preparation of resin composition) 18 parts by weight of octabromodiphenyl oxide (manufactured by Ethyl Corporation) as an organic halogen compound per 100 parts by weight of high impact polystyrene (HIPS492 manufactured by Asahi Kasei Corporation), and the anhydrous zinc antimonate powder 6 0.0 part by weight was blended to prepare a flame-retardant resin composition. This resin composition was kneaded with a Brabender at 220 ° C. for 10 minutes and molded by a press method to obtain a test piece.

Example 2 Polybutylene terephthalate (1401 manufactured by Toray Industries, Inc.)
-X06) 90 parts by weight and 10 parts by weight of polycarbonate (NOVAREX manufactured by Mitsubishi Kasei Corporation) were added to brominated polystyrene (Pyro Ch manufactured by Ferro Corporation).
eck-68PB) 20 parts by weight and 10 parts by weight of anhydrous zinc antimonate described in Example 1 were mixed in a V-type blender, and the obtained mixture was twin-screw extrusion type S manufactured by Kurimoto Iron Works, Ltd.
The pellets were molded at a cylinder temperature of 260 ° C. using a 1.5 KRC kneader pelletizer.

The pellets were dried at 100 ° C. for 10 minutes, and then dried using an injection molding machine (Meiki Seisakusho M-32).
A test piece was formed by injection molding at a cylinder temperature of 260 ° C. and a mold temperature of 80 ° C. Example 3 Polyvinyl chloride (Toyo Soda Co., Ltd. Neuron 70)
0D, average polymerization degree 1000) 100 parts by weight of dioctyl phthalate (produced by Daihachi Chemical Co., Ltd.) 5 as a plasticizer
0 parts by weight, 1.2 parts by weight of a barium-zinc stabilizer (manufactured by Nissan Ferro-Organic Chemical Co., Ltd.), 1.0 parts by weight of epoxidized soybean oil (manufactured by Adeka Argus Co., Ltd.), antimonic anhydride described in Example 1 7.0 parts by weight of zinc was added and mixed with a Henschel mixer. 170 ° C with hot roll
To prepare a PVC sheet.

Comparative Example 1 Instead of the anhydrous zinc antimonate of Example 1, antimony pentoxide powder (San Epoch NA manufactured by Nissan Chemical Industries, Ltd.)
A test piece was prepared in the same manner and in the same manner as in Example 1 except that -1030) was used. Comparative Example 2 Instead of anhydrous zinc antimonate of Example 2, anhydrous sodium antimonate (Sun Epoque 1 manufactured by Nissan Chemical Industries, Ltd.)
070), except that the test piece was prepared in the same manner and in the same manner as in Example 2.

Comparative Example 3 Instead of the anhydrous zinc antimonate of Example 3, an antimony pentoxide powder (Sun Epoch NA manufactured by Nissan Chemical Industries, Ltd.) was used.
A test piece was prepared in the same manner and in the same manner as in Example 3 except that -1030) was used. The performance test is as follows.

(A) Thermal Stability Test of the Resin Mixture upon Heating and Melting The blend mixed with the above-mentioned V-type blender was mixed with a Brabender Plasticorder.
The change in torque was measured using a coder. The measurement conditions were as follows: temperature setting of the mixer head: 260 ° C., rotation speed: 40 r
pm, the amount of the sample was 65 g, and the torque at the time of kneading for 20 minutes after the sample was charged was read and expressed in units of mg. The results are shown in Table 1.

[0026] (B) Flame retardancy test of resin The flame retardancy test was carried out by using the above-mentioned injection-molded test piece according to the oxygen index method (JIS D1201) and UL-9.
4 (underwriters laboratory standard).

The oxygen index (flame retardancy index) is a percentage of oxygen expressed as a volume percentage in a mixture of oxygen and nitrogen necessary for the test piece to maintain combustion at a temperature of the mixed gas of 20 to 25 ° C. Shown at minimum density. A substance having a high oxygen index value can be said to have high flame retardancy. In the vertical combustion test based on UL-94, test materials can be classified into V-0 to V-2 based on the test results. V-0 is that the burning (flaming) after applying the test flame is 10 seconds or less for all the test pieces, and the combustion (fl) when the test flame is applied 10 times to a set of five test pieces.
The sum of the aging times is less than 50 seconds, and no flaking particles that ignite the cotton placed 12 inches below any of the test pieces will not fall. Also,
V-1 was the combustion (fl) after all test pieces were exposed to the test flame.
aging) is 30 seconds or less, and one of five test pieces
Flaming when the test flame is applied to the set 10 times
The total time is less than 250 seconds and all test pieces are 1
Combustion to ignite the cotton placed 2 inches below (flami
ng) The particles do not fall. V-2 indicates the flaming after all test pieces were exposed to the test flame.
Is less than 30 seconds, the sum of the flaming time when applying a test flame 10 times to one set of five test pieces is 250 seconds or less, and the cotton placed 12 inches below There is a drop of flaming particles that ignite. The results are shown in Tables 2 and 3.

Table 2 Measured values of oxygen index ──────────────────────────────── Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 ──────────────────────────────── 28.9 34.2 30.4 22.8 31.8 29.7 ── ────────────────────────────── Table 3 UL-94 measured values ──────────── ────────────────────── (Total burning time after 10 times flame contact) (Cotton ignition) (Category) ───────── ───────────────────────── Example 1 8.1 seconds No firing V-0 Example 3 1.8 seconds No firing V-0 Comparison Example 1 46.3 seconds Ignition V-2 Comparative Example 3 2.0 seconds No ignition V-0ハ (c) Smoke emission test Burn at an oxygen concentration 0.5 point higher than the measured oxygen index, and visually The amount of smoke was observed. Table 4 shows the results.
It was shown to.

[0029] From the test results of (a) to (c) above, in the comparison between Example 1 and Comparative Example 1, the antimony pentoxide used in Comparative Example 1 was used, and in Example 1, the same amount of anhydrous zinc antimonate was used. It is shown from the measured values of oxygen index or UL-94 that high flame retardancy can be obtained by using.

In contrast to Example 2 and Comparative Example 2, the oxygen index was increased by using anhydrous sodium antimonate used in Comparative Example 2 and the same amount of anhydrous zinc antimonate in Example 2. The measured values show that high flame retardancy can be obtained and that the resin mixture also has excellent thermal stability at the time of heating and melting. In addition, in comparison between Example 3 and Comparative Example 3, antimony pentoxide used in Comparative Example 3 was
In Example 3, by using the same amount of anhydrous zinc antimonate, the measured value of oxygen index or UL-94 shows that the flame retardancy is improved and that the halogen-containing resin has less smoke emission. .

[0031]

The flame-retardant resin composition of the present invention exhibits good flame retardancy and low smoke emission for many resins. Good flame retardancy especially for resins (including mixtures and alloys) that do not provide sufficient flame retardancy with antimony pentoxide or sodium antimonate, such as polyethylene, polypropylene, polystyrene, ABS resin, polycarbonate, and polyester. Show. In addition, it shows good thermal stability for resins that are easily depolymerized when melted, such as polyester. Furthermore, it exhibits good flame retardancy and good low smoke emission with respect to halogen-containing resins such as vinyl chloride and resins having large smoke emission such as polystyrene.

Further, the molded article of the flame-retardant resin composition of the present invention is excellent in surface smoothness, coloring property and the like, and also excellent in mechanical properties. Further, the flame-retardant resin composition of the present invention can be molded by a molding method suitable for the resin used. The molded article and fiber product of the flame-retardant resin composition of the present invention can be used in various fields and can be used as electric parts, automobile parts, machine parts, house building materials, clothing and the like.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-57-2357 (JP, A) JP-A-58-191742 (JP, A) JP-A-62-230844 (JP, A) JP-A-62 151448 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 1/00-101/16 C08K 3/00-13/08

Claims (1)

(57) [Claims] 1. A halogen-containing synthetic resin or an organic halogen.
For 100 parts by weight of the synthetic resin containing the compound , 0.
ZnO / Sb ₂ O ₅ molar ratio of 8 to 1.2, _{5 to} 500 n
of anhydrous zinc antimonate having a primary particle size of 0.5 m
A flame-retardant resin composition containing up to 30 parts by weight.