JPH11158329A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant resin composition having high flame retardancy (UL-94, 1/32 inch, V-O), exhibiting good heat-resistance to cause little scorch in molding and giving a molded article with little bleed-out. SOLUTION: This resin composition is composed of (A) 100 pts.wt. of a polyolefin resin, (B) 1-30 pts.wt. of a mixture of (b1) bis(2,3-dibromopropyl) ether of tetrabromobisphenol A and (b2) bis(2,3-dibromopropyl) ether of tetrabromobisphenol S or (b3) tris(2,3-dibromopropyl) isocyanurate, (C) 0.5-20 pts.wt. of antimony oxide and (D) 0.05-2 pts.wt. of a hydrotalcite. The mixing weight ratio of (b1):(b2) or (b1):(b3) is 1:9 to 9:1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition. And a flame-retardant resin composition useful for molding molded articles made of a flame-retardant polyolefin material, such as a substrate holder.

[0002]

2. Description of the Related Art Polyolefins are used in a wide range of fields as molding materials, taking advantage of their excellent properties.
Since polyolefin is flammable, flame retardancy is often required for use as an industrial material. Heretofore, as a method for flame retarding polyolefins, a method of adding various halogen compounds such as decabromodiphenyl oxide has been proposed. There are few resin compositions which show a combustion effect.

As a method for imparting flame retardancy to polyolefins, bis (2,3-dibromopropyl) ether of tetrabromobisphenol A and bis (2,3-dibromopropyl) ether of tetrabromobisphenol S are used as flame retardants. To improve the bleeding property of a molded article by using
Publication) and bis (2,3-dibromopropyl) ether of tetrabromobisphenol A and bis (2,3-dibromopropyl) of tetrabromobisphenol S
A method of blending an aluminum salt of a fatty acid with a mixture with ether (Japanese Patent Application Laid-Open No. 9-87437) has been proposed. However, these flame-retardant resin compositions cannot be said to have sufficient heat resistance, and therefore have a problem that burning tends to occur during molding.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and provides a high degree of flame retardancy (UL-94, UL-94, UL-94).
/ 32 inches, V-0), and has good heat resistance, so that the object is to provide a flame-retardant resin composition which is less likely to burn during processing and has less bleed-out in a molded product.

[0005]

The inventors of the present invention have conducted intensive studies and found that the polyolefin-based resin contains bis (2,3-dibromopropyl) of tetrabromobisphenol A.
By adding a specific amount of hydrotalcites to a mixture of ether and bis (2,3-dibromopropyl) ether of tetrabromobisphenol S or tris (2,3-dibromopropyl) isocyanurate, only flame retardancy is obtained. It was found that a resin composition having improved heat resistance was obtained, and the present invention was completed. That is, the present invention provides (A) 100 parts by weight of a polyolefin resin,
(B) (b1) bis (2,4-tetrabromobisphenol A)
3- (dibromopropyl) ether and bis (2,3-dibromopropyl) of (b2) tetrabromobisphenol S
Ether or (b3) tris (2,3-dibromopropyl)
1 to 30 parts by weight of a mixture with isocyanurate and (C)
Consisting of 0.05 to 2 parts by weight of hydrotalcites, (b1)
It is an object of the present invention to provide a flame-retardant resin composition wherein the mixing ratio of the component and the component (b2) or the mixing ratio of the component (b1) and the component (b3) is 1: 9 to 9: 1 by weight.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the resin composition of the present invention,
Examples of the polyolefin resin of the component (A) include a polypropylene resin, a polyethylene resin, a polybutene resin, and a polypentene resin. Examples of the polypropylene resin include propylene homopolymer (polypropylene) and propylene. A copolymer as a component is exemplified.

The above-mentioned copolymer includes, for example, a propylene / α-olefin copolymer, and the α-olefin includes, for example, ethylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-butene, 1-
Penten and the like.

Examples of the polyethylene resin include an ethylene homopolymer (polyethylene) and a copolymer containing ethylene as a main component.

Examples of the copolymer include ethylene / α-olefin copolymers, and examples of the α-olefin include 1-hexene, 4-methyl-1-pentene, 1-octene and 1-octene. Butene, 1-pentene and the like.

Other polyolefin resins include, for example, ethylene / vinyl acetate copolymer and ethylene / ethyl acrylate copolymer.

The polyolefin resin used in the present invention may be a mixture of the above polyolefin resins. In the present invention, polypropylene is particularly preferred, and from the viewpoint of obtaining good injection moldability and physical properties, 230
The flow rate measured under conditions of 2.16 kg at 1 ° C is 1 to 7.
A polypropylene of 0 is particularly preferred.

The component (B) includes (b1) bis (2,3-dibromopropyl) ether of tetrabromobisphenol A and (b2) bis (2,3-
A mixture of (b1) bis (2,3-dibromopropyl) ether of tetrabromobisphenol A and (b3) tris (2,3-dibromopropyl) isocyanurate. (b1) component and (b
The mixing ratio of the component (2) or the component (b1) and the component (b3) is 1: 9 to 9: 1 by weight, but is 5: 5 to 7: 3.
Is preferred. When the proportion of the component (b1) exceeds 9, the bleeding property of the molded article deteriorates, and when the proportion of the component (b2) exceeds 9, the moldability (workability) deteriorates. Will be expensive. In addition, the molding processability deteriorates because the melting point of bis (2,3-dibromopropyl) ether of tetrabromobisphenol S of the component (b2) is extremely lower than that of the polyolefin resin of the component (A). b2) The reason for this is that as the amount of the component increases, the slip of the screw of the molding machine increases. On the other hand, if the proportion of the component (b3) exceeds 9, the bleeding property is undesirably deteriorated.

The compounding amount of the component (B) is 1 to 30 parts by weight, preferably 3 to 15 parts by weight, based on 100 parts by weight of the polyolefin resin of the component (A). This compounding amount is 1
If the amount is less than 30 parts by weight, sufficient flame-retardant performance cannot be obtained.
If the amount is more than the weight part, the physical properties deteriorate, and it becomes impossible to granulate into pellets, which is uneconomical.

The component (C), antimony oxide, is a flame retardant
[(B) component] is added as a flame retardant aid,
Antimony trioxide (Sb_TwoO_Three), Antimony pentoxide
(Sb_TwoO _Five). With antimony oxide
The addition amount is 100% by weight of the polyolefin resin of the component (A).
0.5 to 20 parts by weight, but 1 to 10 parts by weight
Is preferred. If this addition amount is less than 0.5 parts by weight, it is difficult.
Sufficient synergistic effect with fuel cannot be obtained, and more than 20 parts by weight
Does not improve the flame-retardant effect, and the physical properties are low.
Costly and uneconomical.

(D) Component hydrotalcites
There are natural products and synthetic products, magnesium, calcium
Hydrated basic carbonic acid such as zinc, aluminum, bismuth, etc.
Those which do not contain a salt or water of crystallization are mentioned. With natural products
Is, Mg₆Al_Two(OH)₁₆CO_Three・ 4H_TwoO structure
One having a structure. As a synthetic product, Mg
_0.7Al_0.3(OH)_Two(CO_Three)_0.15・ 0.54H
_TwoO, Mg_4.5Al_Two(OH)₁₃CO_Three・ 3.5H_TwoO,
Mg_4.2Al_Two(OH)_12.4(CO_Three)_0.15, Zn₆A
l_Two(OH)₁₆CO_Three・ 4H_TwoO, Ca₆Al_Two(O
H)₁₆CO_Three・ 4H_TwoO, Mg₁₄Bi_Two(OH)_29.6・
4.2H_TwoO and the like.

The amount of the component (D) in the composition of the present invention is 0.05 to 2 parts by weight based on 100 parts by weight of the polyolefin resin of the component (A). This addition amount is 0.05
If the amount is less than parts by weight, sufficient heat resistance is not exhibited and 2
When the amount is more than the weight part, the flame retardancy is reduced and it is uneconomical.

The flame-retardant resin composition of the present invention may contain, in addition to the above components, fillers, lubricants, and antioxidants which are usually added to the resin composition as needed, within a range not to impair the object of the present invention. Agents, antistatic agents, ultraviolet absorbers, pigments and the like can be appropriately compounded.

The resin composition of the present invention can be produced by melt-kneading the above-mentioned components by any method. For example, there is a method using a high-speed stirrer represented by a Henschel mixer, a single-screw or twin-screw continuous kneader, a roll mixer, or the like, alone or in combination. The molding method of the resin composition thus obtained includes:
There is no particular limitation, and there are injection molding, extrusion molding, blow molding and the like, but injection molding is particularly preferred.

[0019]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The substances used in the following examples and comparative examples are as follows. 1) Polypropylene Idemitsu Polypro J2003GP (MI = 21
(g / 10 min) The MI value of the polypropylene was measured at 230 ° C. and 2.16 kg using a tester (Melt Indexer S-001, manufactured by Toyo Seiki Seisaku-sho, Ltd.). 2) Bis (2,3-dibromopropyl) ether of tetrabromobisphenol A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Pyrogard SR720 3) Bis (2,3-dibromopropyl) ether of tetrabromobisphenol S Marubishi Yuka ( 4) Tris (2,3-dibromopropyl) isocyanurate Asahi Glass Co., Ltd. AFR1002 5) Antimony trioxide Average particle size 1 μm 6) Hydrotalcite Kyowa Chemical Co., Ltd., DHT -4A

Examples 1 to 8 and Comparative Examples 1 to 5 The components shown in Table 1 were mixed in a twin-screw kneader (Ikegai Iron and Steel Co.
The composition was prepared by melt-kneading at 120 to 240 ° C. using trade name PCM45) and pelletized using a strand cut. The composition pellets thus obtained,
Injection molding machine (trade name: FE-12) manufactured by Nissei Plastic Industry Co., Ltd.
0, PS-40), cylinder temperature 190-21
Injection molding was performed at 0 ° C and a mold temperature of 50 ° C to prepare a test piece
The characteristics were evaluated by the following evaluation methods (1) and (2). In addition, the following test (3) was performed. The results are shown in Table 1.

(1) Flame retardancy evaluation (UL-94) Testing machine: HVUL plastic UL combustion test chamber manufactured by Atlas Co., Ltd.
A vertical burn test was performed according to 94. (2) Bleed-out property of the molded product surface An injection-molded plate (80 × 80 × 3.2 mm) was used as a test piece, which was weighed and placed in an oven at 100 ° C. for 120 minutes.
After leaving for a period of time, the flame retardant exuding on the surface of the molded plate is wiped off with acetone, and the molded plate is weighed.
From the weight change before and after the test, the bleed rate (%) is calculated by the following formula.
Was calculated. Bleed ratio = (weight change before and after test) / (initial weight of test piece) x 100 (%) (3) Heat resistance (retention burn test) Injection molding machine: Nissei Plastic Industry Co., Ltd., PS-40 test method : 200 parts of composition in cylinder of injection molding machine
The temperature was maintained at ２２０220 ° C. for 5 minutes, followed by injection molding. 1: very much burning 2: lots of burning 3: moderately burning 4: little burning 5: very little burning

[0022]

[Table 1]

[0023]

[Table 2]

[0024]

According to the present invention, high flame retardancy (UL-
94, 1/32 inch, V-0), and has good heat resistance, so that it is possible to provide a flame-retardant resin composition which is less likely to burn during processing and has less bleed-out in a molded product. .

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3:22 3:26)

Claims (1)

[Claims] (A) 100 parts by weight of a polyolefin resin, (B) (b1) bis (2,3-dibromopropyl) ether of tetrabromobisphenol A, and (b2) bis (2) of tetrabromobisphenol S 1 to 30 parts by weight of a mixture with (3-dibromopropyl) ether or (b3) tris (2,3-dibromopropyl) isocyanurate,
(C) 0.5 to 20 parts by weight of antimony oxide and (D) 0.05 to 2 parts by weight of hydrotalcites, wherein the mixing ratio of the components (b1) and (b2) or the components (b1) and ( b3) A flame-retardant resin composition having a mixing ratio with the components of 1: 9 to 9: 1 by weight.