JPH07157602A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having excellent flame retardancy, high weathering and light resistances, and good coatability and printability. CONSTITUTION:This resin composition contains 100 pts.wt. polyolein, 1-50 pts.wt. tris(brominated neopentyl) phosphate, 0.5-20 pts.wt. antimony trioxide, 0.01-5 pts.wt. weatherproofing agent, and 1-50 pts.wt. acid-modified polyolefin. It has, for example, a flammability rating of V-2, V-1 or V-0 in the UL 94 standard.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is flame-retardant and has high weather resistance.
The present invention relates to a flame-retardant resin composition having both light resistance and paintability / printability.

[0002]

2. Description of the Related Art Polyolefin has various drawbacks in that it has a drawback that it is easily ignited and combustible. In particular, polyolefins used for automobile parts, electric product parts, building materials, etc. tend to be required to have higher flame retardancy. Therefore, various flame retardants are blended to achieve flame retardancy. There are organic and inorganic flame retardants. Especially for polyolefin, organic flame retardants such as decabromodiphenyl oxide, brominated bisphenol A derivative, brominated bisphenol S derivative, brominated isocyanurate derivative are used. In many cases. However, with respect to decabromodiphenyl oxide, it has been reported that dioxins are generated from a resin mixed with it, and restrictions on its use have been screamed mainly in Europe, which is regarded as a problem in Japan.

Further, weather resistance and light resistance are required for use in parts exposed to the sun, mercury lamps, and fluorescent lamps.
Therefore, various weather resistance agents are blended with polyolefin to improve weather resistance and light resistance.

[0004] On the other hand, in the application of painting / printing, various modifiers are blended with polyolefin or surface treatment is performed to impart painting / printability. In general, as a modifier, a resin having a functional group having an affinity for a paint is used, and particularly in polyolefin, an acid-modified polyolefin having good compatibility is generally used.

[0005]

As described above, when imparting weather resistance and light resistance to a polyolefin, it is common to blend a weathering agent such as a benzoate-based, salicylate-based, triazole-based or hindered amine-based compound. .

However, when a flame retardant is added to the polyolefin to impart flame retardancy, even if a weather resistant agent is added to impart weather resistance and light resistance, the flame resistance is improved by improving the weather resistance. The amount is extremely small compared to the non-use type, and a large improvement cannot be expected even if the amount of the weatherproofing agent is increased. Further, when used in combination with the above-mentioned flame retardant, a problem of discoloration occurs.

On the other hand, when an acid-modified polyolefin is blended in order to impart paintability and printability, there arises a problem that discoloration occurs when used in combination with the above-mentioned flame retardant.

For this reason, it has been a problem to impart paintability and printability to a resin composition obtained by flame-retarding a polyolefin while maintaining high weather resistance and light resistance.

[0009]

Means for Solving the Problems As a result of intensive studies in view of the above problems, the present inventor has found that tris (brominated neopentyl) phosphate, antimony trioxide,
The present inventors have found that a resin composition containing a weather resistance agent and an acid-modified polyolefin dramatically improves flame retardancy, weather resistance / light resistance and coating / printability, and completed the present invention.

That is, the present invention relates to (A) polyolefin
100 parts by weight, (B) tris (brominated neopentyl) phosphate 1 to 50 parts by weight, (C) antimony trioxide 0.5 to 20 parts by weight, (D) weathering agent 0.01 to 5 parts by weight (E) acid A flame-retardant resin composition containing 1 to 50 parts by weight of a modified polyolefin.

As the polyolefin used in the present invention, ethylene, propylene, butene-1, pentene-
Α-, such as 1,4-methylpentene-1, hexene-1
Examples thereof include olefin homopolymers, random or block copolymers of the above α-olefins, and mixtures of these homopolymers and copolymers. The above-mentioned copolymer may contain, as a copolymerization component, a monomer other than α-olefin in an amount of, for example, 20 mol% or less as long as the properties of the copolymer are not impaired.

As the tris (brominated neopentyl) phosphate used in the present invention, known compounds can be used without limitation. For example, tris (tribromoneopentyl) phosphate, tris (dibromoneopentyl) phosphate, tris (monobromoneopentyl) phosphate, etc. can be mentioned. This can be used alone or as a mixture of two or more kinds. The amount of tris (brominated neopentyl) phosphate compounded is 1 to 50 parts by weight with respect to 100 parts by weight of the polyolefin.
Parts by weight, preferably 2 to 30 parts by weight. If the blending amount of tris (brominated neopentyl) phosphate is less than the lower limit, sufficient flame retardancy cannot be obtained, and if it is more than the upper limit, moldability, impact resistance decrease, and specific gravity increase. However, stable kneading becomes difficult, which is not preferable.

The antimony trioxide used in the present invention is
Commercial products can be used as they are. The compounding amount of antimony trioxide is 0.5 to 2 with respect to 100 parts by weight of polyolefin.
It is 0 part by weight, preferably 1 to 15 parts by weight. When the compounding amount of antimony trioxide is less than the lower limit value, sufficient flame retardancy cannot be obtained, and when it is more than the upper limit value, flame retardance is not improved, and the specific gravity and impact resistance are not increased. There is a decrease, which is not preferable.

Known compounds can be used without limitation as the weathering agent used in the present invention. For example, bis (2,2,6,6
-Tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2 succinate , 6,6-Tetramethylpiperidine polycondensate, poly [{6- (1,1,
Hindered amine compounds such as 3,3-tetramethylbutyl) imino-1,3,5-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino}]; 2
-Benzo-4-none represented by hydroxy-4-octoxybenzophenone; salicylate represented by 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate; 2- ( 2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5
Examples thereof include benzotriazole compounds represented by chlorobenzotriazole, and hindered amine compounds that cause less discoloration and are effective are particularly preferably used. The blending amount of the weather resistance agent is 0.01 to 5 parts by weight, preferably 0.03 to 3 parts by weight, based on 100 parts by weight of the polyolefin. If the compounding amount of the weather resistance agent is less than the lower limit value, sufficient weather resistance and light resistance cannot be exhibited. On the other hand, when the amount is more than the upper limit, further improvement in weather resistance and light resistance cannot be seen, which is not preferable.

Examples of the acid-modified polyolefin used in the present invention include a reaction product of the above-mentioned polyolefin with an unsaturated carboxylic acid or an anhydride thereof. Examples of unsaturated carboxylic acids or their anhydrides include maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid and their acid anhydrides, with maleic anhydride being preferred. Regarding the reaction method of the polyolefin and the unsaturated carboxylic acid or the anhydride thereof, known methods can be used without any limitation, for example, the presence of the peroxide in the molten state of the polyolefin and the unsaturated carboxylic acid or its anhydride. The method of reacting below can be mentioned. The amount of the acid-modified polyolefin compounded is 1 to 50 parts by weight, preferably 2 to 30 parts by weight. If the blending amount of the acid-modified polyolefin is less than the lower limit value, sufficient coating / printability cannot be exhibited. On the other hand, when the amount is more than the upper limit, no further improvement in coating and printability is observed, which is not preferable.

The flame-retardant resin composition of the present invention contains, in addition to the components described above, if necessary, conventionally known stabilizers, colorants, antistatic agents, lubricants, etc. within the range not impairing the effects of the present invention.
It may contain a nucleating agent, a non-halogen flame retardant, an anti-blooming agent, and a filler.

The mixing order and mixing method of the respective components for preparing the flame-retardant resin composition of the present invention are not particularly limited, and a tumbler type blender, a V type blender, a Henschel mixer, a ribbon mixer and the like are generally used. Done by.

[0018]

[Effect] The flame-retardant resin composition of the present invention is self-extinguishing according to the IEC standard, and therefore has V-2 and V-
It has a flame retardancy of 1 to V-0, and at the same time has weather resistance.
It has light resistance and paintability / printability. The reason why such characteristics are obtained is not clear, but it is presumed that the reactivity of tris (brominated neopentyl) phosphate with the acid-modified polyolefin and the weathering agent is low.

[0019]

EXAMPLES In order to more specifically describe the present invention, examples and comparative examples will be described below, but the present invention is not limited to these examples. The symbols shown in Examples and Comparative Examples are as follows.

1. Polypropylene (manufactured by Tokuyama Soda Co., Ltd .: powder) A: ethylene-propylene block copolymer (melt flow rate 23 g / 10 min, ethylene content 2.0 wt%) B: propylene homopolymer (melt flow rate 2
0 g / 10 min) 2. Flame retardant C: Tetrabromobisphenol A-bis (2,3-dibromopropyl) ether D: Tetrabromobisphenol S-bis (2,3-dibromopropyl) ether E: Decabromodiphenyl ether F: Tris (2,3-dibromo) Propyl) isocyanurate G: Tris (tribromoneopentyl) phosphate H: Tris (dibromoneopentyl) phosphate 3. Flame retardant aid I: Antimony trioxide 4. Weathering agent J: 2,4-di-t-butylphenyl-3,5-di-t
-Butyl-4-hydroxybenzoate K: 2- (2'-hydroxy-3'-t-butyl-5 '
-Methylphenyl) -5-chlorobenzotriazole L: 2-hydroxy-4-octoxybenzophenone M: Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate N: Poly [{6- (1 , 1,3,3-Tetramethylbutyl) imino-1,3,5-diyl} {(2,2,6,6
-Tetramethyl-4-piperidyl) imino}] 5. Acid-modified polyolefin P: Maleic anhydride-modified polypropylene (maleic anhydride content 0.2% by weight) Q: Itaconic acid-modified polypropylene (itaconic acid content 0.3% by weight) Examples and Comparative Examples Flame-retardant resin The composition was adjusted and the test method was carried out as follows, and the results are shown in Table 1. (1) Premixed 100 parts by weight of polypropylene, the flame retardant, the flame retardant aid, and the weather resistance of the composition table of Table 1 Agent, acid-modified polyolefin and 2,6-di-t-butyl-4-methylphenol (Stabilizer BHT manufactured by Sumitomo Chemical Co., Ltd.): 0.1 part by weight, dilauryl thiodipropionate (Sumitomo Chemical Co., Ltd., Sumilizer TPL-R): 0.2 part by weight, calcium stearate (manufactured by Dainippon Ink and Chemicals, Inc.): 0.
1 part by weight was blended and premixed with a Henschel mixer.

(2) Pelletization The above mixture was pelletized using a vented 50 mmφ extruder.

(3) Preparation of test piece (a) Preparation of combustion test piece and weather / weather resistance test plate Combustion test piece (thickness 1 / thickness) compliant with UL94 standard and IEC standard with 2oz injection molding machine from the above pellets 16 inches)
It was created. 40mm x 30mm for weather resistance test
A plate of × 0.5 mmt was prepared by press molding.

(A) Preparation of paintability test piece 80 mm × 48 m from the above pellets using a 2 oz injection molding machine
A test piece of m × 3 mm was prepared.

(4) Effect test (a) Combustion test (i) UL94 standard test Using the test pieces prepared according to the method of (3)-(a) in accordance with UL94 standard, the vertical flammability test was used to combust. The division was judged.

(Ii) IEC Standard Test The flammability classification was judged by a horizontal burning test using a test piece prepared by the method of (3)-(a) in accordance with IEC707 standard.

(A) Weather resistance test Using the test piece prepared by the method of (3)-(a), J
Accelerated exposure was carried out using an accelerated exposure test device based on IS-A1415, and the time until surface microcracks occurred was measured.

(C) Paintability test The test piece prepared by the method (3)-(a) is first treated with a primer (RB-147 manufactured by Nippon Bee Chemical Co., Ltd.), and then a paint (made by Nippon Bee Chemical Co., Ltd.). R-271)
Was applied, and a cross-cut test was carried out 48 hours later according to JIS K-5400, and the number of remaining 100 pieces was measured.

[0028]

[Table 1]

[0029]

[Table 2]

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 23:26)

Claims (1)

[Claims] 1. A polyolefin (A) 100 parts by weight,
(B) Tris (brominated neopentyl) phosphate 1
To 50 parts by weight, (C) antimony trioxide 0.5 to 20
A flame-retardant resin composition comprising 1 part by weight of (D) 0.01 to 5 parts by weight of (D) weathering agent and (E) 1 to 50 parts by weight of acid-modified polyolefin.