JPS62209152A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition outstanding in flame-retardancy and appearance of molded articles therefrom, suitable for electrical insulation materials, by incorporating a random copolymer constituted chiefly by ethylene and propylene with respective specified amounts of inorganic filler and organic halogen flame-retardant. CONSTITUTION:The objective composition can be obtained by incorporating (A) an ethylene-propylene two-component random copolymer with a melt flow rate 1-50g/10min and ethylene content 0.5-10wt% or ethylene-propylene-butene three-component random copolymer with ethylene content 0.5-10wt% and butene content 3-20wt% with (B) 10-70(pref. 10-50)wt% of inorganic filler (e.g. calcium silicate, talc), (C) as an organic halogen flame-retardant, 10-30wt% of either decabromodiphenyl oxide or perchloropentacyclodecane, and, if needed, (D) 20-60wt%, based on the component C, of an antimony compound (e.g. antimony trioxide).

Description

[Detailed description of the invention] (Industrial application field) FIELD OF THE INVENTION This invention relates to flame retardant polypropylene compositions.

More specifically, ethylene-propylene binary random copolymer or ethylene-propylene-butene ternary random copolymer is added with a specific amount of inorganic filler and organic halogen flame retardant such as decabromodiphenyl oxide or perchloropentacyclodecane. The present invention relates to a flame-retardant polypropylene composition which has a high degree of flame retardancy and which provides a molded article with an excellent appearance when formed into a molded article.

(Prior art and its problems) Advanced flame retardant technology for polypropylene involves blending organic halogen flame retardants and inorganic fillers with propylene homopolymer or ethylene-propylene block copolymer containing propylene as the main component. It is well known that

However, when the above-mentioned polypropylene is blended with an organic halogen flame retardant and an inorganic filler, the surface gloss rate of the molded product is low when the composition is used to make a molded product. When used in housings, etc., the appearance is unfavorable and there are practical problems. Therefore, in order to improve the surface gloss rate, it is necessary to reduce the blending ratio of the organic halogen flame retardant and the inorganic filler.

However, if the alloy in which the flame retardant is blended is reduced, a problem arises in that the flame retardancy decreases.

The inventors of the present invention have conducted extensive research into flame-retardant polypropylene compositions that can be used to produce molded articles that have a high surface gloss rate and a high degree of flame retardancy. As a result, a composition made by blending a specific polypropylene with an organic halogen flame retardant and an inorganic filler has a high degree of flame retardancy (U
L-94, ■-0, USA, Underwriter Labora) IJE's flame retardant standards) and found that when molded products were made into molded products, the surface gloss rate was higher. The present invention was completed soon after.

As is clear from the above description, an object of the present invention is to provide a flame-retardant polypropylene composition that has a high degree of flame retardancy and provides a molded article with excellent surface gloss.

(Means for solving problems) The present invention has the following configurations (1) to (4).

(1) Ethylene-containing +1 o, s~10 wt% ethylene-propylene binary random copolymer or ethylene containing tO, 5~10 wt%, butene content 3~20
10 to 70% by weight of an inorganic filler and 10 to 30% by weight of decabromodiphenyl oxide or perchloropentacyclodecane as an organic halogen flame retardant are blended into 3% by weight of an ethylene-propylene-butene ternary random copolymer. A flame-retardant polypropylene composition made of

(2) Ethylene-Globile 72 element random copolymer with a melt 70-rate of 1 to 50 f710 is also a polypropylene composition.

(3) The flame-retardant polypropylene composition according to item (1) above, wherein the inorganic filler is calcium silicate, talc, silica, mica, clay, glass fiber, or a mixture of two or more thereof.

(4) 20 to 60% by weight based on organic halogen flame retardant
The flame-retardant polypropylene composition according to item (1) above, which contains antimony oxide.

The polypropylene used in the present invention is an ethylene-propylene binary random copolymer or an ethylene-propylene-butene ternary random copolymer, and is
For the base random copolymer, ethylene-containing -io
, Discharge of molten resin at 5 to 10 weights 1 to 50 f/1
It is 0 minutes. If the ethylene content is less than 0.5% by weight, the resulting molded product will not have a high surface glossiness, and if it exceeds 10% by weight, practical rigidity will be insufficient, which is undesirable. U also has MFR of 1 y7
If the time is less than 10 minutes, the appearance of the molded product obtained is poor and M
If the FR exceeds 5ON/10 minutes, it is highly flame retardant.
This is not preferable because it does not meet the standards of L-94 and v-O.

In the above-mentioned ternary random copolymer, the ethylene content is 0.5 to 10% by weight, and the butene content is 3 to 20% by weight.
It has an MFR of 1 to 50 g/10 minutes. If the ethylene content is less than 0.5% by weight and the butene content is less than 1% by weight, a molded product with a high gloss rate cannot be obtained; is 2
0 TjL: If it exceeds 1%, practical rigidity will be insufficient, which is not preferable. Further, if the KMFR is less than 1y/10 minutes, the moldability will deteriorate and a molded product with a clean appearance cannot be obtained, and if it exceeds 5011/10 minutes, it will not meet the standards of UL-94, ■-〇, which is not preferable.

In the composition of the present invention, when a propylene homopolymer or an ethylene-propylene block copolymer is used in place of the above-mentioned binary random copolymer or ternary random copolymer, a high gloss rate can be obtained. No composition is obtained which gives shaped articles.

Examples of the inorganic filler used in the present invention include calcium silicate, talc, silica, mica, clay, glass fiber, and mixtures of two or more of these. Further, by blending the inorganic filler, there is an advantage that the blending S-t of the organic inorganic flame retardant can be reduced. % without weight. The blending amount is 10! If it is less than t%, the flame retardancy will decrease, and if it exceeds 70% by weight, the impact strength of the molded article will decrease, and the fluidity of the molten resin during molding will deteriorate, resulting in a decrease in moldability. Therefore, it is not desirable.

The organic halogen flame retardant used in the present invention is decabromodiphenyl oxide or perchloropentacyclodecane. The blending amount of the organic halogen flame retardant is 10 to 3
It is 0% by weight.

If the blending amount is less than 10% by weight, flame retardancy will be insufficient, and 3
If the amount exceeds 0% by weight, not only no further improvement in flame retardance can be obtained, but also the impact strength of the obtained molded article will decrease, which is not preferable.

Furthermore, replacing a part of the organic halogen flame retardant with chlorinated paraffin reduces the rigidity, heat deformation resistance, and impact strength of the obtained molded product, and also causes droplets of molten resin pieces and droplets to drop during combustion. It is not desirable because it promotes sex.

The composition of the present invention may further contain antimony compounds such as antimony trioxide and antimony trichloride as flame retardant aids. The amount of the nuclear antimony compound is 20 to 60% of the organic flame retardant used.
? i amount%.

The use of the flame retardant auxiliary agent is preferable because it has the effect of increasing the flame retardance by acting additively in the composition of the present invention, so that the amount of the organic halogen flame retardant used can be reduced. .

The composition of the present invention can contain all of the following additives as in general polypropylene compositions (1) FF inhibitor, light stabilizer, copper damage inhibitor, antistatic agent, nucleating agent (2) Titanium oxide, carbon black, quinacridone and other pigments (3) Fatty acid metal salts such as calcium stearate, lubricants such as paraffin wax (4) Dispersants such as stearamide (5) Lead salts, organic tin, epoxy compounds,
Stabilizers such as polyhydric alcohols such as pentaerythritol (
6) Foaming agent (7) Crosslinking agent such as polyfunctional monomer (8
) ethylene propylene rubber, styrene butadiene rubber,
A rubber component used to improve impact strength such as impregnated rubber.

The method for producing the composition of the present invention is not particularly limited, but for example, an ethylene-propylene binary random copolymer having an ethylene content of 0.5 to 10% by weight or a butene-containing ethylene content of 0.5 to 10% by weight ethylene-propylene-butene ternary random copolymer in an amount of 3 to 20 ft%;
After stirring and mixing each predetermined amount of an inorganic filler and an organic halogen flame retardant in a mixer equipped with a high-speed agitator such as a Hensel Mixer (trade name) Super Mixer, the resulting mixture is mixed using a single-screw or twin-screw Continuously supplied to an extruder to melt and knead at a temperature of 180 to 300°C, preferably 200 to 200°C.
Examples of methods include melt-kneading extrusion and pelletizing at 50°C.

The thus obtained composition of the present invention can be used to produce various molded products by known methods such as extrusion molding, injection molding, and blow molding, and such molded products not only have good flame retardancy but also good appearance. Moreover, there is no decrease in mechanical strength, and it can be suitably used for desired electrical insulating materials, parts for electrical products, parts for automobiles, and the like.

Hereinafter, the present invention will be explained in detail with reference to Examples and Comparative Examples. The evaluation method of the present invention used in Examples and Comparative Examples was as follows.

(1) Appearance The glossiness of a molded article having a length of 50H, a width of 50M and a thickness of 2 fl, which was molded by injection molding, was determined, and the appearance was determined to be good or bad based on the magnitude of the value. In other words, the appearance is good, the ID gloss rate is high,
Conversely, if the appearance is poor, the gloss rate is low. Measurement of gloss rate is JIS
It was carried out according to Z-8741. In addition, the irradiation angle of the light is
The measurement was carried out at 60 degrees, and a glossy needle GM-30'r manufactured by Murakami Color Technology Research Co., Ltd. was used as the measuring device.

(2) Combustion test Test piece of 127 silk in length, 12.7 in width, 14 in 0.8 MII molded by injection molding method, UL Subject 94
(Underwriters, Laboratories, Inc.) 1. It was investigated whether it corresponds to Il field classification v-0.

Examples 1 to 4 Comparative Examples 1 to 4 MFR 8,0, ethylene-propylene binary random copolymer with ethylene content of 3% by weight or ethylene-propylene-butene 3 with ethylene content of 3% by weight and butene content of 5% by weight The base random copolymer, talc as an inorganic filler, decabromodiphenyl oxide as an organic halogen non-flammable agent, and antimony trioxide as a flame retardant aid are added to a Hensel mixer (trade name) at the mixing ratios listed in Table 1 below. , and stirred and mixed for 5 minutes. The resulting mixture was melt-kneaded using a single-screw extruder with a diameter of 45 mm at a temperature of 230°C.
The strands are melt-kneaded and extruded to form strands, and the resulting strands are cooled, solidified, cut, and granulated into pellets. This granulated product was molded into 50x50x2 pieces by injection molding. f
A flat plate of No. f was prepared and all appearance properties (gloss ratio) were measured. Also 1
A flat plate of 27 x 127 x 0.8 fl was prepared and its flammability was measured.

In addition, as Comparative Examples 1 to 4, each compounded component was put into a Henschel mixer at the compounding ratio shown in Table 1 below, and Examples 1 to 4 were mixed.
The mixture was stirred and mixed according to 4.

The resulting mixture was melt-kneaded and extruded to granulate according to Examples 1 to 4. Next, predetermined test pieces were prepared by injection molding, and the appearance (gloss rate) and flammability were measured.

These results are summarized in Table 1.

As is clear from the description in Table 1, the flame retardant polypropylene compositions of the present invention shown in Examples 1 to 4 related to the present invention all have flame retardance that is higher than that of the UL-94 standard. It can be seen that it passed V-〇, and also had a gloss rate of 79% or more, showing a good value for appearance.

On the other hand, the flame-retardant polypropylene compositions shown in Comparative Examples 1 to 4 pass the UL-94 standard V-○ in flame retardancy, but the gloss rate is less than 51% and the appearance is poor. It shows the value.

Claims (4)

[Claims] (1) Ethylene with an ethylene content of 0.5 to 10% by weight
Propylene binary random copolymer or ethylene content 0.5-10% by weight, butene content 3-20% by weight
The ethylene-propylene-butene ternary random copolymer is blended with 10 to 70% by weight of an inorganic filler and 10 to 30% by weight of decabromodiphenyl oxide or perchloropentacyclodecane as an organic halogen flame retardant. Flame retardant polypropylene composition. (2) The flame-retardant polypropylene according to claim 1, which uses an ethylene-propylene binary random copolymer or an ethylene-propylene-butene tertiary random copolymer with a melt flow rate of 1 to 50 g/10 minutes. Composition. (3) The flame-retardant polypropylene composition according to claim 1, wherein the inorganic filler is calcium silicate, talc, silica, mica, clay, glass fiber, or a mixture of two or more thereof. (4) 20 to 60% by weight based on organic halogen flame retardant
Claim 1 comprising an antimony compound of
Flame retardant polypropylene composition.