JPS6399253A - Flame-retardant polyolefin composition - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to flame-retardant polyolefin compositions. Specifically, the present invention relates to a flame-retardant polyolefin composition that prevents flame retardant from seeping out or bleeding.

[Conventional technology]

Conventionally, there is a method of adding a flame retardant to make polyolefin flame retardant, and it is well known that organic compounds containing halogen atoms are effective as flame retardants.

However, when an organic halogen flame retardant is blended with polyolefin, the flame retardant leaches onto the surface of the polyolefin, a phenomenon called bleed.
There was a drawback that the biconvex value of the molded product was significantly reduced.

[Problem that the invention seeks to solve]

It is believed that the bleed phenomenon is caused by separation of the flame retardant and polyolefin due to their poor compatibility. The inventors of the present invention have conducted extensive research into the possibility of preventing bleeding by interposing a mutual solubilizer that is soluble in both organic halogen flame retardants and polyolefins, and have finally arrived at the present invention. did.

That is, an object of the present invention is to provide a flame-retardant polyolefin composition that prevents bleeding without impairing flame retardancy and other properties such as electrical properties and mechanical properties.

[Means to solve the problem]

According to the present invention, a flame-retardant polyolefin composition without bleeding can be obtained by blending an organic halogen flame retardant and a carbonate ester represented by the general formula (I) into a polyolefin. Hereinafter, one aspect of the present invention will be explained in detail.

As the polyolefin constituting the composition of the present invention, crystalline and non-crystalline thermoplastic polymers, or various polyolefin derivatives obtained by chemically or physically treating these thermoplastic polymers can be used. can. For example, high-pressure polyethylene, medium-low pressure polyethylene, low-pressure polyethylene, isotactic polypropylene, syndiotactic polypropylene, atactic polypropylene, polybutene, polyethylene with maleic anhydride,
Examples include grafted polyethylene grafted with fumaric acid, acrylic acid, methacrylic acid, and the like. Also,
Random copolymers of ethylene and α-olefins and block copolymers thereof, copolymers of ethylene or α-olefins and other vinyl monomers, alternating copolymers of ethylene or α-olefins and conjugated dienes. etc. can also be used. Examples of these copolymers are ethylene-propylene copolymers and ethylene-vinyl acetate copolymers.

Examples include ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, propylene-butadiene alternating copolymer, ethylene-diallyl ester copolymer, and the like.

Various known organic halogen flame retardants can be used. For example, hexabrombenzene, decaglombiphenyl, degaglombifenyl, f)
57” rombisphenol, hexaphromcyclododecane, dodecachloropentacyclodecane, U, corbis[:t, S-difuromor≠-(allyloxy)phenyl 17'0pan, coanibis[3,5-dibromo-
Hiro-(3-cyfuromoproboxy)phenyl]propane, tris-(λ,3-dibromoglobil)isocyanurate), /,/'-sulfonylbis[3,j-dibromo-
(2+3-Schif'lomoproboxy)]benzene, etc.

As the carbonate ester, a compound represented by the general formula (I) is used. Here, R1R' is an alkyl group, an alkenyl group, or an alkynyl group.

It represents a cycloalkyl group, an aralkyl group, or an aryl group, and R and R' may be the same or different. 2 represents an aliphatic, aromatic, or alicyclic diol residue;
fi represents an integer of Q or /. The following are specific examples of representative examples of 2.

-0-CHlCH,-0+, -o-C)I,C)(,
-0-CH, CH, -0+, -0-C>O+.

-0-CH,CHl-o-C)-o-cn,cH,-o
-, -o-c*, Ocu, -o-.

-o%o-, -0-CH,CH, -o%o-CH,CH
, -0-.

-o-an, %cn, -o-, -o-C>oOo--O
-CH, (yOriyCH, -0-.

-〇〇HtC)lx-0-C)-0&0-CHzCI
I2-0.

-〇(Σcoco-.

-0-C14C horse-o-C>coQo-c bird CH, -0
−.

-o-C5-so, (yo-, -o-c4cn, -0-
CΣ0-CM, CH, -0-.

As the carbonate ester, it is preferable to use one that has low volatility and is liquid at the molding temperature of the polyolefin composition. Therefore, it is usually a liquid at 1 (2j°C) or a solid at room temperature but with a melting point of 120°C or lower. Examples of such carbonate esters include the following.

The organic halogen flame retardant is usually added in an amount of 1 to 5 parts by weight as halogen atoms per 100 parts by weight of the polyolefin.

The amount of carbonate ester added to polyolefin varies depending on the type of polyolefin and the type and amount of organic halogen flame retardant, but usually 100% of polyolefin is added.
It is selected from the range of /-5 parts by weight. If the amount added is less than 1 part by weight, the bleed prevention effect will be small, and if it is added in 5 parts by weight or more, the bleed prevention effect will not increase significantly.

The composition of the present invention is usually produced by kneading a polyolefin, a flame retardant, and a carbonate ester under heating using a mixer such as a mixing roll, a calendar roll, a niegu, or an extruder. The flame retardant and carbonate ester may be mixed in advance and added to the polyolefin. In addition, in the case of crosstalk, fillers, stabilizers, antioxidants, ultraviolet absorbers, pigments, lubricants, and antimony oxide, aluminum hydroxide, magnesium hydroxide, etc., which are usually used in combination with organic halogen flame retardants, can be used as flammable agents. There is no problem in adding adjuvants, etc.

The present invention will be explained in more detail with reference to Examples below.

Examples 1 to 6, Comparative Example 1 Polypropylene (manufactured by Mitsubishi Chemical Industries, Ltd.)

Tsubachik P-dazoos) too parts by weight, basic magnesium aluminum hydroxycarbonate (manufactured by Kyowa Chemical Industry Co., Ltd., DHT-1IA) as a stabilizer
-Y) 1 part by weight, carbon black (manufactured by Mitsubishi Chemical Corporation, N-76θM) Ha! Overlapping parts, 7 parts of antimony dioxide, 1 part by weight, organic halogen flame retardants, parts by weight of U, Nibis [3°5-dibroey-(U,J-dibromoproboxy)phenyl]grobank, and Tris- (U,3-dibromoglovir) incyanurate 7 parts by weight,
and 3 parts by weight of various carbonate esters shown in Table 1 using a twin screw extruder (manufactured by Ikegai Iron Works Co., Ltd.).

20ρ″CPCM-, io) was used for kneading, and then an injection molding machine (manufactured by Niigata Iron Works Co., Ltd., IIIN-qs) was used.
Mold the test piece with Yu 10C using These test pieces have bleedability, S flammability,! The test results for mechanical properties and tensile strength were as shown in Table 1.

In addition, in the bleedability test, the test piece is
After heating for 96 hours in an open environment at ℃, the sample was returned to room temperature and one surface was visually observed. In addition, the measurement of the bleed rate is
After weighing a test piece with a length of 1 m and a thickness of 3 m, the bleed rate was calculated using the 9th equation from the weight change of the test piece before and after cutting off at 00C.

Addition amount of flame retardant Examples 7 to io, comparative examples Polyethylene (manufactured by Mitsubishi Chemical Industries, Ltd.)

ET-010M) / 00 parts by weight, 4' Otit part of decaflorobiphenyl ether as a flame retardant, 20 parts by weight of antimony tria, benzotriazole ultraviolet absorber (manufactured by Ciba Geigy, Tinuvin P-J Cob') or
1 part, a hindered phenolic antioxidant (manufactured by Ciba Geigy, Irganox-toto) 0/part by weight, and 3 parts by weight of various carbonate esters shown in Table 2. Test specimens were molded at the same temperature using an extruder and an injection molding machine, and the test specimens were tested for bleedability, flame retardancy, etc. in the same manner as in Examples 1 to 6. Feeling.

A tensile strength test was conducted. The results are shown in Table 1. Note that the bleeding rate was measured in the same manner as in Examples 1 to 6.

For comparison, Table 1 also shows the test results of test pieces molded from compositions to which no carbonate ester was added.

〔Effect of the invention〕

According to the present invention, by using a carbonate ester in combination with a polyolefin composition containing an organic halogen flame retardant, bleeding of the flame retardant can be prevented without impairing the flame retardancy and other properties of the polyolefin composition. A flame retardant polyolefin composition can be obtained.

Claims (1)

[Claims] (1) Organic halogen flame retardant and general formula (I)▲mathematical formula,
There are chemical formulas, tables, etc. may be the same or different.Z represents an aliphatic, aromatic, or alicyclic diol residue, and n represents an integer of 0 or 1). Flammable polyolefin composition.