JPH021849B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a flame retardant composition of an olefin polymer or a copolymer between olefins (hereinafter collectively referred to as polyolefin), and more specifically, by using a specific flame retardant in combination. , provides a polyolefin composition that exhibits flame retardancy even when incorporated in a small amount. [Prior Art and Problems] Since polyolefin is composed of hydrocarbons, it has the disadvantage of being easily ignited and combustible, and therefore it is necessary to make polyolefin flame retardant. In particular, polyolefins used in electrical appliances, building materials, etc. tend to require high flame retardancy, such as a flame retardancy of V-2 to V-0 according to the U.S. UL standard. Against this background, various proposals have been made for making polyolefin flame retardant. For example, the most common method involves blending an organic or inorganic flame retardant with polyolefin. However, in order to exhibit the desired flame retardant effect in the conventional flame retardant polyolefin compositions described above, it is necessary to incorporate a large amount of flame retardant, and in this case, it is expensive and requires poor moldability and base material. Problems such as deterioration of the physical properties of the polymer arise.
Moreover, even if this is done, the desired flame retardant effect, especially a high degree of self-ignition property, may not be obtained in some cases. [Means for Solving the Problem] As a result of various studies on polyolefin compositions containing a small amount of flame retardant having flame retardant properties, the present inventors found that by blending a specific flame retardant with polyolefin, The inventors have discovered that the above problem can be solved and have come to propose the present invention. That is, the present invention comprises (a) 100 parts by weight of polyolefin, (b) 12 to 25 parts by weight of an aromatic bromine compound in which bromine is directly bonded to the nucleus (excluding compounds in which bromine is bonded to the side chain), (c) General formula

[Chemical formula] (However, R ¹ and R ² are the same or different atomic groups selected from phenyl or substituted phenyl, R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different,
A group selected from H, alkyl, cycloalkyl, halogen, cyano group, and nitro group, and three or more of R ³ , R ⁴ , R ⁵ , and R ⁶ are cyano groups or nitro groups at the same time. must not. ) A flame-retardant polyolefin composition containing 0.1 to 2.0 parts by weight or more of (a), (b), and (c). Preferably, it is a flame-retardant polyolefin composition to which 3 to 10 parts by weight of antimony trioxide is added as a fourth component, and more preferably 5 to 25 parts by weight of an inorganic filler as a fifth component. A flame retardant polyolefin composition is also provided. The polyolefin used in the present invention is a polymer of olefin, that is, a monomer consisting of ethylene series hydrocarbons, or a copolymer of one type of olefin and one or more types of other olefins. For example, homopolymers of α-olefins such as ethylene, propylene, and butylene, copolymers of α-olefins and other α-olefins, block copolymers of these, for example, ethylene-
Random or block copolymers of propylene, random or block copolymers of ethylene-butylene, random or block copolymers of propylene-butylene, or mixtures of homopolymers and copolymers or copolymers, etc. be. In particular, polyolefin containing polypropylene as a main component is preferably used. The most important thing in the present invention is to use a flame retardant having a specific structure in combination with the polyolefin. That is, 100 parts by weight of polyolefin,
Aromatic bromine compounds with bromine directly bonded to the nucleus (excluding compounds with bromine bonded to the side chain)12
~25 parts by weight, and general formula:

Compound 0.1
~2.0 parts by weight. Conventionally, it has been proposed to use each of the above flame retardants alone or in combination with other flame retardants. For example, a composition consisting of an aromatic bromine compound in which bromine is directly bonded to the (benzene) nucleus and antimony trioxide,
Alternatively, according to Japanese Patent Application No. 132,848/1984, a composition containing an aromatic bromine compound in which bromine is directly bonded to the nucleus cannot exhibit the effects as in the present invention. In addition, the special public service
No. 9821 describes organic bromine compounds and the general formula

A method for making polystyrene flame retardant using [chemical formula] is shown, and for polystyrene, a combination of an organic bromine compound and component (c) of the present invention is shown, but this method was applied directly to polyolefin. In this case, it is not possible to obtain a high degree of flame retardancy of V-2 or higher according to the UL standard. Furthermore, many of the organic bromine compounds disclosed in the same patent cause fire dripping, so it has been impossible to achieve V-0 no matter what. On the other hand, according to the present invention, as described above, a specific organic bromine compound called an aromatic bromine compound in which bromine is directly bonded to the nucleus and the general formula;

By simply blending a small amount of each of the compounds of By adding a filler, a composition with excellent flame retardancy can be obtained. The aromatic bromine compounds used in the present invention are compounds in which bromine is directly bonded to the (benzene) nucleus, such as brominated benzenes such as hexabromobenzene and pentabromobenzene; bromine compounds such as pentabromotoluene and tetrabromotoluene. brominated toluene; brominated xylenes such as tetrabromxylene and tripromxylene; pentabromphenol;
Brominated phenols and their metal salts such as tetrabromo resorcinol, triprompyrogallol, sodium pentabromo ferate; Brominated anilines such as pentabromoaniline and tetrabromoaniline; pentabromobenzoic acid, tetrabromobenzoic acid and their derivatives; tetrabromo salicylic acid ,
Brominated benzene heterosubstituted products such as tetrabromotoluic acid and tetrabromucresol; brominated phthalic anhydrides such as tetrabrominated phthalic anhydride; brominated biphenyl; bromination of brominated diphenyl ether, brominated diphenyl thioether, etc. Diphenyl derivatives; brominated naphthalene derivatives; brominated anthracene derivatives; and brominated aromatic polymers such as triprompolystyrene. Among these, those having a bromine content of 55% or more are particularly preferably used. In the present invention, it is important to use an aromatic bromine compound in which bromine is directly bonded to a particularly selected nucleus among aromatic bromine compounds known as flame retardants. That is, even if bromine is directly bonded to the nucleus, compounds with bromine bonded to the side chain, such as tetrabromide bisphenol A bis (dibromide propyl ether), tetrabromide dihydroxy diphenyl sulfone ( Propyl ether dibromide) etc. cause fire spots,
This is inappropriate for the present invention. Furthermore, aliphatic bromine compounds, such as tetrapromobutane and tribromopropane, which are frequently used as flame retardants for polyolefins, also cause fire blisters and cannot be used in the present invention. The blending amount of the aromatic bromine compound of the present invention is 12 to 25 parts by weight per 100 parts by weight of the polyolefin. Even if the blending amount of the above-mentioned aromatic bromine compound is less than 12 parts by weight, a flame retardant effect can be expected, but it is not sufficient.In particular, in order to ensure self-extinguishing property, 12 parts by weight is required. is generally required. On the other hand, if the amount exceeds 25 parts by weight, not only will the flame retardant effect reach a plateau, but it will also have an adverse effect on the physical properties of the polymer. General formula used in the present invention:

In the compound represented by [Chemical formula], R ¹ and R ² are the same or different atomic groups selected from phenyl or substituted phenyl, and R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different H, alkyl , cycloalkyl, halogen, cyano group, and nitro group, and two or more of R ³ , R ⁴ , R ⁵ , and R ⁶ must not be cyano groups or nitro groups at the same time. Examples of such compounds include 2,3-diethyl-2,3-diphenylbutane, 2,3-dimethyl-2,3-P-tolylbutane, 2,3-di-methyl-2,3-di-p- Bromphenylbutane, 2,3-diethyl-2,3-di-p-chlorophenylbutane, 2,3-dimethyl-2,3-di-p-ethoxyphenylbutane, 2,2,3,3
-Tetraphenylbutane, 1,2-dibrome-
1,2-dimethyl-1,2-diphenylethane,
1,2-dibromo-1,2-diphenylethane,
1,2-dinitro-1,2-diphenylethane,
1,2-dinitro-1,2-di-p-tolylethane, 2,3-dicyan-2,3-diphenylbutane, 1,2-dichloro-1,2-diphenylethane and mixtures of these compounds. The compound is added in an amount of 0.1 parts by weight per 100 parts by weight of the polyolefin composition.
~2.0 parts by weight, preferably 1.0 to 2.0 parts by weight. If the amount is less than 0.1 part by weight, the flame retardant effect will not be sufficiently exhibited. On the other hand, if the amount is more than 2.0 parts by weight, no particularly significant effect will be exhibited, and the result will instead be an adverse effect on the physical properties of the polymer. In the present invention, the above-mentioned polyolefin, aromatic bromine compound, general formula:

By using antimony trioxide or antimony trioxide and an inorganic filler in combination with [chemical], the antimony trioxide or antimony trioxide and the inorganic filler act synergistically to increase the flame retardant effect. shows high flame retardancy. The above-mentioned effects are remarkable effects that would not be expected from adding each component alone or two components to a polyolefin. Antimony trioxide preferably has an average particle size of 2 to 20 μm, and is added in an amount of 3 to 10 parts by weight, preferably 4 to 7 parts by weight, per 100 parts by weight of polyolefin. As the inorganic filler used in the present invention, known ones such as talc, magnesium hydroxide, calcium carbonate, magnesium carbonate, etc. can be used without particular limitation. In particular, those having an average particle size of 2 to 20 μm are preferably used. The inorganic filler is polyolefin
5 to 25 parts by weight, preferably 15 parts by weight per 100 parts by weight
~20 parts by weight is blended. In the present invention, if the amount of antimony trioxide or antimony trioxide and inorganic filler blended into the polyolefin is less than the above-mentioned specific range, an even better flame retardant effect can be obtained by adding these compounds. I can't. Further, if the amount exceeds the specified range, no significant improvement in the flame retardant effect will be observed, and rather there is a risk of deterioration of physical properties, etc., which is not preferable. In the present invention, polyolefin, aromatic bromine compound and general formula:

The order of mixing the compound represented by [C], antimony trioxide, or antimony trioxide and the inorganic filler is not particularly limited, and each component may be mixed at the same time, or several components may be mixed in advance and the rest mixed later. You may. The mixing method is also not particularly limited, and is generally carried out using a tumbler blender, a V-type blender, a Henschel mixer, a ribbon mixer, or the like.
Furthermore, mix the types in advance with a Henschel mixer,
It is also possible to adopt a method of changing the mixing order and device, such as adding the remaining ingredients and mixing in a tumbler blender. Further, the extrusion method is not particularly limited either, and the composition of the present invention mixed in a predetermined ratio may be extruded and pelletized at once, or some components may be mixed and pelletized in advance, and then the remaining components may be mixed to achieve the desired ratio of the predetermined ratio. A composition may be obtained. The polyolefin composition in the present invention basically consists of the above-mentioned polyolefin, a specific aromatic bromine compound (component b), and the general formula:

It consists of a compound represented by [chemical formula] (component c), antimony trioxide alone or an inorganic filler, and in addition to these components, conventionally known stabilizers, colorants, antistatic agents, and lubricants. , a nucleating agent, etc. may be added. [Effect] By blending a specific flame retardant, the polyolefin composition of the present invention exhibits flame retardancy even with a small amount of blending due to the synergistic action of these flame retardants. Therefore,
The compounding operation is easy, the moldability is easy, and the physical properties of the base polymer are not adversely affected. Furthermore, it is possible to have a high degree of flame retardancy corresponding to V-0 to V-2 in the UL (94) standard mentioned above. In the present invention, by using components (b) and (c) for polyolefin, it is possible to reduce the self-extinguishing time to 15 seconds or less according to UL standards, and in addition, antimony trioxide By adding, it is possible to reduce the time to 10 seconds or less, and furthermore, when an inorganic filler is used in combination, the time can be shortened to 6 seconds or even 0 seconds. [Examples] In order to explain the present invention more specifically, Examples and Comparative Examples will be described below, but the present invention is not limited to these Examples. The experimental results shown in Examples and Comparative Examples were conducted in accordance with the vertical method of the UL standard, and the average self-extinguishing time was
The average self-extinguishing time after ignition of fire twice for each of the 10 combustion test specimens, that is, 20 times in total, is shown. The degree to which the test pieces of cotton ignited due to "flame" from the test piece was expressed by how many of the five cotton pieces were ignited. For example, if 3 out of 5 lights were ignited, it would be displayed as 3/5. The shape of the test piece is 5 inches x 0.5 inches x 1/1
I went with 6 inches. Example 1 100 weight polyolefins of one of polypropylene (P.P, manufactured by Tokuyama Soda Co., Ltd.) with a melt index (MI) of 6, polyethylene (PE) with an MI of 2, and polybutene (PB) with an MI of 5 For the part, the first
Aromatic bromine compounds in the proportions shown in Tables 2 and 3, general formula:

The compound represented by the following formula, antimony trioxide, and an inorganic filler were mixed in a tumbler blender and pelletized using an extruder. This pellet is molded using a 1.50z extrusion machine.
(manufactured by Kawaguchi Churchill Co., Ltd.) to obtain a test piece. Using this test piece, we conducted a combustion test (UL standard SB94 vertical method) and measured the self-extinguishing time, cotton ignition rate, and UL self-extinguishing classification, and the values are shown in Tables 1, 2, and 3. Indicated.

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Claims (1)

[Scope of Claims] 1 (a) 100 parts by weight of an olefin polymer or a copolymer between olefins (b) An aromatic bromine compound in which bromine is directly bonded to the core and has a bromine content of 55% or more (however, (excluding compounds with bromine bonded to the side chain) 12 to 25 parts by weight, (c) General formula: (However, R ¹ and R ² are selected from the same or different phenyls or substituted phenyls. A type of
R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different groups selected from hydrogen, alkyl, cycloalkyl, halogen, cyano group, and nitro group, and R ³ , R ⁴ , Three or more of R ⁵ and R ⁶ must not be cyano groups or nitro groups at the same time. ) A flame-retardant polyolefin containing 0.1 to 2.0 parts by weight of the compound represented by (a), (b), and (c). 2 (a) 100 parts by weight of an olefin polymer or a copolymer between olefins (b) Aromatic bromine compounds in which bromine is directly bonded to the core and the bromine content is 55% or more (however, bromine compounds with bromine in the side chain) (excluding bonded compounds) 12 to 25 parts by weight, (c) General formula: (However, R ¹ and R are the same or different atomic groups selected from phenyl or substituted phenyl, R ³ , R ⁴ , R ⁵ , R ⁶ are the same or different and are groups selected from H, alkyl, cycloalkyl, halogen, cyano group, and nitro group, and R ³ , R ⁴ , R ⁵ , R ⁶ must not be cyano groups or nitro groups at the same time.)
0.1 to 2.0 parts by weight of a compound represented by (d) 3 to 10 parts by weight of antimony trioxide A flame-retardant polyolefin composition comprising (a), (b), (c), and (d). 3 (a) 100 parts by weight of an olefin polymer or a copolymer between olefins (b) Aromatic bromine compounds in which bromine is directly bonded to the core and the bromine content is 55% or more (however, bromine compounds in which bromine is bonded to the side chain) 12 to 25 parts by weight (excluding compounds that combine), (c) General formula: (However, R ¹ and R ² are the same or different atomic groups selected from phenyl or substituted phenyl, R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different and are groups selected from H, alkyl, cycloalkyl, halogen, cyano group, and nitro group, and R ³ , R ⁴ , Three or more of R ⁵ and R ⁶ must not be cyano groups or nitro groups at the same time.)
0.1 to 2.0 parts by weight of a compound represented by (d) 3 to 10 parts by weight of antimony trioxide (e) 5 to 2.5 parts by weight of an inorganic filler (a), (b), (c), (d), ( A flame retardant polyolefin composition comprising e).