JPS61151251A - Flame-retardant polyolefin composition - Google Patents

Abstract

PURPOSE:To obtain a flame-retardant polyolefin compsn. which is highly self- extinguishing, by blending an arom. compd. contg. bromine directly attached to its nucleus and a specified compd. with a polyolefin compsn. CONSTITUTION:A compsn. consists of 100pts.wt. polyolefin compsn., 7-25pts.wt. arom. bromine compd. where a bromine atom is directly attached to its nucleus (excluding compds. where the bromine atom is attached to its side chain) and 0.1-2.0pts.wt. compd. of the formula (wherein R<1>, R<2> are each phenyl, substd. phenyl; R<3>, R<4>, R<5>, R<6> are each H, alkyl, cycloalkyl, halogen, cyano, nitro exclud ing the cases where two or more of R<3>, R<4>, R<5>, R<6> are cyano or nitro at the same time). If desired, 3-10pts.wt. antimony trioxide alone or a mixture of 3.10pts.wt. antimony nitroxide and 5-25pts.wt. inorg. filler may be added to the compsn. to thereby obtain a compsn. having excellent flame retardance.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a polyolefin composition having flame retardancy,
1#)'7+ provides a polyolefin composition having flame retardancy with a small amount of blending by using a specific flame retardant in combination. “Prior Art and Problems” Since polyolefins are composed of hydrocarbons, they have the disadvantage of being easily ignited and producing flames and smoke.Therefore, it is necessary to make polyolefins flame retardant.Especially for electrical products, building materials, etc. For polyolefins to be used, for example, there is a trend for high flame retardancy, such as the flame retardance of V-2 to V-0 according to U.S. standards. Various proposals have been made regarding flame retardation.For example, the most common method involves blending organic or inorganic flame retardants with polyolefin. In order to achieve the desired flame retardant effect in conventional flame retardant polyolefin compositions, it is necessary to incorporate a flame retardant on each side, which requires expensive, moldable, and paste polymer additives. Problems such as poor physical properties may occur.Also, even if this method is used, the desired flame retardant effect, especially high self-extinguishing property, may not be achieved.[To solve the problem] [Hand IQ] The present inventors have formulated a flame retardant that is flame retardant in small amounts.

[As a result of various studies on polyolefin compositions, it was discovered that the above problems could be solved by blending the polyolefin with a specific flame retardant.
I came up with plan F'. That is, the present invention comprises (a) 100 parts by weight of a polyolefin composition (b) an aromatic bromine compound in which one bromine is still tangentially bonded to the nucleus (IH Si, 111 parts by weight)
7 to 25 (excluding compounds in which bromine is bonded to the 11 chain)
Part by weight 1'1) Do) A group selected from H, alkyl, cycloalkyl halogen, cyano group, and nitro group, and two or more of R', R', and R' are at the same time a hiscyano group or a nitro group. This is a flame-retardant polyolefin composition comprising 0.1 to 2.0 parts by weight of a compound represented by the following formula. Preferably, this is a flame-retardant polyolefin composition to which 1 to 10 parts by weight of antimony trioxide is added as a fourth component, and more preferably, 5 to 10 parts by weight of an inorganic filler is added to this as a fifth component. ~25 parts by weight are added to also provide a 7-flame retardant polyolefin composition. The polyolefin used in the present invention is, for example, a homopolymer of α-olefin such as ethylene, propylene, butylene, a copolymer or block copolymer of the α-olefin and other α-olefins, or a block copolymer thereof. Among them, polyolefins containing polypropylene as a main component are particularly preferred. In the present invention, the most important thing is to use a flame retardant having a specific structure in combination with the L polyolefin. That is, polyolefin 100 electrolyte moieties are directly bonded to the core of 1 or aromatic 9 element compounds (excluding compounds in which 11' and side chains of ζ and C are bonded) 7 to 25 heavy metals. It is necessary to mix 1 to 2.0 Φ parts of the mold. Conventionally, it has been proposed to use each of the "combustible retardants listed in Chapter 1" in combination with other flame retardants or other flame retardants. A composition consisting of antimony 11, or Japanese Patent Application No. 12848, bromine is directly bonded to the nucleus.
A composition containing an aromatic nine element compound was also published in
No. 4-91121 has the general formula; R'-(: -<:
-R2-containing compositions have been described, but these may involve methods other than formulation, such as the above-mentioned t, 1) 1)
．． In order to obtain a high degree of flame retardancy such as ■-0 to Gold V-2 according to the standards, there is a drawback that the total number of flame retardants to be blended is large. On the other hand, according to the present invention, bromine is directly bonded to the nucleus as described in 1-1. By simply combining the aromatic bromine compound with the general formula; a composition having the desired flame retardancy is obtained due to the synergistic action of both flame retardants;
, antimony M-ide or antimony pentoxide inorganic material
By blending the Yi agent, the composition is made flame retardant.
:It is something that can be done. Aromatics used in the present invention 9. An elementary compound is a compound in which a hydrogen atom is directly bonded to a (benzene) nucleus, such as nonatomized benzenes such as hexabromobenzene and pentabromobenzene; pentabromotoluene. Silinated toluene such as tetrabromotoluene; 1,000 toluene
brominated xylenes such as m1muxilone and tribromoxylene, brominated phenols and their metal salts such as pentabromophenol, tetrabromoresorcin, trifluoronobilogallol, and sodium pendabromoferate; pentabromoaniline, Brominated anilines such as tetrabromoaniline; pentabromobenzoic acid, tetrabromobutane m and derivatives thereof; heterosubstituted brominated benzenes such as tetrabromosalicylic acid, tetrabromotoluic acid, tetrabrono, and Fresol; tetrabrominated phthalic anhydride, etc. Anhydrous anhydride; 9-substituted biphenyls; brominated diphenyl ether, brominated diphenylthioether, etc.; brominated naphthalene derivatives; brominated anthracene derivatives; 9-substituted aromatics such as tribrono, polystyrene, etc. Examples include polymers. Among these, those having a bromine content of 55% or more are particularly preferably used. In the present invention, bromine is directly bonded to a particularly selected nucleus among aromatic bromine compounds known as sister combustion agents.1. It is important to use aromatic bromine compounds that are I'll also refer to compounds with bromine attached directly to the nucleus (), but compounds with tows attached to the side chain, such as bisphenol A bis(2IN(hpropyl ether)), tetrabromide Dihydroxy diphenyl sulfone (propyl ether di1) and the like cause flame leakage and are therefore unsuitable for the present invention.Furthermore, aliphatic silicon compounds, which are often used as flame retardants for olefins in item 1. For example, tetrabromobutane, tribromopropane, etc. are similarly unusable and cannot be used in the present invention. Parts. Rima1 is 12 to 20 parts by weight.If the amount of the aromatic bromine compound in L is less than 7 parts by weight, the flame retardant effect, especially the self-extinguishing property, is insufficient. On the other hand, if the amount is more than 25 heavy electric type, the flame retardant effect not only reaches its peak, but also has a negative effect on the physical properties of the polymer.R3R'+ -CIn the compound shown, R', R2 are the same or so4 (Kyoshidan°C phenyl or ζ-substituted phenyl, R3, R'', R's R%f the same or different, I+, alkyl, cycloalkyl, halogen,
A group selected from a cyano group and a nitro group, R
3, R', R must not contain two or more cyano groups or 'nitro groups at the same time. Examples of such compounds include 2. ;)-diethyl-2,3-diphenylbutane, 2. ;3-dimethyl-2
+ 3-p-) rilbudan, 2. ;)-di-methyl-2
, :3-di-p-bromphenylbutane, 2. ;)-diethyl-2,;)-di-p-chlorophenylbutane, 2
．． ;3-dimethyl-2,3-di)-ethoxyphenylbutane, 2,2,3.3-tetraphenylbutane, 1
,2-dibromo-1゜2-dimethyl-1,2-diphenylethane, 1゜2-dibromo-1,2-diphenylethane, 1゜2-dinitro-1,2-diphenylethane, 1
゜2-dinitrirJ-1,2-jp-)lylethane, 2
, ;3-dicyan-2,3-diphenylbutane, 1.2
-dichloro-1,2-diphenylethane and mixtures of these compounds. The compound is preferably used in an amount of 0.1 to 2.0 parts per 100 parts of the polyolefin composition.
Noku is 1.0-2. () Mold portion 11 is fitted. If the blending ratio is less than 0.1 part by weight, the combustion effect will not be sufficiently exhibited. On the other hand, if the amount is more than 2.0 type part, no particularly remarkable effect will be exhibited, and the result will instead have a negative effect on the physical properties of the polymer. In the present invention, the above-mentioned polyolefin, aromatic compound, general formula: R'-C-C-R2 is combined with antimony oxide or antimony pentoxide and an inorganic filler. As a result, the antimony pentoxide or antimony vide and the inorganic filler act synergistically to increase the flame retardant effect, and exhibit high flame retardancy with a small amount of flame retardant. (This effect is not expected at all from the case where only one component or two components are added to a polyolefin.1) There is a negative effect. Antimony pentoxide is generally preferably one with an average particle size of 2 to 20/Z; Antimony is added in an amount of 3 to 10 parts by weight, preferably 4 to 10 parts by weight, based on 100 parts of polyolefin.
Contains less than 7 parts by weight. As the inorganic filler used in the present invention, known inorganic fillers such as DARC, magnesium hydroxide, calcium carbonate, and magnesium carbonate can be used without particular limitation. In particular, those having an average particle size of 2 to 207z are preferably used. The inorganic filler is contained in an amount of 5 to 25 parts per 100 parts per year of polyolefin.
Heavy electric parts, preferably 15 to 20 parts by weight, are blended. In the present invention, if the amount of antimony pentoxide or '-' antimony oxide and inorganic filler blended into the polyolefin is less than the above-mentioned specific range, it is difficult to obtain a sufficient flame retardant effect of the resulting polyolefin composition. Can not. Further, if the amount exceeds the specified range, it is not preferable because the flame retardant effect may not be significantly improved and the physical properties of the flame retardant may be deteriorated. In the present invention, the polyolefin, aromatic brominated R
6 Compound, φ to X:, antimony oxide 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, it is also possible to adopt a method of changing the mixing order and equipment, such as mixing several types in advance in a Henschel mixer, then adding the rest and mixing in a tumbler blender. Further, the extrusion method is not particularly limited either, and the composition of the present invention mixed at 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 obtain a predetermined ratio of 14 A targeted composition may be obtained. The polyolefin composition of the present invention basically consists of the above-mentioned polyolefin, an aromatic bromine compound, F oxidized anti-chloride, or an inorganic filler, but in addition to these components, Conventionally known stabilizers, colorants, antistatic agents, lubricants, nucleating agents, etc. may be added.Efficacy: The polyolefin composition of the present invention can improve these properties by blending a specific flame retardant. Due to the synergistic effect of the flame retardants in
It also has excellent moldability and does not adversely affect the physical properties of the base polymer. Moreover, the above-mentioned IJ 1. (94,
> It is also possible to have a flame retardancy of ^ degree corresponding to V-O to v-2 [in the case of I"! [Example] To specifically explain the present invention to φ Hereinafter, the present invention will be explained by giving examples and comparative examples, but the present invention is not limited to these examples.The experimental results shown in the examples and comparative examples are based on the vertical method of The average self-extinguishing time was calculated by showing the average self-extinguishing time after each of the 10 combustion test specimens was ignited twice, i.e., 20 times in total. The degree to which the cotton below ignited due to 1' fire from the test piece is shown below, indicating how many of the five cotton strands were ignited. For example, if 3 out of 5 were ignited, the total would be 315 and 1. Ta. The shape of the test piece is 5 inches x 0.5 inches x 1/16
I went in inches. Example 1 Polypropylene (P
, P, manufactured by Toku 111 Soda Co., Ltd.), polyethylene with MT = 2 (P, E), polybutene with Ml = Fi (1).
Below, among the aromatic groups shown in Tables 1, 2 and 3, elementary compounds, general formula: R'-C-C-R2
T This pellet was molded using a 1°5oz extrusion molding machine (manufactured by Rochurchille) to form a test piece.
-I got it. Using this test piece, a combustion test (TL standard S B94 vertical method) was conducted, and self-extinguishing time, cotton ignition rate, and 111
．． Measure the amount of self-extinguishing. Table 1 shows this value. It is shown in Table 2 and Table 3. 17-1

Claims (3)

[Claims] (1) (a) 100 parts by weight of polyolefin composition (b)
Aromatic bromine compounds in which bromine is directly bonded to the nucleus (however, compounds in which bromine is bonded to the side chain are excluded) 7 to 25 parts by weight (c) General formula: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (However, , R^1, R^2 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, H, alkyl, A group selected from cycloalkyl halogen, cyano group, and nitro group, R^3, R^4, R^5, R^
Two or more of 6 must not be cyano groups or nitro groups at the same time. ) A flame-retardant polyolefin composition comprising 0.1 to 2.0 parts by weight of the compound represented by: (2) (a) 100 parts by weight of polyolefin composition (b)
Aromatic bromine compounds in which bromine is directly bonded to the nucleus (however, compounds in which bromine is bonded to the side chain are excluded) 7 to 25 parts by weight (c) General formula: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (However, , R^1, R^2 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, H, alkyl, A group selected from cycloalkyl halogen, cyano group, and nitro group, R^3, R^4, R^5, R^
Two or more of 6 must not be cyano groups or nitro groups at the same time. ) A flame-retardant polyolefin composition comprising 0.1 to 2.0 parts by weight of a compound represented by (d) 3 to 10 parts by weight of antimony trioxide. (3) (a) 100 parts by weight of polyolefin composition (b)
Aromatic bromine compounds in which bromine is directly bonded to the nucleus (however, compounds in which bromine is bonded to the side chain are excluded) 7 to 25 parts by weight (c) General formula: ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ (However, , R^1, R^2 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, H, alkyl, A group selected from cycloalkyl halogen, cyano group, and nitro group, R^3, R^4, R^5, R^
Two or more of 6 must not be cyano groups or nitro groups at the same time. ) A flame-retardant polyolefin composition comprising 0.1 to 2.0 parts by weight of a compound represented by (d) 3 to 10 parts by weight of antimony trioxide, and (e) 5 to 25 parts by weight of an inorganic filler.