JPH11263885A - Flame-retardant polyolefin resin composition and molded article comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin-based resin composition having excellent flame retardancy with a small amount of addition by using an inorganic phosphorus-containing flame retardant containing no halogen in combination with an inorganic flame retardant and a molded article comprising the same. Offer. SOLUTION: As a flame retardant for polyolefin resin,
(A) The following general formula (1) (Wherein X ¹ and X ² are each independently selected from the group consisting of an alkoxy group, an aryloxy group and an amino group, and n is an integer of 3 to 10.) , (B) the following general formula (2): Wherein M is a metal of the second main group, a metal of the third main group, a metal of the second subgroup, and a metal of the third subgroup of the periodic table, and m is 2 or 3. A flame-retardant polyolefin-based resin composition comprising the metal hydroxide and, if necessary, (C) red phosphorus, and a molded article comprising the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel flame-retardant polyolefin-based resin composition and a molded article comprising the same.

[0002]

2. Description of the Related Art Conventionally, polyolefin-based resins have been widely used in the fields of industrial and household electric appliances, taking advantage of their advantages such as processability, chemical resistance, weather resistance, electrical properties and mechanical strength. As a result, the amount of polyolefin resin used has been increasing. However, polyolefin resins are also strongly required to have flame retardancy, and the degree of the demand is gradually increasing in recent years.

[0003] In particular, recently, halogen-containing compounds, which have been the main substances in the conventional flame-retarding of electric wires and cables, are used alone or in combination with an antimony compound such as antimony oxide to form a flame retardant. This has been problematic because the flame-retardant resin composition mixed with the polyolefin-based resin generates a halogen-based gas at the time of combustion or molding. Further, it is said that generation of these gases often impairs electrical characteristics and electric transmission characteristics. Therefore, a flame-retardant resin composition that does not generate these halogen-based gases at the time of combustion or molding has been required.

In order to meet these demands, in recent years, the endothermic reaction of dehydration pyrolysis at the resin combustion temperature has caused the thermal decomposition of the resin,
Certain metal hydrates that can increase the flame retardant effect by occurring in a temperature range that overlaps with the combustion start temperature have been used as inorganic flame retardants. However, inorganic flame retardants alone do not have a significant effect of imparting flame retardancy, so that they must be blended in large amounts, and this has the disadvantage of adversely affecting the mechanical strength of the resulting molded article.

[0005]

Accordingly, an object of the present invention is to provide a polyolefin-based resin composition having excellent flame retardancy with a small amount of addition by using an organic phosphorus-based flame retardant containing no inorganic flame retardant halogen. An object of the present invention is to provide an article and a molded article made thereof.

[0006]

Means for Solving the Problems The first aspect of the present invention is to provide a polyolefin resin as a flame retardant (A) having the following general formula (1):

Embedded image (Wherein X ¹ and X ² are each independently selected from the group consisting of an alkoxy group, an aryloxy group and an amino group, and n is an integer of 3 to 10.) And (B) the following general formula (2)

Embedded image Wherein M is a metal of the second main group, a metal of the third main group, a metal of the second subgroup, and a metal of the third subgroup of the periodic table, and m is 2 or 3. The present invention relates to a flame-retardant polyolefin resin composition containing the metal hydroxide shown below.

A second aspect of the present invention is to use a polyolefin resin as a flame retardant (A) represented by the following general formula (1):

Embedded image (Wherein X ¹ and X ² are each independently selected from the group consisting of an alkoxy group, an aryloxy group and an amino group, and n is an integer of 3 to 10.) , (B) the following general formula (2)

Embedded image Wherein M is a metal of the second main group, a metal of the third main group, a metal of the second subgroup, and a metal of the third subgroup of the periodic table, and m is 2 or 3. The present invention relates to a flame-retardant polyolefin-based resin composition comprising the metal hydroxide shown below and (C) red phosphorus.

[0008] A third aspect of the present invention relates to a molded article comprising the flame-retardant polyolefin resin composition.

The amount of the flame retardant composed of the components (A) and (B) or the flame retardant composed of the components (A), (B) and (C) depends on the amount of the polyolefin resin and the flame retardant. It is 10 to 60% by weight, preferably 30 to 50% by weight based on the total weight.

[0010] When the flame retardant is used in an amount of 10 to 60% by weight, when the component (A) and the component (B) are used,
The component (A) is 1 to 40% by weight, preferably 5 to 30% by weight, and the component (B) is 99 to 60% by weight, preferably 95 to 95% by weight.
70% by weight, and when the flame retardant comprises the component (A), the component (B) and the component (C), the components (A) 1 to 40
% By weight, preferably 4 to 30% by weight,
It is 60% by weight, preferably 94 to 69% by weight, 0.1 to 15% by weight, preferably 1 to 10% by weight of the component (C).

The nitrogen-containing organic phosphorus compound, that is, the phosphazene derivative, which is one of the components of the flame-retardant polyolefin resin composition according to the present invention, is present in the polyolefin resin together with the other components according to the present invention. In this case, it is a compound that generates a non-flammable gas by heat due to ignition or ignition or contact with a flame, and also forms a carbon residue or promotes the formation of the carbon residue. Specifically, the compound is represented by the following general formula (3) )

Embedded image The basic unit of the phosphazene monomer structure represented by is represented by the following formula. Representative examples of the groups X ¹ and X ^{2 in} the formula can be illustrated below.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group and an iso-butoxy group. preferable.
Examples of the aryloxy group include an unsubstituted or methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-octyl group, a methoxy group, an ethoxy group, and a 2,3-dimethyl group. A 2,4-dimethyl group, a 2,5-dimethyl group, a 2,6-dimethyl group,
Examples thereof include a phenyloxy group substituted with a 3,5-dimethyl group, a phenyl group, and the like. Further, examples of the aryl group include a naphthyl group.

The phosphazene derivative represented by the general formula (1) is represented by the following general formula (4)

Embedded image (Where n is 3 to 10) and a chlorophosphazene derivative represented by the following general formula (5)

Embedded image Wherein Ar is a phenyl group, p-, m- or o-tolyl group, p-, m- or o-anisyl group, 2,3-, 2,4
-, 2,5-, 2,6- or 3,5-xylyl group, 1-
Or an aromatic group such as a 2-naphthyl group or a biphenyl group) or a phenol represented by the following general formula (6):

Embedded image (Wherein, R is a linear or branched saturated alkyl group having 1 to 8 carbon atoms), an organic or inorganic base such as a trialkylamine, a metal alcoholate, It is obtained by reacting in the presence of sodium hydride, sodium amide and the like.

Specific examples of the phosphazene derivative represented by the general formula (1) used in the present invention include 1,1,3,3,5,5-hexa (methoxy) cyclotriphosphazene and 1,1,3 , 3,5,5-hexa (ethoxy) cyclotriphosphazene, 1,1,3,
3,5,5-hexa- (n-propoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa- (is
o-propoxy) cyclotriphosphazene, 1,1,
3,3,5,5-hexa- (n-butoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa- (i
so-butoxy) cyclotriphosphazene, 1,1,
3,3,5,5-hexa (phenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa- (p-tolyloxy) cyclotriphosphazene, 1,1,3
3,5,5-hexa- (m-tolyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa- (o
-Tolyloxy) cyclotriphosphazene, 1,1,
3,3,5,5-hexa- (p-anisyloxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa- (m-anisyloxy) cyclotriphosphazene,
1,1,3,3,5,5-hexa- (o-anisyloxy) cyclotriphosphazene, 1,1,3,3,5,5
-Hexa (4-ethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-n-propylphenoxy) cyclotriphosphazene, 1,1,
3,3,5,5-hexa (4-iso-propylphenoxy) cyclotriphosphazene, 1,1,3,3,5
5-hexa (4-tert-butylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (4-tert-octylphenoxy) cyclotriphosphazene, 1,1,3,3,5 5-hexa (2,3-
Dimethylphenoxy) cyclotriphosphazene, 1,
1,3,3,5,5-hexa (2,4-dimethylphenoxy) cyclotriphosphazene, 1,1,3,3,5
5-hexa (2,5-dimethylphenoxy) cyclotriphosphazene, 1,1,3,3,5,5-hexa (2
6-dimethylphenoxy) cyclotriphosphazene,
1,1,3,3,5,5-hexaaminocyclotriphosphazene, 1,1,3,3,5,5-hexa (4-phenylphenoxy) cyclotriphosphazene, 1,3,5
-Tris (methoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5 Tris (n-propoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (iso-propoxy) -1,3,5-tris (phenoxy) cyclotriphosphazene, , 3,5-Tris (n-butoxy)-
1,3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (iso-butoxy) -1,
3,5-tris (phenoxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (p-tolyloxy) cyclotriphosphazene,
1,3,5-tris (methoxy) -1,3,5-tris (m-tolyloxy) cyclotriphosphazene,
3,5-tris (methoxy) -1,3,5-tris (o
-Tolyloxy) cyclotriphosphazene, 1,3,5
-Tris (methoxy) -1,3,5-tris (p-anisyloxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (m-anisyloxy) cyclotriphosphazene, , 3,5-Tris (methoxy) -1,3,5-tris (o-anisyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-tris (p-tolyloxy) cyclo Triphosphazene 1,3,5-tris (ethoxy) -1,3,5-tris (m-tolyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy)-
1,3,5-tris (o-tolyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,
3,5-tris (p-anisyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,3
5-tris (m-anisyloxy) cyclotriphosphazene, 1,3,5-tris (ethoxy) -1,3,5-
Tris (o-anisyloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,3
5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,3
5-tris (m-tolyloxy) cyclotriphosphazene 1,3,5-tris (n-propoxy) -1,3,3
5-tris (o-tolyloxy) cyclotriphosphazene 1,3,5-tris (n-propoxy) -1,3,3
5-tris (p-anisyloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,
3,5-tris (m-anisyloxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy)-
1,3,5-tris (o-anisyloxy) cyclotriphosphazene, 1,3,5-tris (iso-propoxy) -1,3,5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5 -Tris (n-butoxy) -1,3,5-tris (p-tolyloxy) cyclotriphosphazene, 1,3,5-tris (iso-butoxy) -1,3,5-tris (p-tolyloxy) cyclo Triphosphazene, 1,3,5-tris (methoxy)
-1,3,5-tris (4-tert-butylphenoxy) cyclotriphosphazene, 1,3,5-tris (methoxy) -1,3,5-tris (4-tert-octylphenoxy) cyclotriphosphazene, 1,3,5-
Tris (n-propoxy) -1,3,5-tris (4-
tert-butylphenoxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,3
5-tris (4-tert-octylphenoxy) cyclotriphosphazene, 1,3,5-tris (methoxy)
-1,3,5-tris (4-phenylphenoxy) cyclotriphosphazene, 1,3,5-tris (ethoxy)
-1,3,5-tris (4-phenylphenoxy) cyclotriphosphazene, 1,3,5-tris (n-propoxy) -1,3,5-tris (4-phenylphenoxy) cyclotriphosphazene, 3,5-Tris (i
so-propoxy) -1,3,5-tris (4-phenylphenoxy) cyclotriphosphazene, 1,3,5-
Tris (n-butoxy) -1,3,5-tris (4-phenylphenoxy) cyclotriphosphazene, 1,3
5-tris (iso-butoxy) -1,3,5-tris (4-phenylphenoxy) cyclotriphosphazene,
1,1-diamino-3,3,5,5-tetrakis (methoxy) cyclotriphosphazene, 1,1-diamino-
3,3,5,5-tetrakis (ethoxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (n-propoxy) cyclotriphosphazene,
1,1-diamino-3,3,5,5-tetrakis (is
o-propoxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (n-butoxy)
Cyclotriphosphazene, 1,1-diamino-3,3,
5,5-tetrakis (isobutoxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (phenoxy) cyclotriphosphazene, 1,1-
Diamino-3,3,5,5-tetrakis (p-tolyloxy) cyclotriphosphazene, 1,1-diamino-
3,3,5,5-tetrakis (m-tolyloxy) cyclotriphosphazene, 1,1-diamino-3,3,5
5-tetrakis (o-tolyloxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (p-anisyloxy) cyclotriphosphazene,
1,1-diamino-3,3,5,5-tetrakis (m-
Anisyloxy) cyclotriphosphazene, 1,1-diamino-3,3,5,5-tetrakis (o-anisyloxy) cyclotriphosphazene, 1,1-diamino-
3,3,5,5-tetrakis (4-phenylphenoxy) cyclotriphosphazene and the like.

Among the phosphazene derivatives represented by the general formula (1), aminophosphazene [trade name: SA
100; in the general formula (1), X ¹ and X ² are both amino groups, n is 3 to 10], hexaphenoxyphosphazene, propoxyphosphazene [trade name: SPR100;
In the general formula (1), X ¹ and X ² are both n-propoxy groups, and n is 3 to 10]; a mixture of hexaphenoxyphosphazene and octaphenoxyphosphazene [trade name: SP134; , X ¹ and X ² are both phenoxy groups, n is 2 to 3], or in the general formula (1), X ¹ and X ² are both phenoxy groups;
Since a phenoxyphosphazene derivative (trade name: SP100) composed of a mixture of n of 3 to 10 is commercially available (Otsuka Chemical Products), it can be used as it is.

The general formula (2)

Embedded image Wherein M is a metal of the second or third main group of the periodic table, a metal of the second or third subgroup, especially aluminum, calcium, zinc or preferably magnesium, and m is 2 Or 3) may be the compound alone or an organic compound,
For example, it may be coated with a metal salt of a second main group or a third main group of a higher aliphatic carboxylic acid, or a metal salt of a second subgroup or a third subgroup. The metal hydroxide, particularly magnesium hydroxide, is 5A, B, E, J (trade name, manufactured by Kyowa Chemical),
Water mug 200, water mug 10, water mug 10A, star mug UM, star mug M, star mug L, star mug S, star mug C, CY (trade name Kamishima Chemical), FR
Since it is commercially available as -20 (trade name, manufactured by Promochem Far East), it may be used as it is.

The red phosphorus may be used alone, or may be coated with an appropriate inorganic or organic compound, or may be diluted with a non-halogen organic polymer composition. Commercial products of the red phosphorus include no pallets 120, 120 UF, 120 UFA, Nopa Excel ST, W, MG, RX series, various Nope pallets (trade name, manufactured by Rin Kagaku), Hishigard CP, CP-1
5, UR-15, TP-10, Safe TP-10 (manufactured by Nippon Chemical), RP-120 (manufactured by Suzuhiro Chemical) and the like can be used as they are.

The flame-retardant polyolefin resin composition according to the present invention may further contain, for example, conventional additives, for example, may contain an antioxidant, a light stabilizer and a metal deactivator. In addition, if necessary, various fillers, conductive powders and the like may be contained.

Antioxidants which may be added in addition to the compounds according to the invention include, for example, 2,6-di-tert-
Butyl-4-methylphenol, 2-tert-4,6
-Dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert
-Butyl-4-isobutylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol,
2,6-dioctadecyl-4-methylphenol, 2,
4,6-tricyclohexylphenol, 2,6-dinonyl-4-methylphenol, 2,6-di-tert-
Butyl-4-methoxymethylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl)-
Phenol, 2,4-dimethyl-6- (1'-methyl-
Heptadec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyl-trideca-1'-yl)-
Phenol and mixtures thereof, 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,
4-di-octylthiomethyl-6-methylphenol,
2,4-di-octylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol and mixtures thereof, 2,6-di-tert-
Butyl-4-methoxyphenol, 2,5-di-ter
t-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4
-Hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert
-Butyl-4-hydroxyphenylstearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate and mixtures thereof, 2,4-bis-octylmercapto-6- (3,5-diphenyl -Tert-
Butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3
5-di-tert-butyl-4-hydroxyanilino)
-1,3,5-triazine, 2-octylmercapto-
4,6-bis (3,5-di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,
4,6-tris (3,5-di-tert-butyl-4-
Hydroxyphenoxy) -1,2,3-triazine,
1,3,5-tris (3,5-di-tert-butyl-
4-hydroxybenzyl) -isocyanurate, 1,
3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -isocyanurate,
2,4,6-tris (3,5-di-tert-butyl-
4-hydroxyphenylethyl) -1,3,5-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) -hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclohexyl-4-hydroxybenzyl) -isocyanurate and the like and 2,2′-methylenebis (6-tert-butyl-4-methylphenol),
2,2'-methylenebis (6-tert-butyl-4-
Ethylphenol), 2,2'-ethylidenebis (4,
6-di-tert-butylphenol), 2,2'-ethylidenebis (6-tert-butyl-4-isobutylphenol), 4,4'-methylenebis (2,6-di-
tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methylphenol),
1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, ethylene glycol bis [3,3'-bis (3'-tert-butyl-4'-)
Hydroxyphenyl) butyrate] and 1,3,
5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene,
1,4-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-
4-hydroxybenzyl) -phenol and the like.

Light stabilizers which may be added in addition to the compounds according to the invention include, for example, 2- (2'-hydroxy-
5'-methylphenyl) benzotriazole, 2-
(3'5'-di-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (5'-tert
-Butyl-2'-hydroxyphenyl) benzotriazole, 2- [2'-hydroxy-5 '-(1,1,3,
3-tetramethylbutyl) phenyl] benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-
(Hydroxyphenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-4'-octo) (Xyphenyl) benzotriazole, 2- (3 ', 5'-di-t
ert-amyl-2'-hydroxyphenyl) benzotriazole, 2- [3'-tert-butyl-2'-hydroxy-5 '-(2'-octyloxycarbonylethylphenyl) -5-chlorobenzotriazole, etc .: 4
-Hydroxy-, 4-methoxy-, 4-octoxy-,
4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy-, 4,2 ', 4'-trihydroxy-,
2'-hydroxy-4,4'-dimethoxy- or 4-
(2-ethylhexyloxy) -2-hydroxybenzophenone derivatives and the like: 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis (4-tert-butylbenzoylresorcinol),
2,4-di-tert-butylphenyl 3,5-di-t
tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, etc .: ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β
-Diphenyl acrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p
-Methoxycinnamate and the like: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2
2,6,6-tetramethyl-4-piperidyl) succinate, bis (1,2,2,6,6-pentamethyl-4-)
Piperidyl) sebacate, bis (1-octyloxy-
2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4)
-Piperidyl) adipate and the like: 4,4'-di-octyloxyoxanilide, 2,2'-diethoxyoxyoxanilide, 2,2'-di-octyloxy-5,5'-
Di-tert-butyl oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl oxanilide, 2-ethoxy-2'-ethyl oxanilide,
N, N'-bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2'-
Ethoxy oxanilide and the like: 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5
-Triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl)- 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6
-(2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl)-
1,3,5-triazine and the like.

Metal deactivators which may be added in addition to the compounds according to the invention include, for example, N, N'-diphenyloxalic acid diamide, N-sartilal-N'-salicyloylhydrazine, N, N ' -Bis (salicyloyl) hydrazine, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,3-triazole, bis (benzylidene) ) Oxalic acid hydrazide, isophthalic acid dihydrazide, N, N'-diacetal-adipic dihydrazide, N, N'-bis-salicyloyl oxalic acid dihydrazide, N, N'-bis-salicyloyl-thiopropionic acid dihydrazide and the like. Can be

The flame-retardant polyolefin-based resin composition of the present invention is used for various molded articles, and is used for coatings, especially electric wires, cables, electric parts, machine parts, plugs, mounts, casings, covers, It is useful as a material for producing a fire protection coating for an exterior.

The polyolefin resin includes polyethylene, polypropylene, ethylene-propylene copolymer, polybutylene, polymethylpentene, ethylene-
Examples thereof include a vinyl acetate copolymer and an ethylene-methyl acrylate (ethyl) copolymer.

[0024]

EXAMPLES The present invention will be specifically described below with reference to synthesis examples of the compounds of the present invention. However, these are merely examples of preferred embodiments, and the present invention is not limited to these examples. .

Synthesis Example 1 Synthesis of hexa (phenoxy) cyclotriphosphazene [in the general formula (1), X ¹ and X ² are both phenoxy groups, and n is 3]. After replacing the 200-ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser with nitrogen, 30 m
l of tetrahydrofuran (THF) and 60% NaH
(6.90 g) and stirred at room temperature. A solution obtained by diluting phenol (16.2 g) with 30 ml of THF was gradually dropped from a dropping funnel. After the completion of the dropwise addition, the mixture was heated and stirred at 40 ° C. for 30 minutes. Next, the temperature is returned to room temperature.
The obtained THF solution of sodium phenolate is used directly in the next reaction. A 10 ml flask was equipped with a thermometer, a stirrer, a dropping funnel, and a condenser.
Add 0 ml of THF and hexachlorocyclotriphosphazene (10.0 g) and stir at room temperature. When the phosphazene was completely dissolved, the above-mentioned THF solution of sodium phenolate was gradually dropped from the dropping funnel. After completion of the dropwise addition, heating and stirring are continued for 24 hours. After the completion of the reaction, the mixture is cooled, and insolubles are removed by filtration. The filtrate was concentrated to 22.1
g of crude product are obtained. By recrystallization from heptane, 19.2 g of hexa (phenoxy) cyclotriphosphazene having a melting point of 112 to 114 ° C. was obtained. Infrared spectrum: (KBr) cm ^-1 1275 (O-Car), 118
0 (P = N), 1160 (P-OCar), 950 (P
-O-Car).

Synthesis Example 2 Synthesis of hexa (phenoxy) cyclotriphosphazene and octa (phenoxy) cyclotetraphosphazene (in the general formula (1), X ¹ and X ² are both phenoxy groups, and n is 3 to 4). After replacing the 200-ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser with nitrogen, 30 m
Add 1 THF and 60% NaH (6.90 g) and stir at room temperature. 30 m of phenol (16.2 g)
The solution diluted with 1 liter of THF was gradually dropped from the dropping funnel. After the completion of the dropwise addition, the mixture was heated and stirred at 40 ° C. for 30 minutes. Next, the temperature is returned to room temperature. The obtained THF solution of sodium phenolate is used directly in the next reaction. 30 with thermometer, stirrer, dropping funnel, and cooling tube
100 ml of THF and a mixture of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene (mixing ratio: 8: 2, 10.0 g) are added to a 0 ml four-necked flask, and the mixture is stirred at room temperature. When the phosphazene was completely dissolved, the above-mentioned THF solution of sodium phenolate was gradually dropped from the dropping funnel. After completion of the dropwise addition, heating and stirring are continued for 24 hours. After the reaction, cool down
The insoluble material is filtered off. Concentration of the filtrate gives 25.6 g of crude product. When thoroughly washed with heptane, 17.5 g of a mixture of hexa (phenoxy) cyclotriphosphazene and octa (phenoxy) cyclotetraphosphazene having a melting point of 95 to 109 ° C. was obtained. Infrared spectrum: (KBr) cm ^-1 1275 (O-Ca
r), 1180 (P = N), 1160 (P-OCa)
r), 958 (PO-Car).

Synthesis Example 3 Hexa (p-tolyloxy) cyclotriphosphazene [In the general formula (1), both X ¹ and X ² are p-
Synthesis of a tolyloxy group and n is 3]. After replacing the 200-ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser with nitrogen, 30 m
Add 1 THF and 60% NaH (6.90 g) and stir at room temperature. p-Cresol (18.6 g)
The solution diluted with 0 ml of THF was gradually dropped from the dropping funnel. After the completion of the dropwise addition, the mixture was heated and stirred at 40 ° C. for 30 minutes. Next, the temperature is returned to room temperature. The obtained THF solution of sodium phenolate is used directly in the next reaction. 3 equipped with thermometer, stirrer, dropping funnel, and cooling tube
100 ml of THF and hexachlorocyclotriphosphazene (10.0 g) are added to a 00 ml four-necked flask and stirred at room temperature. When the phosphazene was completely dissolved, the above-mentioned THF solution of sodium phenolate was gradually dropped from the dropping funnel. After completion of the dropwise addition, heating and stirring are continued for 24 hours. After the completion of the reaction, the mixture is cooled, and insolubles are removed by filtration. Concentration of the filtrate gives 19.4 g of crude product. Melting point 123.5-12 by recrystallization from heptane
16.2 g of hexa (p-tolyloxy) cyclotriphosphazene at 4.5 ° C. was obtained. Infrared spectrum: (KBr) cm ^-1 1270 (O-Ca
r), 1180 (P = N), 1160 (P-OCa)
r), 946 (PO-Car).

Synthesis Example 4 Mixture of hexa (p-tolyloxy) cyclotriphosphazene and octa (p-tolyloxy) cyclotetraphosphazene [In the general formula (1), X ¹ and X ² are both p-tolyloxy groups and n is 3-4]. After replacing the 200-ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser with nitrogen, 30 m
Add 1 THF and 60% NaH (6.90 g) and stir at room temperature. 30 m of phenol (18.6 g)
The solution diluted with 1 liter of THF was gradually dropped from the dropping funnel. After the completion of the dropwise addition, the mixture was heated and stirred at 40 ° C. for 30 minutes. Next, the temperature is returned to room temperature. The obtained THF solution of sodium phenolate is used directly in the next reaction. 30 with thermometer, stirrer, dropping funnel, and cooling tube
100 ml of THF and a mixture of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene (mixing ratio: 8: 2, 10.0 g) are added to a 0 ml four-necked flask, and the mixture is stirred at room temperature. When the phosphazene was completely dissolved, the above-mentioned THF solution of sodium phenolate was gradually dropped from the dropping funnel. After completion of the dropwise addition, heating and stirring are continued for 24 hours. After the reaction, cool down
The insoluble material is filtered off. Concentration of the filtrate gives 25.6 g of crude product. When sufficiently washed with heptane, hexa (p-tolyloxy) having a melting point of 87.5 to 117.5 ° C.
15.6 g of a mixture of cyclotriphosphazene and octa (p-tolyloxy) cyclotetraphosphazene was obtained. Infrared spectrum: (KBr) cm ^-1 1282 (O-Ca
r), 1180 (P = N), 1162 (P-OCa)
r), 958 (PO-Car).

Preparation Example 1 Preparation of magnesium hydroxide containing phosphazene derivative obtained in Synthesis Example 1. After adding 250 ml of acetone to a 500 ml round bottom flask, the phosphazene derivative (5.
0g) and stirred at room temperature. When the phosphazene derivative is completely dissolved, the magnesium hydroxide (9
5.0 g) was added in small portions. Stirring is continued for 30 minutes after the addition is completed. The acetone is recovered and the powdery solid is
Vacuum dry at ° C.

Preparation Example 2 Preparation of magnesium hydroxide containing phosphazene derivative obtained in Synthesis Example 2. After adding 250 ml of acetone to a 500 ml round bottom flask, the phosphazene derivative obtained in Synthesis Example 2 (5.
0g) and stirred at room temperature. When the phosphazene derivative is completely dissolved, the magnesium hydroxide (9
5.0 g) was added in small portions. Stirring is continued for 30 minutes after the addition is completed. The acetone is recovered and the powdery solid is
Vacuum dry at ° C.

Preparation Example 3 Preparation of magnesium hydroxide containing phosphazene derivative obtained in Synthesis Example 3. After adding 250 ml of acetone to a 500 ml round bottom flask, the phosphazene derivative obtained in Synthesis Example 3 (5.
0g) and stirred at room temperature. When the phosphazene derivative is completely dissolved, the magnesium hydroxide (9
5.0 g) was added in small portions. Stirring is continued for 30 minutes after the addition is completed. The acetone is recovered and the powdery solid is
Vacuum dry at ° C.

Preparation Example 4 Preparation of magnesium hydroxide containing phosphazene derivative obtained in Synthesis Example 4. After adding 250 ml of acetone to a 500 ml round bottom flask, the phosphazene derivative obtained in Synthesis Example 4 (5.
0g) and stirred at room temperature. When the phosphazene derivative is completely dissolved, the magnesium hydroxide (9
5.0 g) was added in small portions. Stirring is continued for 30 minutes after the addition is completed. The acetone is recovered and the powdery solid is
Vacuum dry at ° C.

Preparation Example 5 Preparation of magnesium hydroxide containing phosphazene derivative and red phosphorus obtained in Synthesis Example 1. After adding 250 ml of acetone to a 500 ml round bottom flask, the phosphazene derivative (4.
0 g) and red phosphorus (1.0 g) were added, and the mixture was stirred at room temperature. When the phosphazene derivative was completely dissolved, a small amount of magnesium hydroxide (95.0 g) was added with stirring.
Stirring is continued for 30 minutes after the addition is completed. The acetone is recovered and the powdery solid is vacuum dried at 40 ° C.

Preparation Example 6 Preparation of magnesium hydroxide containing phosphazene derivative and red phosphorus obtained in Synthesis Example 2. After adding 250 ml of acetone to a 500 ml round bottom flask, the phosphazene derivative obtained in Synthesis Example 2 (4.
0 g) and red phosphorus (1.0 g) were added, and the mixture was stirred at room temperature. When the phosphazene derivative was completely dissolved, a small amount of magnesium hydroxide (95.0 g) was added with stirring.
Stirring is continued for 30 minutes after the addition is completed. The acetone is recovered and the powdery solid is vacuum dried at 40 ° C.

Preparation Example 7 Preparation of magnesium hydroxide containing phosphazene derivative and red phosphorus obtained in Synthesis Example 3. After adding 250 ml of acetone to a 500 ml round bottom flask, the phosphazene derivative obtained in Synthesis Example 3 (4.
0 g) and red phosphorus (1.0 g) were added, and the mixture was stirred at room temperature. When the phosphazene derivative was completely dissolved, a small amount of magnesium hydroxide (95.0 g) was added with stirring.
Stirring is continued for 30 minutes after the addition is completed. The acetone is recovered and the powdery solid is vacuum dried at 40 ° C.

Preparation Example 8 Preparation of magnesium hydroxide containing phosphazene derivative and red phosphorus obtained in Synthesis Example 4. After adding 250 ml of acetone to a 500 ml round bottom flask, the phosphazene derivative obtained in Synthesis Example 4 (4.
0 g) and red phosphorus (1.0 g) were added, and the mixture was stirred at room temperature. When the phosphazene derivative was completely dissolved, a small amount of magnesium hydroxide (95.0 g) was added with stirring.
Stirring is continued for 30 minutes after the addition is completed. The acetone is recovered and the powdery solid is vacuum dried at 40 ° C.

Production of Flame Retardant Polyolefin Composition and Evaluation of Flame Retardancy In evaluating the flame retardancy, UL Subject 94 (Underwriter Laboratories, Inc.) was used.
Complies with the vertical combustion test specified in "Plastic material combustion test for equipment parts". The thickness of the test piece is 1.6 mm. The oxygen index indicating the degree of flame retardancy is based on Japanese Industrial Standard JIS K
Complies with 7201 (combustion test method for polymer materials by oxygen index method).

Example 1 45% by weight of the phosphazene derivative-containing magnesium hydroxide obtained in Preparation Example 1 and 55% by weight of polypropylene as a polyolefin resin were inserted into a mixer.
Stir and mix for minutes. The obtained mixture was melt-kneaded (temperature: 170 ° C.) using a screw extruder and extruded to obtain pellets of the flame-retardant resin composition. 10 pellets obtained
After drying at a temperature of 0 ° C., the pellets were formed into predetermined test pieces using an injection molding machine (cylinder temperature set to 200 ° C.), and the flame retardancy was evaluated. Table 1 shows the results.

Example 2 A flame-retardant resin composition was obtained according to Example 1, except that the phosphazene derivative obtained in Preparation Example 2 was used instead of the phosphazene derivative obtained in Preparation Example 1. Each test piece was prepared in accordance with Example 1, and the flame retardancy was evaluated. Table 1 shows the results.

Example 3 A flame-retardant resin composition was obtained according to Example 1 except that the phosphazene derivative obtained in Preparation Example 3 was used instead of the phosphazene derivative obtained in Preparation Example 1. Each test piece was prepared in accordance with Example 1, and the flame retardancy was evaluated. Table 1 shows the results.

Example 4 A flame-retardant resin composition was obtained according to Example 1, except that the phosphazene derivative obtained in Preparation Example 4 was used instead of the phosphazene derivative obtained in Preparation Example 1. Each test piece was prepared in accordance with Example 1, and the flame retardancy was evaluated. Table 1 shows the results.

Example 5 A flame-retardant resin was prepared according to Example 1, except that a mixture of the phosphazene derivative obtained in Preparation Example 5 and red phosphorus was used instead of the phosphazene derivative obtained in Preparation Example 1. The composition was obtained, each test piece was prepared in accordance with Example 1, and the flame retardancy was evaluated. Table 1 shows the results.

Example 6 A flame-retardant resin was prepared according to Example 1, except that a mixture of the phosphazene derivative obtained in Preparation Example 6 and red phosphorus was used instead of the phosphazene derivative obtained in Preparation Example 1. The composition was obtained, each test piece was prepared in accordance with Example 1, and the flame retardancy was evaluated. Table 1 shows the results.

Example 7 A flame-retardant resin according to Example 1 except that a mixture of the phosphazene derivative obtained in Preparation Example 7 and red phosphorus was used instead of the phosphazene derivative obtained in Preparation Example 1. The composition was obtained, each test piece was prepared in accordance with Example 1, and the flame retardancy was evaluated. Table 1 shows the results.

Example 8 A flame-retardant resin was prepared in the same manner as in Example 1 except that a mixture of the phosphazene derivative obtained in Preparation Example 8 and red phosphorus was used instead of the phosphazene derivative obtained in Preparation Example 1. The composition was obtained, each test piece was prepared in accordance with Example 1, and the flame retardancy was evaluated. Table 1 shows the results.

[0046]

[Table 1]

[0047]

(1) According to the present invention, a novel flame-retardant polyolefin resin composition can be provided. (2) The flame-retardant polyolefin-based resin composition of the present invention comprises:
Since no halogen-based gas is generated when heated or burned, it is environmentally friendly and does not deteriorate electrical characteristics. (3) The composition of the present invention is lighter in weight than those using only an inorganic flame retardant that does not generate halogen, and the electrical properties thereof are stable with a large amount of resin. , And excellent.

Claims (6)

[Claims] 1. A polyolefin resin as a flame retardant,
(A) The following general formula (1) (Wherein X ¹ and X ² are each independently selected from the group consisting of an alkoxy group, an aryloxy group and an amino group, and n is an integer of 3 to 10.) And (B) the following general formula (2): Wherein M is a metal of the second main group, a metal of the third main group, a metal of the second subgroup, and a metal of the third subgroup of the periodic table, and m is 2 or 3. A flame-retardant polyolefin-based resin composition comprising the metal hydroxide shown below. 2. A polyolefin resin as a flame retardant,
(A) The following general formula (1) (Wherein X ¹ and X ² are each independently selected from the group consisting of an alkoxy group, an aryloxy group and an amino group, and n is an integer of 3 to 10.) , (B) the following general formula (2): Wherein M is a metal of the second main group, a metal of the third main group, a metal of the second subgroup, and a metal of the third subgroup of the periodic table, and m is 2 or 3. A flame-retardant polyolefin-based resin composition comprising the metal hydroxide shown below and (C) red phosphorus. 3. A polyolefin resin and the above (A),
(B) or the total amount of the flame retardant is 10 with respect to the total weight of the flame retardant comprising (A), (B) and (C).
The flame-retardant polyolefin-based resin composition according to claim 1, wherein the content is from about 60% by weight to about 60% by weight. 4. The flame-retardant polyolefin resin composition according to claim 1, which has an oxygen index of 28 or more. 5. The method according to claim 1, wherein the component (A) and the component (B) are (B)
(A) on the surface of a powder or a particle mainly composed of
The flame-retardant polyolefin resin composition according to any one of claims 1 to 4, wherein the composition is used in a state of being subjected to a component coating treatment or a microencapsulation treatment. 6. A molded article comprising the flame-retardant polyolefin-based resin composition according to claim 1.