JP2002167482A - Flame-resistant rubber composition and flame-resistant elastomer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-resistant rubber composition, low in decrease in mechanical strength of a vulcanized material even if it has a high content of a non-halogen based flame retardant, and capable of obtaining an elastomer having good mechanical properties, and to obtain a flame-resistant elastomer. SOLUTION: The flame-resistant rubber composition is composed of (A) an olefinic copolymer, (B) a vulcanizing agent and/or a crosslinking agent, and (C) the non-halogen based flame retardant. The olefinic copolymer (A) has (a-1) a structural unit derived from ethylene, (a-2) a structural unit derived from a 3-10C α-olefinic compound, (a-3) a structural unit derived from an unsaturated compound having a functional group, and (a-4) a structural unit derived from a nonconjugated diene based compound, which is contained if necessary, wherein the functional group having a limiting viscosity [η] of 0.1-10 dL/g, measured in decalin at 135 deg.C, is contained in (a-4). The flame-resistant elastomer is obtained by vulcanizing the above flame-resistant rubber composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant rubber composition and an elastomer based on an olefin-based copolymer, and more particularly, to an excellent machine even when a large amount of a non-halogen-based flame retardant is contained. The present invention relates to a flame-retardant rubber composition from which an elastomer having mechanical properties can be obtained, and a flame-retardant elastomer made thereby.

[0002]

2. Description of the Related Art In recent years, elastomers using non-halogen flame retardants have been demanded in the field of rubber from the viewpoint of environmental protection. Generally, a water-containing compound is used as a non-halogen flame retardant, but it is necessary to mix a considerably large amount of a water-containing compound in order to obtain sufficient flame retardancy in an elastomer. However, when the content ratio of the hydrated compound is high, there is a problem that the elastomer has a reduced mechanical strength.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a vulcanizate having a small decrease in mechanical strength, even if the content of a non-halogen flame retardant is high, and therefore to provide good mechanical properties. An object of the present invention is to provide a flame-retardant rubber composition from which an elastomer having the same is obtained. Another object of the present invention is to provide a flame-retardant elastomer having a small decrease in mechanical strength of a vulcanizate and therefore having good mechanical properties even if the content of a non-halogen flame retardant is high. Is to do.

[0004]

According to the present invention, the following flame-retardant rubber composition is provided, thereby achieving the object of the present invention. 1. (A) (a-1) a structural unit derived from ethylene,
(A-2) a structural unit derived from an α-olefin compound having 3 to 10 carbon atoms, (a-3) a structural unit derived from a functional group-containing unsaturated compound, and if necessary, (a- 4) An olefin copolymer having a functional group having a structural unit derived from a non-conjugated diene compound and having an intrinsic viscosity [η] of 0.1 to 10 dL / g measured in decalin at 135 ° C. And (B) a vulcanizing agent and / or a cross-linking agent; and (C) a non-halogen flame retardant.

[0005] 2. The functional group-containing unsaturated compound derived from the structural unit (a-3) in the functional group-containing olefin copolymer (A) is a compound represented by the following formula (1) and / or the following formula (2). The above 1 characterized in that there is
3. The flame-retardant rubber composition according to item 1.

[0006]

Embedded image

In the equation (1), R¹Is a hydrogen atom or carbon
X is -OR ^Two, -COOH,
-NHR^TwoOr -CONHR^TwoThe functional group represented by (R
^TwoIs a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.
You. ), And n is an integer of 0 to 6. ]

[0008]

Embedded image

[In the formula (2), R ³ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and Y ¹ , Y ² and Y ³ are each independently a hydrogen atom or a C 1 to C 10 group. hydrocarbon group or -OR ^2, -COOH, -NHR ² or -
Functional groups represented by CONHR ² (R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) Indicates, Y ^1,
At least one of Y ² and Y ³ is a functional group, Y ^1, when Y ² and two or more of Y ³ is a functional group, they were formed by linking each other acid An anhydride group (—CO—O—CO—) or an imide group (—CO
—NH—CO—). p is an integer of 0 to 2,
q is an integer of 0-5. ]

[0010] 3. The functional group X in the formula (1) or the formula
Y in (2)¹, Y^TwoAnd Y ^ThreeAt least of
Is also characterized in that one functional group is a -COOH group
3. The flame-retardant rubber composition according to the above item 2.

4. In the olefin copolymer (A) having a functional group, the ratio of the structural unit (a-1) is 35 to 9
0 mol%, the ratio of the structural unit (a-2) is 5 to 50 mol%, the ratio of the structural unit (a-3) is 0.01 to 5 mol%,
And the proportion of the structural unit (a-4) is 0 to 10 mol%.

5. (D) ethylene / α having no functional group
The flame-retardant rubber composition according to any one of the above items 1 to 4, comprising an olefin-based copolymer.

6. The proportion of the non-halogen flame retardant (C) is 5 per 100 parts by mass of the total of the olefin copolymer having a functional group (A) and the ethylene / α-olefin copolymer having no functional group (D). The flame-retardant rubber composition according to any one of the above items 1 to 5, which is not less than part by mass.

According to the present invention, there is provided a flame-retardant elastomer obtained by vulcanizing the flame-retardant rubber composition according to any one of the above 1 to 6,
Thereby, the object of the present invention is achieved.

[0015]

According to the above-mentioned flame-retardant rubber composition, the non-halogen flame-retardant coexisting is chemically stable because the olefin-based copolymer which is an elastomer-forming component has a functional group in a structural unit. Because of the state, the obtained elastomer, even when the blending ratio of the non-halogen flame retardant is high, the degree of decrease in mechanical strength caused by the non-halogen flame retardant is small, and therefore, An elastomer having high flame retardancy and excellent mechanical properties can be obtained.

[0016]

Embodiments of the present invention will be described below in detail. The flame-retardant rubber composition of the present invention contains the following components (A), (B) and (C) as essential components. Component (A) comprises (a)
-1) a structural unit derived from ethylene (hereinafter, also referred to as "structural unit (a-1)"), (a-2) having 3 to 1 carbon atoms.
0 structural units derived from an α-olefin compound (hereinafter, referred to as
Also referred to as “structural unit (a-2)”. ), (A-3) a structural unit derived from a functional group-containing unsaturated compound (hereinafter, also referred to as “structural unit (a-3)”), and (a-4) non-conjugated, if necessary, It has a structural unit derived from a diene-based compound (hereinafter, also referred to as “structural unit (a-4)”), and has an intrinsic viscosity [η] of 0.1 to 10 dL / measured in decalin at 135 ° C. g is an olefin copolymer having a functional group. Component (B) is a vulcanizing agent and / or a crosslinking agent. Component (C) is a non-halogen flame retardant.

The flame-retardant rubber composition of the present invention contains, as the component (D), an ethylene / α-olefin-based copolymer having no functional group as far as it does not impair the achievement of the object of the present invention. Can be.

In the olefin copolymer (A) having a functional group used in the present invention, the structural unit (a-1) based on ethylene is in the range of 35 to 90 mol% of the total structural units in the component (A). Is preferably contained in,
It is more preferably 40 to 85 mol%, particularly preferably 45 to 80 mol%. When the content of the structural unit (a-1) is less than 35 mol%, the proportion of ethylene copolymerized to produce the olefin-based copolymer (A) is too small, so that the structural unit It is difficult to copolymerize a functional group-containing cyclic olefin represented by the formula (2), which is suitable for forming (a-3), and as a result, an olefin copolymer (A) having a suitable functional group is obtained.
Is difficult to obtain, and the elastomer finally obtained may have reduced mechanical strength and abrasion resistance. On the other hand, the ratio of the structural unit (a-1) is 90
If it exceeds mol%, the resulting elastomer may have insufficient elasticity.

Structural unit (a-2) in component (A)
Is a structural unit derived from an α-olefin compound having 3 to 10 carbon atoms. Here, as the α-olefin compound having 3 to 10 carbon atoms, propylene, 1-butene,
-Pentene, 4-methyl-pentene-1, 1-hexene, 1-heptene, 1-octene, 1-decene, styrene, p-methylstyrene and the like. Of these, propylene, 1-butene, 1-hexene, 1
-Octene is preferably used, and propylene and 1-butene are particularly preferable. These α-olefin compounds can be used alone or in combination of two or more. In the production of the copolymer of the component (A), by using the α-olefin compound forming the structural unit (a-2), the copolymerization in the monomer composition for obtaining the component (A) is performed. The property becomes good.

In the component (A), the structural unit (a-2)
Is preferably contained in the range of 5 to 50 mol%, more preferably 10 to 45 mol% of the total structural units.
And particularly preferably 15 to 40 mol%. When the content ratio of the structural unit (a-2) is less than 5 mol%, the resulting elastomer may have insufficient elasticity. On the other hand, when the proportion of the structural unit (a-2) exceeds 50 mol%, the resulting elastomer may have reduced mechanical strength and abrasion resistance.

The structural unit (a-3) in the component (A)
Is a structural unit derived from a functional group-containing unsaturated compound. Specific examples of such a functional group-containing unsaturated compound include those represented by the formula (1) and / or the formula (2).

In the formula (1), R ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X represents —OR ² ,
-COOH, it represents a functional group represented by -NHR ² or -CONHR ^2. Here, R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. N is an integer of 0 to 6.

Examples of the functional group-containing unsaturated compound represented by the formula (1) include methyl vinyl ether, ethyl vinyl ether, acrylic acid, acrylamide, N-methylacrylamide, N-ethylacrylamide, allyl alcohol, allyl methyl ether, Allyl ethyl ether, vinyl acetic acid, allylamine, N-methylallylamine, N-ethylallylamine, vinylacetamide, N
-Methylvinylacetic acid amide, N-ethylvinylacetic acid amide, methacrylic acid, methacrylamide and the like. Among these, acrylic acid, acrylamide, N-methylacrylamide, N-ethylacrylamide, allyl alcohol, vinyl acetic acid, allylamine, N-methylallylamine, N-ethylallylamine, vinylacetic acid Amide, N
-Methylvinylacetic acid amide and N-ethylvinylacetic acid amide are preferred.

In the formula (2), R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. Y ¹ , Y ² and Y ³ each independently represent a hydrogen atom,
Hydrocarbon group or -OR ² in 10, -COOH, -NH
R ² or a functional group represented by —CONHR ² (R ² is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms)
Are shown, at least one of Y ^1, Y ² and Y ³ is a functional group, if more than two of Y ^1, Y ² and Y ³ being a functional group, they linked together May be an acid anhydride group (—CO—O—CO—) or an imide group (—CO—NH—CO—) formed. Also,
p is an integer of 0 to 2, and q is an integer of 0 to 5.

[0025] In the above, the hydrocarbon group having 1 to 10 carbon atoms in R ^1, R ² and R ^3, an alkyl group, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl Group, octyl group, nonyl group or decyl group. Examples of Y ¹ , Y ² or Y ³ include a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms (specifically, an alkyl group), a hydroxy group, a methoxy group, an ethoxy group, a carboxyl group, and an amino group. , N-methylamino group, N-ethylamino group, amide group, N-methylamide group, and N-ethylamide group.

In the formula (2), the number of repetitions p is 0 to 2
When p is 3 or more, it becomes difficult to copolymerize the functional group-containing unsaturated compound with another monomer. On the other hand, in equation (2), the number of repetitions p is 0.
Alternatively, the compound of 1 is preferable in that the copolymerization reaction is easy, and particularly a compound in which p is 0 is preferable.

The unsaturated compound having a functional group represented by the formula (2) can be produced by condensing cyclopentadiene and an unsaturated compound having a functional group by a Diels-Alder reaction. Specific examples of the functional group-containing unsaturated compound represented by the formula (2) include the following.

(In the formula (2), p is 0)
5,6-dimethyl-5,6-dihydroxy-bicyclo [2.2.1] -2-heptene, 5,6-dimethyl-
5,6-dicarboxy-bicyclo [2.2.1] -2-
Heptene, 5,6-diethyl-5,6-dicarboxy-
Bicyclo [2.2.1] -2-heptene, 5,6-dimethyl-5,6-bis (carboxymethyl) -bicyclo [2.2.1] -2-heptene, 5,6-diethyl-
5,6-bis (carboxymethyl) -bicyclo [2.
2.1] -2-Heptene, 5,6-dimethyl-5,6-
Bis (hydroxymethyl) -bicyclo [2.2.1]-
2-heptene, 5,6-diethyl-5,6-bis (hydroxymethyl) -bicyclo [2.2.1] -2-heptene, 5,6-dimethyl-5,6-bis (aminomethyl)
-Bicyclo [2.2.1] -2-heptene, 5,6-diethyl-5,6-bis (aminomethyl) -bicyclo [2.2.1] -2-heptene, 5,6-dimethyl-
5,6-bis (aminopropyl) -bicyclo [2.2.
1] -2-heptene,

5,6-dimethyl-5,6-bis (aminocarbonyl) -bicyclo [2.2.1] -2-heptene, 5,6-dimethyl-5,6-bis (N-methyl-aminocarbonyl ) -Bicyclo [2.2.1] -2-heptene, 5,6-dimethyl-5,6-bis (N-propyl-aminocarbonyl) -bicyclo [2.2.1] -2-
Heptene, 5,6-diethyl-5,6-bis (aminocarbonyl) -bicyclo [2.2.1] -2-heptene,
5,6-diethyl-5,6-bis (N-ethyl-aminocarbonyl) -bicyclo [2.2.1] -2-heptene, 5,6-dimethyl-bicyclo [2.2.1] -2-
Heptene-5,6-dicarboxylic imide, 5-methyl-
5-hydroxy-bicyclo [2.2.1] -2-heptene, 5-methyl-5-carboxy-bicyclo [2.2.
1] -2-heptene, 5-ethyl-5-carboxy-bicyclo [2.2.1] -2-heptene, 5-carboxy-5-carboxymethyl-bicyclo [2.2.1] -2
-Heptene,

5-methyl-5-hydroxymethyl-bicyclo [2.2.1] -2-heptene, 5-ethyl-5
Hydroxymethyl-bicyclo [2.2.1] -2-heptene, 5-methyl-5-carboxymethyl-bicyclo [2.2.1] -2-heptene, 5-ethyl-5-carboxymethyl-bicyclo [2 2.1] -2-heptene, 5-methyl-5-aminomethyl-bicyclo [2.
2.1] -2-Heptene, 5-ethyl-5-aminomethyl-bicyclo [2.2.1] -2-heptene, 5-methyl-5-aminopropyl-bicyclo [2.2.1] -2
-Heptene, 5-methyl-5-aminocarbonyl-bicyclo [2.2.1] -2-heptene, 5-methyl-5-
N-methyl-aminocarbonyl-bicyclo [2.2.
1] -2-heptene, 5-methyl-5-N-propyl-
Aminocarbonyl-bicyclo [2.2.1] -2-heptene, 5-ethyl-5-aminocarbonyl-bicyclo [2.2.1] -2-heptene, 5-ethyl-5-N-
Ethyl-aminocarbonyl-bicyclo [2.2.1]-
2-heptene,

(Equation (2) where p is 1)
8,9-dimethyl-8,9-dicarboxy - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene,
8,9-diethyl-8,9-dicarboxy - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] -3-dodecene,
8,9-dimethyl-8,9-bis (hydroxymethyl)
-Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-
Dodecene, 8,9-diethyl-8,9-bis (hydroxymethyl) -tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, 8,9-dimethyl-8,9-bis (aminomethyl) -tetracyclo [4.4.0.1
^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-diethyl-
8,9-bis (aminomethyl) -tetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8,9-dimethyl-8,9-bis (aminocarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,
8,9-dimethyl-8,9-bis (N-methyl-aminocarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1
^7,10 ] -3-dodecene, 8,9-diethyl-8,9-bis (aminocarbonyl) -tetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -3-dodecene, 8,9-diethyl-
8,9-bis (N-ethyl-aminocarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene,

8-methyl-8-carboxy-tetracyclic
B [4.4.0.1^2,5. 1^7,10] -3-dodecene, 8
-Ethyl-8-carboxy-tetracyclo [4.4.
0.1^2,5. 1^7,10] -3-dodecene, 8-methyl-8
-Hydroxymethyl-tetracyclo [4.4.0.1
^2,5. 1 ^7,10] -3-Dodecene, 8-ethyl-8-hydr
Roxymethyl-tetracyclo [4.4.0.1^2,5. 1
^7,10] -3-dodecene, 8-methyl-8-aminomethyl
-Tetracyclo [4.4.0.1^2,5. 1^7,10] -3-
Dodecene, 8-ethyl-8-aminomethyl-tetracycline
B [4.4.0.1^2,5. 1^7,10] -3-dodecene, 8
-Methyl-8-aminocarbonyl-tetracyclo [4.
4.0.1.^2,5. 1 ^7,10] -3-dodecene, 8-methyl
-8-N-methyl-aminocarbonyl-tetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene, 8-
Ethyl-8-aminocarbonyl-tetracyclo [4.
4.0.1.^2,5. 1 ^7,10] -3-dodecene, 8-ethyl
-8-N-ethyl-aminocarbonyl-tetracyclo
[4.4.0.1^2,5. 1^7,10] -3-dodecene

The structural unit (a-3) in the component (A)
Is preferably contained in the range of 0.01 to 5 mol% of all the structural units, more preferably 0.05 to 4 mol%, and particularly preferably 0.1 to 3.5 mol%. . When the content ratio of the structural unit (a-3) is less than 0.01 mol%, the obtained elastomer has poor adhesion, compatibility, or coatability to elastomers and resins other than metals and olefin polymers. May drop.
On the other hand, when the proportion of the structural unit (a-3) exceeds 5 mol%, a monomer that forms the structural unit (a-3) includes:
Copolymerization with monomers other than olefin-based monomers may be difficult, and the resulting elastomer tends to have insufficient rubber elasticity, and it is necessary to use a large amount of a polymerization catalyst. In some cases, formation of a high molecular weight body becomes difficult.

The structural unit (a-4) in the component (A)
Is a structural unit derived from a non-conjugated diene-based compound, and is a component of the copolymer constituting the component (A), if necessary. Specific examples of the non-conjugated diene-based compound from which the structural unit (a-4) is derived include: (1) 1,4-hexadiene, 1,6-hexadiene,
(2) 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethyl-
Branched non-cyclic dienes such as 1,6-octadiene, 3,7-dimethyl-1,7-octadiene, 7-methyl-1,6-octadiene and dihydromyrcene; (3) tetrahydroindene, methyltetrahydroindene; Dicyclopentadiene, bicyclo- (2,2,
1) -Hepta-2,5-diene, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-
And alicyclic dienes such as propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2-norbornene. These non-conjugated diene compounds can be used alone or in combination of two or more. Preferred examples of the non-conjugated diene-based compound include 1,4-hexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and the like.

The structural unit (a-4) is preferably contained in an amount of 0 to 10 mol% of all the structural units in the component (A), more preferably 0 to 8 mol%,
Particularly preferably, it is 0 to 5 mol%. Structural unit (a-
If the content of 4) exceeds 10 mol%, the activity of the polymerization catalyst in the copolymerization reaction for producing the component (A) is significantly reduced, which is not preferable in terms of cost.

The olefin copolymer (A) having a functional group containing the structural units (a-1) to (a-4) has an intrinsic viscosity measured in decalin at 135 ° C. [Η] is in the range of 0.1 to 10 dL / g, preferably 0.1 to 7 dL / g, and more preferably 0.1 to 5 dL / g. A copolymer having an intrinsic viscosity [η] of less than 0.1 dL / g is difficult to knead when blending with another olefin-based copolymer rubber. On the other hand, this intrinsic viscosity [η] is 10 dL / g
If it exceeds, the resulting elastomer will have reduced moldability.

The olefin copolymer (A) having a functional group in the present invention has a weight average molecular weight Mw of 1,0 in terms of polystyrene measured by gel permeation chromatography at 135 ° C. using o-dichlorobenzene as a solvent.
It is preferably from 00 to 3,000,000, more preferably from 3,000 to 1,000,000, and particularly preferably from 5,000 to 700,000. The olefin copolymer (A) preferably has a polystyrene reduced number average molecular weight Mn of 500 to 1,000,000, more preferably 1,000 to 500,000.
000, particularly preferably 2,000 to 300,000.

The glass transition temperature of the olefin copolymer (A) having a functional group is preferably from -90 to 50.
° C, more preferably -70 to 10 ° C. Thereby, an elastomer having sufficient elasticity can be obtained. Here, the glass transition temperature of the olefin copolymer (A) can be measured by a differential scanning calorimeter (DSC).

In the present invention, a vulcanizing agent and / or a crosslinking agent is used as the component (B). The vulcanizing agent to be used is not particularly limited, for example, sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, and insoluble sulfur;
Inorganic vulcanizing agents such as sulfur chloride, selenium and tellurium; and organic compounds containing sulfur such as morpholine disulfide, alkylphenol disulfides, thiuram disulfides and dithiocarbamates. These vulcanizing agents can be used alone or in combination of two or more. The mixing ratio of the vulcanizing agent is 100
It is usually 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass with respect to parts by mass.

A vulcanization accelerator can be used together with the vulcanizing agent. Examples of the vulcanization accelerator include aldehyde ammonias such as hexamethylenetetramine; guanidines such as diphenylguanidine, di (o-tolyl) guanidine and o-tolylbiguanide; thiocarbanilide, di (o-tolyl) thiourea, N, Thioureas such as N'-diethylthiourea, tetramethylthiourea, trimethylthiourea, dilaurylthiourea; mercaptobenzothiazole, dibenzothiazole disulfide, 2- (4-morpholinothio) benzothiazole,
Thiazoles such as 2- (2,4-dinitrophenyl) -mercaptobenzothiazole, (N, N′-diethylthiocarbamoylthio) benzothiazole; Nt-butyl-2-benzothiazylsulfenamide; N'-
Sulfenamides such as dicyclohexyl-2-benzothiazylsulfenamide, N, N'-diisopropyl-2-benzothiazylsulfenamide, N-cyclohexyl-2-benzothiazylsulfenamide; tetramethylthiuram disulfide Thiurams such as tetraethylthiuram disulfide, tetra-n-butylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram tetrasulfide; zinc dimethylthiocarbamate, zinc diethylthiocarbamate, di-n-butylthiocarbamate Carbamine such as zinc, zinc ethylphenyldithiocarbamate, sodium dimethyldithiocarbamate, copper dimethyldithiocarbamate, tellurium dimethylthiocarbamate and iron dimethylthiocarbamate Acid salts; xanthate salts such as zinc butylthioxanthogenate; These vulcanization accelerators can be used alone or in combination of two or more. The compounding amount of the vulcanization accelerator is usually 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the elastomer component.

Further, in addition to the vulcanizing agent and the vulcanization accelerator, a vulcanization accelerating auxiliary may be added as required. Examples of such vulcanization accelerating aids include metal oxides such as magnesium oxide, zinc oxide (zinc white), litharge, lead red, lead white; organic acids such as stearic acid, oleic acid, and zinc stearate; Examples thereof include salts thereof, and among these, zinc oxide and stearic acid are particularly preferable. The vulcanization accelerator may be used alone or in combination of two or more. The compounding amount of the vulcanization accelerator is usually 0.5 to 20 parts by mass with respect to 100 parts by mass of the elastomer component.

In the present invention, examples of the crosslinking agent used as the component (B) include 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, di-tert-butyl peroxide, dicumyl peroxide, t-
Butyl cumyl peroxide, 2,5-dimethyl-2,5
Organic peroxides such as -di (t-butylperoxy) hexane and 1,3-bis (t-butylperoxyisopropyl) benzene. These crosslinking agents can be used alone or in combination of two or more. The compounding amount of the crosslinking agent is usually 0.1 to 15 parts by mass, preferably 0.5 to 1 part by mass with respect to 100 parts by mass of the elastomer component.
0 parts by mass.

A crosslinking aid may be used together with the crosslinking agent. Examples of the crosslinking assistant include sulfur and sulfur compounds such as sulfur and dipentamethylenethiuram tetrasulfide; ethylene di (meth) acrylate, polyethylene di (meth) acrylate, divinylbenzene, diallyl phthalate, triallyl cyanurate, and metaphenylene bis Polyfunctional monomers such as maleimide and toluylenebismaleimide; and oxime compounds such as p-quinone oxime and p, p'-benzoylquinone oxime. These crosslinking assistants can be used alone or in combination of two or more. The compounding amount of the crosslinking assistant is usually 0.5 to 100 parts by mass of the elastomer component.
20 parts by mass.

In the present invention, a non-halogen flame retardant is used as the component (C). Here, the non-halogen flame retardant includes an inorganic flame retardant and an organic flame retardant. Specific examples of inorganic flame retardants include aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, hydrate of tin oxide, borax and the like. Hydrate, red phosphorus, ammonium polyphosphate and the like. Of these inorganic flame retardants, aluminum hydroxide and magnesium hydroxide are preferred. Examples of the organic flame retardant include organic phosphates such as triphenyl phosphate, tricresyl phosphate, resorcinol bis (diphenyl) phosphate, aromatic phosphate and aromatic condensed phosphate, and other ammonium phosphate amides. Can be Of these organic flame retardants, organic phosphate esters are preferred. These inorganic flame retardants and organic flame retardants can be used alone or in combination of two or more. In particular, by using a phosphorus-based flame retardant such as an ammonium polyphosphate-based flame retardant or an organic phosphate ester, which is an inorganic flame retardant, in combination with another flame retardant, a more excellent flame retardant effect can be obtained.

When the above-mentioned inorganic flame retardant is used as the component (C), a fatty acid such as stearic acid, oleic acid, palmitic acid or a metal salt thereof, paraffin, natural wax is applied to the surface of the inorganic flame retardant. , A synthetic wax such as polyethylene wax, or a modified product thereof, an organic borane, an organic titanate, a silane coupling agent, or the like, and the surface treatment can be performed. Particularly, the surface treatment is preferably performed using a silane coupling agent. In addition, in the flame-retardant rubber composition, a silicone compound, quartz glass, or the like;
Water glass or frit as a flame retardant aid; silicon nitride short fiber or the like can be blended to prevent drip.

The content of the non-halogen flame retardant (C) in the flame-retardant rubber composition of the present invention depends on the elastomer-forming component, specifically, the olefin copolymer (A) having a functional group (the functional group When using the ethylene / α-olefin copolymer (D) having no olefin copolymer (D), the total of the olefin copolymer (A) and the olefin copolymer (D))
The amount is 5 parts by mass or more, preferably 25 parts by mass or more, and more preferably 50 parts by mass or more based on 100 parts by mass. If the content of the component (C) is less than 5 parts by mass, the elastomer obtained from the rubber composition will not have sufficient flame retardancy. The upper limit of the content of the component (C) is not particularly limited, but is not more than 500 parts by mass per 100 parts by mass of the elastomer-forming component.
Preferably 450 parts by mass or less, more preferably 400 parts by mass
Not more than parts by mass.

Further, the flame-retardant rubber composition of the present invention comprises
Reinforcing agents, fillers, softeners and other additives can be included. As the reinforcing agent, for example, SRF, FEF,
Carbon black such as HAF, ISAF, SAF, FT, and MT, white carbon, fine particles of magnesium silicate, calcium carbonate, magnesium carbonate, clay,
And inorganic fillers such as talc. These reinforcing agents and fillers can be used alone or in combination of two or more. The compounding amount of the reinforcing agent and the filler is usually 10 to 20 with respect to 100 parts by mass of the elastomer component.
0 parts by mass, preferably 10 to 100 parts by mass.

Examples of the softener include process oils such as aromatic oils, naphthenic oils, and paraffin oils, vegetable oils such as coconut oil, and synthetic oils such as alkylbenzene oil. ,
Process oils are preferred, especially paraffin oils. These softeners can be used alone or in combination of two or more. The compounding amount of the softening agent is usually 10 to 130 parts by mass, preferably 20 to 100 parts by mass with respect to 100 parts by mass of the elastomer component.

The flame-retardant rubber composition of the present invention contains an olefin-based copolymer (A) having a functional group as an elastomer-forming component.
Has a structural unit (a-3) having a functional group. However, the functional group in the structural unit (a-3) is in a state where it is or slightly changed in the three-dimensional structure derived from the olefin copolymer (A) in the elastomer which is a vulcanized product of the rubber composition. And the coexisting non-halogen flame retardant (C) is in a chemically stable state by the functional group. Therefore, even if the elastomer has a high blending ratio of the non-halogen flame retardant (C), the degree of decrease in mechanical strength caused by the non-halogen flame retardant is small, and after all, , Despite being used in non-halogen flame retardants
A flame-retardant elastomer having excellent mechanical properties can be obtained while realizing high flame retardancy.

In the present invention, it is not essential that the olefin-based copolymer (A) having a functional group be used alone as the elastomer-forming component, and the olefin-based copolymer (A) may be used together with the olefin-based copolymer (A). Can be used in combination with a normal ethylene / α-olefin copolymer (D) having no. As the ethylene / α-olefin-based copolymer (D) having no functional group, a structural unit derived from ethylene, a structural unit derived from an α-olefin compound having 3 to 10 carbon atoms, and if necessary, And a structural unit derived from a non-conjugated diene-based compound contained therein. Here, α having 3 to 10 carbon atoms
-Specific examples of the olefin compound include those exemplified as those derived from the structural unit (a-2) in the component (A). Specific examples of the non-conjugated diene-based compound include those exemplified as those derived from the structural unit (a-4) in the component (A).

When the component (D) is used in combination, the mass ratio of the component (A) to the component (D) ((A) / (D)) is usually 1/99 to 99/1, preferably 1/99. 99-50 / 5
0, more preferably 3/97 to 30/70. In this case, the olefin-based copolymer (A) having a functional group may be a high-molecular-weight polymer having a high molecular weight or a low-molecular-weight substance close to a liquid.

The olefin copolymer (A) having a functional group has high compatibility with a polymer other than the olefin polymer, and therefore, an elastomer material other than the olefin polymer, for example, nitrile rubber, chloroprene rubber, Chlorinated polyethylene rubber, halogenated butyl rubber, acrylic rubber, ethylene / acrylic copolymer rubber, hydrogenated nitrile rubber, silicone rubber, fluorine rubber and the like can also be used as a mixture.

The olefin copolymer (A) having a functional group can be produced as follows. The unsaturated compound having a functional group is first reacted with an organometallic compound of a metal selected from Groups 2, 12, and 13 of the periodic table (hereinafter, referred to as “specific organometallic compound”). Thereby, the functional groups of the functional group-containing unsaturated compound are masked.

Specific examples of the specific organometallic compound used for the masking treatment include diethyl zinc, dibutyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, diisobutyl hydride and the like. Aluminum, diethylaluminum hydride, ethylaluminum dihydride, diethylaluminum ethoxide, ethylaluminum diethoxide, dibutylaluminum ethoxide, dibutylaluminum butoxide, diisobutylaluminum dibutoxide, diisobutylaluminum isopropoxide, diisobutylaluminum 2-ethylhexide, Isobutyl aluminum butoxide, isobutyl aluminum 2-ethylhexide, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquichloride, ethylaluminum dichloride, methylalumoxane, ethylalumoxane obtained by reaction of water or copper sulfate hydrate with trialkylaluminum And butylalumoxane. Among these, organoaluminum compounds are preferred, and particularly preferred organoaluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, diisobutylaluminum hydride, diethylaluminum chloride, ethylaluminum sesquichloride and the like.

The reaction with the specific organometallic compound for masking the functional group-containing unsaturated compound is carried out in the presence of an inert solvent or diluent and under an inert gas such as nitrogen gas, argon gas, helium gas or the like. It is preferably performed in an atmosphere. Here, as the inert solvent or diluent,
Aliphatic hydrocarbons such as butane, pentane, hexane, heptane, octane, cyclopentane, cyclohexane,
Cyclic hydrocarbons such as methylcyclopentane, benzene,
Aromatic compounds such as toluene, xylene, chlorobenzene, dichloroethane, and dichloromethane, and halogenated hydrocarbon compounds can be used.

In the reaction for the masking treatment, the specific organometallic compound is at least 0.8 equivalent, preferably 0.9 to 1.5 equivalent, per equivalent of the functional group in the unsaturated compound having a functional group. It is preferable to use them in proportion. If this ratio is too small, a large amount of unmasked functional groups will remain, so that the activity of the polymerization catalyst may decrease in the polymerization treatment described below and the polymerization reaction may not proceed sufficiently. Reaction conditions for the functional group-containing unsaturated compound and the specific organometallic compound vary depending on the type of the functional group-containing unsaturated compound and the specific organometallic compound used, but the reaction time is usually 2 minutes to 10 hours, preferably Is 10 minutes to 2 hours, and the reaction temperature is usually -10 to
The temperature is set to 60 ° C, preferably 10 to 40 ° C.

The functional group-containing unsaturated compound thus masked is subjected to a polymerization process until it is subjected to a polymerization process.
It is preferably stored at a temperature of 30 ° C. or lower, whereby the occurrence of side reactions can be prevented. In addition, the masked functional group-containing unsaturated compound may have an unreacted metal-carbon bond and thus may have an unstable structure, and therefore has a branched structure to improve the stability during storage. Isopropanol, sec-butanol, tert-
Alcohols such as butanol and 2-ethylhexanol; 2,6-di-tert-butylcresol;
Phenols such as -di-tert-butylphenol, 2,6-dimethylcresol and 2,6-dimethylphenol can also be added.

Then, the above-mentioned functionalized unsaturated compound having a masking treatment, which is a raw material monomer of the structural unit (a-1), and ethylene, which is a raw material monomer of the structural unit (a-2), Specific α which is a raw material monomer of the structural unit (a-3)
-Polymerizing an olefin compound and a non-conjugated diene-based compound which is a raw material monomer of the structural unit (a-4) used as required. In this polymerization reaction, a polymerization catalyst comprising a transition metal compound, preferably a compound of a metal selected from Groups 4 and 5 of the periodic table, and an organoaluminum compound is used.

As the polymerization catalyst, a catalyst which gives a relatively random monomer arrangement in the copolymerization reaction of the monomer composition for synthesizing the olefin copolymer (A) is preferably used. Specific examples of the catalyst system include the following.

(1) A catalyst system comprising a vanadium compound soluble in a hydrocarbon compound and an organoaluminum compound, wherein either the vanadium compound or the organoaluminum compound contains at least one chlorine atom. Further, in this catalyst system, an oxygen-containing electron donor or a nitrogen-containing electron donor such as an ester of an organic acid or an inorganic acid, an ether, an amine, a ketone, or an alkoxysilane is further added to the above-mentioned vanadium compound or organic aluminum compound. can do.

(2) A catalyst system comprising a titanium or zirconium halide supported on silica or magnesium chloride and an organic aluminum. As the titanium halide or the zirconium halide, titanium tetrachloride, titanium tetrabromide, zirconium tetrachloride, or the like can be used. As the organic aluminum compound, trimethylaluminum, triethylaluminum, triisobutylaluminum, methylalumoxane and the like can be used. In this catalyst system, dioctyl phthalate, tetraalkoxysilane, diphenyldimethoxysilane and the like can be further added.

(3) The ligand is selected from titanium, zirconium and hafnium having one or two cyclopentadienyl or indenyl groups having a substituent selected from a hydrogen atom, an alkyl group and an allyl group. A catalyst system comprising a transition metal compound of a selected metal and an organoaluminum compound containing at least 50 molar equivalents of methylalumoxane.

(4) A catalyst system comprising bisalkyl-substituted or N-alkyl-substituted salicylaldimine, titanium, zirconium or hafnium dichloride, and methylalumoxane (MAO).

The polymerization reaction is preferably carried out in the presence of an appropriate solvent or diluent. As such a solvent or diluent, for example, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halides thereof can be used. Specifically, butane, pentane, hexane, heptane, 2-butene, 2-methyl-2
-Butene, cyclopentane, methylcyclopentane, cyclohexane, isooctane, benzene, toluene, xylene, chlorobenzene, dichloromethane, dichloroethane and the like. It is preferable to use those solvents or diluents having a water content of 20 ppm or less, for example, by a distillation treatment or an adsorption treatment.

The polymerization reaction is carried out at 0 to 150 ° C., particularly at 10 to 1
It is preferably performed at a temperature of 00 ° C. In the polymerization reaction, a molecular weight regulator can be used as necessary, and specific examples thereof include hydrogen, diethylzinc, diisobutylaluminum hydride and the like. Further, the reactor for performing the polymerization reaction may be any of a batch type and a continuous type. As the continuous reactor, a tube reactor, a tower reactor, a tank reactor, or the like can be used.

After the polymerization is carried out as described above, the resulting copolymer is subjected to a demasking treatment, whereby an olefin copolymer (A) having a functional group can be obtained. The demasking treatment is performed in the case where a functional group-containing unsaturated compound whose functional group is a hydroxyl group, a carboxyl group, an alkoxy group, an acid anhydride group or an imide group is used, formic acid, oxalic acid, fumaric acid, Lactic acid, dioctyl monophosphate, trifluoroacetic acid, dodecylbenzenesulfonic acid, monophosphate of nonylphenoxypolyethylene glycol, diphosphate of nonylphenoxypolyethylene glycol, monophosphate of lauroxypolyethylene glycol, diphosphate of lauroxypolyethylene glycol And the like, using an acid having a relatively high acidity.

On the other hand, when an unsaturated compound having a functional group is an amino group or an amide group, an alcoholate of t-butanol with lithium, sodium or potassium; an amyl alcohol with lithium, sodium Or alcoholates with potassium; lithium, sodium or potassium salts of octanoic acid;
The demasking treatment can be performed using a strongly basic alcoholate such as a lithium salt or a potassium salt of nonylphenol or an alkali metal salt of phenol or an organic carboxylic acid.

The copolymer solution containing the olefin-based copolymer thus obtained is passed through an adsorption column filled with silica, alumina, diatomaceous earth, or the like, or added to the copolymer solution. It is preferable to remove the remaining demasking agent, polymerization catalyst, and the like by washing with a large amount of water or alcohol.

For the purpose of improving the stability of the olefin-based copolymer, a known anti-aging agent such as a phenol-based, phosphorus-based or sulfur-based anti-aging agent is added to the copolymer solution. be able to.

After removing the solvent by blowing steam into the copolymer solution, the solid matter is separated from the obtained slurry, and further separated using, for example, a screw-type squeezing machine, an extruder, a heating roll, or the like. Dehydration
By drying, an olefin copolymer (A) having a solid functional group is obtained. Alternatively, the obtained copolymer solution is concentrated by heating, and then dried using a vented extruder,
An olefin copolymer (A) having a solid functional group is obtained.

According to the method described above, since the masking treatment is performed with the specific organometallic compound, the functional group in the functional group-containing cyclic olefin is surely masked, so that the activity of the polymerization catalyst is reduced in the polymerization reaction. In addition, there is no problem in the polymerization reaction, and as a result, the olefin copolymer (A) having a desired functional group can be reliably produced.

The flame-retardant rubber composition of the present invention can be prepared by using a kneader known in the art, for example, an open roll mill, a Banbury mixer or a kneader, to obtain the above-mentioned component (A).
Alternatively, it can be prepared by kneading the component (C) and, if necessary, the component (D). The resulting rubber composition is preferably prepared so that its blended Mooney viscosity (ML1 + 4, 100 ° C) is in the range of 20 to 50.

The prepared flame-retardant rubber composition is formed into a desired shape by an extruder or a mold, and then vulcanized by a heating device such as a high-frequency heating device, an air oven, a PCM, or an LCM. An elastomeric material or product that is a vulcanizate is obtained. Alternatively, the elastomer may be manufactured by a method of molding and vulcanizing in a mold using a vulcanizing apparatus known per se.

According to the above flame-retardant rubber composition, the vulcanized elastomer becomes flame-retardant by containing a flame retardant, and the elastomer has a non-flammable property. Since it is a halogen-based flame retardant, it is a non-halogen-based substance itself and does not hinder human life.Moreover, even when the content of the non-halogen-based flame retardant is high, excellent elastic properties and It has mechanical properties. Accordingly, the elastomer is excellent in mechanical properties such as ease of installation, impact resistance, and fracture resistance, and is a non-halogen-based material and is flame-retardant. It is suitably used for the production of elastomer products to be used for the above-mentioned applications, specifically, sealants for fire prevention such as window frames and floor materials.

[0075]

EXAMPLES Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to the following examples.

(Production of functional group-containing olefin copolymer (A)) Production Example 1 Hexane 2 was placed in a nitrogen-substituted 3 L separable flask.
000 mL and a concentration of 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene (MCBH) of 0.
20 mL of a 5 mol / L hexane solution (5-methyl-5
The content of -carboxy-bicyclo [2.2.1] -2-heptene is 10 mmol. ) Was put. Then
While stirring this system, 12 mmol of triisobutylaluminum was added as a catalyst and reacted at 20 ° C., whereby the carboxyl group of 5-methyl-5-carboxy-bicyclo [2.2.1] -2-heptene was converted. A masking process was performed. In this system, 5-ethylidene-
After adding 5 mL of 2-norbornene (ENB), ethylene was supplied at a rate of 5.5 L / min, and propylene was added at 4.5.
While continuously supplying a mixed gas obtained by mixing hydrogen gas at a supply rate of 0.5 L / min at a supply rate of L / min, Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ was used as a polymerization catalyst. 30 mL of a hexane solution having a concentration of 0.81 mol / L (Al
The content of ₂ (C ₂ H ₅ ) ₃ Cl ₃ is 24 mmol. ) And then a concentration of VCl ₄ of 0.10 mo
24 mL of a 1 / L hexane solution (the content of VCl ₄ is 2.4 mmol) was added, and ethylene, propylene, MCBH and EN were added at 25 ° C. for 10 minutes.
A copolymerization reaction was performed with the four monomers of B.

To the obtained copolymer solution, 180 mmol
Was removed by adding a butanol solution containing lactic acid and stirring for 10 minutes. Next, after adding 1 L of water to the copolymer solution and stirring for 10 minutes, only the copolymer solution as an organic layer is recovered, and the copolymer solution is washed three times with 1 L of water,
After removing residual lactic acid and the like, the solvent was removed by blowing steam into the copolymer solution. Thereafter, a solid content is separated from the obtained slurry, and the solid content is dried by a heating roll, whereby an olefin-based copolymer (A1) 38 having a solid functional group is obtained.
g was obtained.

The olefin copolymer (A1) having a functional group was analyzed by infrared absorption spectroscopy. As a result, the content of the structural unit (a-1) derived from ethylene was 66.1 mol%, and Structural units (a
The content of -2) is 30.8 mol%, and 5-methyl-5-
The content ratio of the structural unit (a-3) derived from carboxy-bicyclo [2.2.1] -2-heptene is 0.23 mol%, and the structural unit derived from 5-ethylidene-2-norbornene (a- The content ratio of 4) was 2.9 mol%. The intrinsic viscosity [η] of this copolymer (A1) measured in decalin at 135 ° C. is 2.30 dL / g.
Met.

Production Examples 2 and 3 In Production Example 1, MC
The amount of BH, the amount of triisobutylaluminum in the masking treatment catalyst, and the amount of Al ₂ (C ₂ H ₅ ) ₃ Cl _{3 in the} polymerization catalyst
By the same method as in Production Example 1 except that the amount of
The olefin copolymers (A2) and (A3) having the functional groups shown in Table 1 were produced.

Production Example 4 The supply amount of ethylene was 5.5 L / m
In, by changing the supply amount of propylene to 4.5 L / min and the supply amount of hydrogen gas to 5.0 L / min, except for changing the composition of the mixed gas, the same method as in Production Example 3 was used. An olefin copolymer (A4) having a functional group shown in Table 1 was produced.

Comparative Production Example 1 In Production Example 1, MCBH
Except not using, by the same method as in Production Example 1,
An olefin-based copolymer (X1) having no functional group shown in Table 1 was produced.

[0082]

[Table 1]

Example 1 The olefin copolymer (A) obtained as described above
1) 100 parts by mass, 30 parts by mass of white carbon as a reinforcing agent (manufactured by Nippon Silica Co., trade name: Nipsil VN3), and magnesium hydroxide as a non-halogen flame retardant (manufactured by Kyowa Chemical Company, trade name: Kisuma) 5A) 200 parts by mass, stearic acid 1 part by mass, and a process oil as a softener (trade name: Diana Process PW3 by Idemitsu Kosan Co., Ltd.)
80) 20 parts by mass were converted to 1 part under a condition of a rotation speed of 60 rpm and 60 ° C. by a Banbury device having a content of 1700 mL.
By kneading for 80 seconds, a compound material was obtained. Next, 5 parts by mass of zinc oxide as a vulcanization accelerator, 0.2 parts by mass of sulfur as a vulcanizing agent, and an organic peroxide as a crosslinking agent (trade name, manufactured by NOF CORPORATION, : Park Mill D-40), and kneaded with a 10-inch roll maintained at 60 ° C for 10 minutes to obtain a compound (1) which is a rubber composition of the present invention.
Manufactured

Example 2 The same procedure as in Example 1 was repeated except that the olefin copolymer (A2) was used in place of the olefin copolymer (A1) to obtain the rubber composition of the present invention. A compound (2) was produced.

Example 3 The same procedure as in Example 1 was carried out except that the olefin copolymer (A3) was used instead of the olefin copolymer (A1). A compound (3) was produced.

Example 4 A rubber composition of the present invention was obtained by performing the same operation as in Example 3 except that the amount of magnesium hydroxide "Kisuma 5A" which was a non-halogen flame retardant was changed to 100 parts by mass. A compound (4) was produced.

Example 5 The rubber composition of the present invention was obtained by performing the same operation as in Example 3 except that the amount of magnesium hydroxide “Kisuma 5A”, which was a non-halogen flame retardant, was changed to 300 parts by mass. A compound (5) was produced.

Example 6 Instead of 100 parts by mass of the olefin-based copolymer (A1), 10 parts by mass of the olefin-based copolymer (A4) and an ethylene / propylene / 5-ethylidene-2-norbornene copolymer (commercially available) Name: EP65, manufactured by JSR Corporation, ethylene content 66.6 mol%, propylene content 30.8 mol%, 5-ethylidene-2-norbornene content 2.6 mol%, [η]: 2.07 dL / g) Compound (6), which is the rubber composition of the present invention, was produced by performing the same operation as in Example 1 except that 100 parts by mass of the mixture consisting of 90 parts by mass was used.

Comparative Example 1 A rubber composition for comparison was prepared by performing the same operation as in Example 1 except that the olefin copolymer (X1) was used instead of the olefin copolymer (A1). A compound (Xa) was produced.

Comparative Example 2 The same operation as in Example 3 was carried out except that magnesium hydroxide “Kisuma 5A”, a non-halogen flame retardant, was not used to obtain a compound (Xb) as a comparative rubber composition. ) Manufactured.

Each of the compounds obtained in Examples 1 to 6 and Comparative Examples 1 and 2 was compression-vulcanized at 170 ° C. for 30 minutes using a steam vulcanizing press to obtain a vulcanized sheet having a thickness of 2 mm. Was.

Various properties of the vulcanized sheet were measured by the following methods. Table 2 shows the results. (1) in compliance with the physical property testing JIS K 6251, initial modulus (M100), tensile strength T _B (MPa), elongation at break E _B (%), the hardness was measured (Duro A). The conditions of the tensile test are as follows. Test temperature 1: room temperature (23 ± 2 ° C.) Test piece shape: JIS-2 Tensile speed: 200 mm / min (2) Flame retardancy According to ASTM D 2863-70
The oxygen index was measured.

[0093]

[Table 2]

From the results shown in Table 2, according to the rubber composition containing the olefin copolymer (A) having a functional group obtained by using a functional group-containing unsaturated compound as a monomer, It is understood that the present invention provides an elastomer exhibiting high mechanical strength without impairing flame retardancy, as compared with a rubber composition containing only an olefin copolymer having no group. That is, for example, the compound 3 of Example 3 and the compound Xa of Comparative Example 1 have the same content ratio of the non-halogen flame retardant and can obtain almost the same flame retardancy. According to this, all of the physical properties of the elastomer are excellent.

Further, Embodiments 3, 4 and 5
In the above, only the content ratio of the non-halogen flame retardant is different, but as the content ratio of the non-halogen flame retardant increases, high flame retardancy corresponding thereto can be obtained, but the mechanical strength other than the hardness increases. It is understood that the decrease in the physical properties shown is slight.

[0096]

According to the flame-retardant rubber composition of the present invention, the non-halogen flame-retardant coexisting with the olefin-based copolymer which is an elastomer-forming component has a functional group in the structural unit. Therefore, even when the blending ratio of the non-halogen flame retardant is high, the degree of decrease in mechanical strength caused by the non-halogen flame retardant is small. Thus, an elastomer having high flame retardancy and excellent mechanical properties can be obtained.

Further, according to the elastomer of the present invention, since it has high flame retardancy and excellent mechanical properties, various elastomer products can be provided by utilizing the properties.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiyuki Hayakawa 2--11-24 Tsukiji, Chuo-ku, Tokyo Inside JSR Co., Ltd. (72) Inventor Minoru Tanaka 2-11-24 Tsukiji, Chuo-ku, Tokyo JSR Inside (72) Inventor Fumio Tsutsumi F-term (reference) 4J002 BB051 BB151 DA047 DE076 DE096 DE146 DE286 DK006 EK038 EV047 EV147 EW046 FD136 FD148

Claims (7)

[Claims] 1. (A) (a-1) a structural unit derived from ethylene, (a-2) a structural unit derived from an α-olefin compound having 3 to 10 carbon atoms, and (a-3) a functional group-containing It has a structural unit derived from an unsaturated compound and, if necessary, a structural unit derived from a (a-4) non-conjugated diene compound, and has an intrinsic viscosity [η] measured in decalin at 135 ° C. ] Containing an olefin copolymer having a functional group of 0.1 to 10 dL / g, (B) a vulcanizing agent and / or a crosslinking agent, and (C) a non-halogen flame retardant. Flame-retardant rubber composition. 2. An olefin copolymer having a functional group.
(A) including a functional group derived from the structural unit (a-3)
The unsaturated compound is represented by the following formula (1) and / or
A compound represented by the formula (2):
2. The flame-retardant rubber composition according to 1. Embedded image[In the formula (1), R¹Is a hydrogen atom or a group having 1 to 10 carbon atoms
A hydrocarbon group, X is -OR ^Two, -COOH, -NHR^TwoMa
Or -CONHR^TwoThe functional group represented by (R^TwoIs a hydrogen atom
Alternatively, it is a hydrocarbon group having 1 to 10 carbon atoms. ),
n is an integer of 0-6. [Chemical formula 2][In the formula (2), R^ThreeIs a hydrogen atom or a group having 1 to 10 carbon atoms
Hydrocarbon group, Y¹, Y^TwoAnd Y^ThreeAre independent
A hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or -O
R^Two, -COOH, -NHR^TwoOr -CONHR^Two
The functional group represented by (R^TwoIs a hydrogen atom or a carbon number of 1 to 1
0 hydrocarbon group. ) And Y¹, Y^TwoAnd Y
^ThreeAt least one of which is a functional group;¹, Y^Two
And Y^ThreeWhen two or more of the groups are functional groups,
They are linked to each other to form an acid anhydride group (-CO
-O-CO-) or an imide group (-CO-NH-CO
−). p is an integer of 0-2, q is 0-5
It is an integer. ] 3. The functional group X in the formula (1) or at least one of Y ¹ , Y ² and Y ³ in the formula (2) is a —COOH group. 3. The flame-retardant rubber composition according to item 1. 4. In the olefin copolymer (A) having a functional group, the ratio of the structural unit (a-1) is 35 to 9
0 mol%, the ratio of the structural unit (a-2) is 5 to 50 mol%, the ratio of the structural unit (a-3) is 0.01 to 5 mol%,
The flame-retardant rubber composition according to any one of claims 1 to 3, wherein the proportion of the structural unit (a-4) is 0 to 10 mol%. 5. (D) Ethylene • α- having no functional group
The flame-retardant rubber composition according to any one of claims 1 to 4, further comprising an olefin-based copolymer. 6. A non-halogen flame retardant (C) based on a total of 100 parts by mass of the olefin copolymer having a functional group (A) and the ethylene / α-olefin copolymer having no functional group (D). ) Is 5 parts by mass or more, the flame-retardant rubber composition according to any one of claims 1 to 5. 7. A flame-retardant elastomer obtained by vulcanizing the flame-retardant rubber composition according to any one of claims 1 to 6.