JP2857893B2 - Flame-retardant cyclic olefin polymer composition - Google Patents

Description

The present invention relates to heat resistance, chemical resistance, solvent resistance, dielectric properties, electrical properties, rigidity, dimensional stability, moldability, impact resistance, and bending. The present invention relates to a flame-retardant cyclic olefin polymer composition having excellent mechanical properties such as strength and flexural modulus and also having excellent flame retardancy.

[Conventional technology]

Polyolefin resins such as polyethylene and polypropylene are widely used as resins having excellent chemical resistance, solvent resistance and dielectric properties. However, since polyolefin resins are easily combustible, their use has been restricted from the viewpoint of safety in applications where flame retardancy is strongly required, such as electric parts.

Incidentally, as a composition having improved flame retardancy, a fire-resistant composition comprising a propylene polymer, an organic bromine compound, antimony trioxide and a fluororesin (Japanese Patent Publication No. 51-39911), a polyolefin, a halogen-based flame retardant and Flame retardants such as antimony oxide, flame-retardant polyolefin compositions comprising low molecular weight polytetrafluoroethylene powder (JP-A-57-162734), thermoplastic resins, flame retardants such as halogen-based flame retardants, antimony compounds, etc. Flame retardant resin composition comprising a flame retardant auxiliary and a fluororesin (JP-A-63
-110257), a flame-retardant rubber-reinforced resin composition comprising a rubber-reinforced resin, a bromine-based flame retardant, an antimony compound and polytetrafluoroethylene having a specific molecular weight (Japanese Patent Application Laid-Open No. 63-63).
No. 135442) is known.

However, JP-B-51-39911 only discloses a propylene polymer as a resin to be blended with a flame retardant, and this refractory composition has a heat distortion temperature.
The temperature is as low as 50 to 60 ° C (according to ASTM D648), and there is a problem that heat resistance is poor.

JP-A-57-162734 also only describes an example in which polyethylene is used as the resin to be blended with the flame retardant. However, the flame-retardant composition using polyethylene as the resin to be compounded has a problem that heat resistance is poor.

Also in JP-A-63-110257, polycarbonate resin (PC resin), acrylonitrile-butadiene-styrene copolymer (ABS resin) or acrylonitrile-styrene copolymer (AS Only examples using (resin) are described. However, the flame-retardant composition using a PC resin as the resin to be blended has a high heat distortion temperature and excellent heat resistance, but has a problem of poor moldability and electrical properties. A flame-retardant composition using an ABS resin is excellent in moldability and electrical properties, but has a problem of poor mechanical properties. A flame-retardant composition using an AS resin has a problem of poor moldability.

JP-A-63-135442 only describes an example using an ABS resin or a mixture of an ABS resin and an AS resin as a resin to be blended with a flame retardant. These flame-retardant compositions are not said to be excellent in the balance among heat resistance, electrical properties, moldability, dimensional stability and mechanical properties, and have advantages and disadvantages.

As described above, with the conventional flame-retardant composition, a composition excellent in balance in all of heat resistance, electrical properties, moldability, dimensional stability and mechanical properties has not been obtained. For this reason, it needs flame retardancy, heat resistance, and electrical properties like housing and parts of electrical products, home appliances, OA equipment, etc.
Further, there has been a demand for a flame-retardant composition which can be suitably used for those requiring moldability, dimensional stability and mechanical properties.

On the other hand, JP-A-60-26024, tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-dodecene of the ring-opening homopolymer hydrogenated to hydrogenated ring-opening polymer obtained Has been proposed as a resin having improved heat resistance and heat aging resistance. However, this polymer has problems that it is brittle and has poor impact resistance and poor flame retardancy.

To solve these problems, Japanese Patent Application Laid-Open No. 61-292601 has been proposed.
In the publication, a cyclic olefin-based random copolymer composed of an ethylene component and a cyclic olefin component represented by the following general formula [I] is described. Is required.

[Problems to be solved by the invention]

The object of the present invention is to solve the problems associated with the prior art as described above, and has excellent flame retardancy and heat resistance, chemical resistance, solvent resistance, dielectric properties, electrical properties, rigidity, An object of the present invention is to provide a flame-retardant cyclic olefin polymer composition excellent in impact resistance, dimensional stability, moldability, and mechanical properties such as flexural strength and flexural modulus.

[Means for solving the problem]

The present invention is the following flame-retardant cyclic olefin polymer composition.

(1) [A] An intrinsic viscosity [η] measured in decalin at 135 ° C of 0.01 to 10 dl / g and a softening temperature (TMA) of 70 ° C or more (a) An ethylene component and the following general formula [I] Or (b) a ring-opened polymer of a cyclic olefin component represented by the following general formula [I] or a hydrogenated product thereof, [Wherein, R ^{1 to} R ¹² are a hydrogen atom, a hydrocarbon group, or a halogen atom, and may be the same or different. R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other. You may. n is 0 or a positive integer, and when R ^{5 to} R ⁸ are repeated a plurality of times, they may be the same or different. ] [B] a halogen-based flame retardant, [C] an antimony-based flame retardant, [D] polytetrafluoroethylene, and [E] magnesium hydroxide, and [B] component based on 100 parts by weight of [A] component. Is 3 to 50 parts by weight, [C] component is 1 to 30 parts by weight, [D] component is 0.01 to 5 parts by weight, and [E] component is 2 to 150 parts by weight. Cyclic olefin polymer composition.

(2) [F] an amorphous or low-crystalline α-olefin copolymer formed from at least two kinds of α-olefins, and styrene or a derivative thereof as one of the monomer components, and at least a glass transition temperature. One selected from an amorphous or low-crystalline copolymer having a temperature of 0 ° C. or lower.
At least 100% by weight of the component (A).
The above (1) in which the component [F] is mixed in an amount of 5 to 100 parts by weight.
The flame-retardant cyclic olefin polymer composition according to claim 1.

(3) The halogen-based flame retardant is hexabromobenzene, hexabromodiphenyl oxide, octabromodiphenyl oxide, decabromodiphenyl oxide, tetrabromobisphenol S and its derivatives, tetrabromophthalic anhydride and its derivatives, ethylenebis (5,
6-dibromonorbornene-2,3-dicarboximide), tris- (2,3-dibromopropyl-1) -isocyanurate, adduct of Diels-Alder reaction of hexachlorocyclopentadiene, ethylenebistribromophenylether, ethylenebis Pentabromophenyl ether, tetradecabromodiphenoxybenzene,
(1) or (2), which is brominated polystyrene, brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, polypentabromobenzyl acrylate, bis (tribromophenyl) fumaramide, or N-methylhexabromodiphenylamine. Flame-retardant cyclic olefin polymer composition.

(4) The flame-retardant cyclic olefin polymer composition according to any one of the above (1) to (3), wherein the antimony-based flame retardant is antimony trioxide, antimony pentoxide, sodium antimonate, or antimony trichloride.

The component [A] used in the present invention may be any of the above-mentioned cycloolefin random copolymer (a), a ring-opened polymer or a hydrogenated product thereof (b).

The cyclic olefin-based random copolymer (a) of the component (A) in the present invention is a cyclic olefin-based random copolymer containing an ethylene component and a specific cyclic olefin component as monomer components. The specific cyclic olefin component is a cyclic olefin represented by the general formula [I].

The specific cyclic olefin component constituting the cyclic olefin random copolymer (a) in the present invention is at least one type of cyclic olefin selected from the group consisting of unsaturated monomers represented by the general formula [I]. It is.

In the cyclic olefin-based random copolymer (a), the cyclic olefin represented by the general formula [I] is
It mainly forms a repeating unit having a structure represented by the following general formula [II].

[In the formula, n and R ^{1 to} R ¹² are the same as described above. Examples of R ^{1 to} R ⁸ in the general formula [I] include a hydrogen atom; a halogen atom such as fluorine, chlorine and bromine; a lower alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group. Which may be different, partially different, or identical in front.

R ^{9 to} R ¹² in the general formula [I] include, for example, a hydrogen atom; a halogen atom such as fluorine, chlorine, and bromine; a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, Examples thereof include an alkyl group such as a stearyl group; a cycloalkyl group such as a cyclohexyl group; R ⁹ and R ¹⁰ , or R ¹¹ and R ¹²
And may form a divalent hydrocarbon group by combining with R ⁹
Alternatively, R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other.

Examples of the divalent hydrocarbon group formed by integrating R ⁹ and R ¹⁰ or R ¹¹ and R ¹² include an alkylidene group such as an ethylidene group, a propylidene group and an isopropylidene group.

The ring formed from R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may be a single ring or a condensed polycyclic ring, may be a cross-linked polycyclic ring, and may be a ring having an unsaturated bond, Or a ring composed of a combination of these rings. Specifically as such a ring, for example, And so on. These rings may have a substituent such as a methyl group. In the above chemical formula, the carbon atom with 1 or 2 represents the carbon atom to which R ^{9 to} R ¹² are bonded in the general formula [I].

The cyclic olefin represented by the general formula [I] can be easily produced by condensing a cyclopentadiene and a corresponding olefin or cyclic olefin by a Diels-Alder reaction.

Specific examples of the cyclic olefin represented by the general formula [I] include the compounds shown in Table 1.

The cyclic olefin-based random copolymer (a) in the present invention contains an ethylene component and the above-mentioned cyclic olefin component as essential components. In addition to these two essential components, a range that does not impair the object of the present invention is provided. If necessary, it may contain another copolymerizable unsaturated monomer component. Specific examples of the unsaturated monomer which may be optionally copolymerized include, for example, propylene, 1-butene and 4-methyl-1 in an amount less than equimolar to the ethylene component unit in the produced random copolymer. -Pentene, 1-hexene, 1-
Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, α-olefins having 3 to 20 carbon atoms, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2
-Methylbutyl) -1-cyclohexene, styrene, α
-Methylstyrene, dicyclopentadiene, ethylidene norbornene, 2,3,3a, 7a-tetrahydro-4,7-methano-1H-indene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene And the like.

In the cyclic olefin-based random copolymer (a) of the present invention, the structural unit derived from the ethylene component is in the range of 10 to 90 mol%, preferably 50 to 75 mol%, and the structural unit derived from the cyclic olefin component is 10 to 90 mol%. 90 mol%, preferably 25 to
The range of 50 mol% is appropriate, and the structural unit derived from the ethylene component and the structural unit derived from the cyclic olefin component form a substantially linear cyclic olefin-based random copolymer randomly arranged. The fact that the cyclic olefin-based random copolymer is substantially linear and does not have a gel-like crosslinked structure can be confirmed by completely dissolving the copolymer in decalin at 135 ° C.

The intrinsic viscosity [η] of the cyclic olefin random copolymer (a) constituting the composition of the present invention measured in decalin at 135 ° C. is in the range of 0.01 to 10 dl / g, preferably 0.05 to 5 dl / g. -The softening temperature (TMA) measured with a mechanical analyzer is 70C or more, preferably 90 to 250C, more preferably 100 to 200C.

The cyclic olefin-based random copolymer (a) constituting the composition of the present invention has a glass transition temperature (Tg) in the range of usually 50 to 230 ° C, preferably 70 to 210 ° C, and is measured by an X-ray diffraction method. Crystallinity is 0-10%, preferably 0%
It is preferable to use one having a thermal decomposition temperature of usually 350 to 420 ° C, preferably 370 to 400 ° C.

As the cyclic olefin-based random copolymer (a), the bending elastic modulus is usually 1 × 10 ^{4 to} 5 as mechanical properties.
× 10 ⁴ kg / cm ² range, bending yield strength is usually 300 ~ 15
It is preferable to use one in the range of 00 kg / cm ² .

The cyclic olefin-based random copolymer (a) has a density of usually 0.86 to 1.10 g / cm ³ , preferably 0.88 to 1.0 g / cm ³ .
8g / cm ³ range, refractive index (ASTM D 542) is usually 1.47-1.5
8, preferably in the range of 1.48 to 1.56 and is substantially amorphous, so haze (ASTM D 1003) is usually 20%
It is preferable to use those having a content of 10% or less, preferably 10% or less.

The cyclic olefin-based random copolymer (a) has a dielectric constant (1 kHz) according to ASTM D150 as an electrical property.
z) is 1.5 to 3.0, preferably 1.9 to 2.6, and the dielectric loss tangent is 9 × 1
It is preferable to use one having a range of 0 ^-4 to 8 × 10 ^-5 , preferably 3 × 10 ^{-4 to} 9 × 10 ^-5 .

As the cyclic olefin-based random copolymer (a) in the present invention, a copolymer consisting of only those having physical properties in the above range may be used, but a copolymer having physical properties outside the above range is partially included. In this case, it is sufficient that the entire physical property value is included in the above range.

The cyclic olefin-based random copolymer (a) used in the present invention comprises a known Ziegler-based catalyst comprising an ethylene component, a cyclic olefin component represented by the above general formula [I], and optionally other copolymerized monomer components. Can be produced by polymerizing in the presence of

Examples of the Ziegler-based catalyst include (A) a catalyst comprising a complex containing at least magnesium, titanium and halogen and an organoaluminum compound;
A catalyst comprising a vanadium compound and an organoaluminum compound can be used. Among these, the latter (a) catalyst is preferred, and a catalyst composed of a soluble vanadium compound and an organoaluminum compound is particularly preferred.

Specific methods for producing the cyclic olefin-based random copolymer (a) are described in JP-A-60-168708 and JP-A-61-1208.
No. 16, JP-A-61-115912, JP-A-61-115916
And Japanese Patent Application Laid-Open Nos. Sho 61-271308, 61-272216, 62-252406, and 62-252407.

As the component (A) of the present invention, a ring-opened polymer of the cyclic olefin component represented by the general formula [I] or a hydrogenated product thereof (b) instead of the cyclic olefin random copolymer (a) is used. The same effect may be obtained. In this case, a flame-retardant cyclic olefin polymer composition having similar properties can be obtained in the same manner as in the cyclic olefin random copolymer (a). Such ring-opened polymers of cyclic olefins are disclosed, for example, in
It is disclosed in JP-A-26024.

In the ring-opened polymer before hydrogenation of the hydrogenated product (b) of the ring-opened polymer, the cyclic olefin component represented by the general formula [I] has a structure represented by the following general formula [III]. Is mainly formed, and in the ring-opened polymer after hydrogenation, the repeating unit having the structure represented by the following general formula [IV] is mainly formed.

[In the formula, n and R ^{1 to} R ¹² are the same as described above. The ring-opened polymer before the hydrogenation is represented by the general formula [I]
Can be produced by a usual ring-opening polymerization method of a cyclic olefin using, as raw materials, a monomer component selected from the above and other monomer components to be polymerized if necessary. As the polymerization catalyst, for example, ruthenium, rhodium, palladium, osmium, iridium, platinum, molybdenum, halides such as tungsten, a nitrate or acetylacetone compound and an alcohol, a system comprising a reducing agent such as a tin compound, or titanium, vanadium, zirconium, A system including a halogen compound such as tungsten or molybdenum, an acetylacetone compound or the like and an organic aluminum compound can be used.

The hydrogenated product of the ring-opening polymer is obtained by hydrogenating the ring-opening polymer obtained as described above. Hydrogenation of the ring-opening polymer is performed by a usual hydrogenation method.

As the hydrogenation catalyst, those used for hydrogenation of olefin compounds can be generally used.
Specifically, as a heterogeneous catalyst, nickel, palladium, platinum or the like, or these metals are carbon, silica,
Solid catalyst supported on a carrier such as diatomaceous earth, alumina, titanium oxide, such as nickel / silica, nickel / diatomaceous earth, palladium / carbon, palladium / silica,
Examples include palladium / diatomaceous earth and palladium / alumina. As a homogeneous catalyst, the periodic table VIII
Some are based on metals of the group III, such as nickel naphthenate / triethylaluminum, cobalt octenoate
/ n-butyllithium, nickel acetylacetonate /
Examples thereof include compounds comprising Ni and Co compounds such as triethylaluminum and organometallic compounds of metals of Groups I to III of the periodic table, and Rh compounds.

The hydrogenation reaction of the ring-opening polymer is carried out in a homogeneous or heterogeneous system under a hydrogen pressure of 1 to 150 atm and at a temperature of 0 to 180 ° C, preferably 20 to 100 ° C, depending on the type of catalyst. Will be The hydrogenation rate can be adjusted by the hydrogen pressure, the reaction temperature, the reaction time, the catalyst concentration, and the like. However, in order for the hydrogenated product to exhibit excellent heat deterioration resistance and light deterioration resistance, the main chain in the polymer must be used. More than 50% of heavy bonds, preferably 80
% Or more, more preferably 90% or more is hydrogenated.

In the flame-retardant cyclic olefin polymer composition of the present invention,
A halogen-based flame retardant [B] is blended. As the halogen-based flame retardant [B], various chlorine- and bromine-based flame retardants can be used, but the flame retardant effect, heat resistance during molding, dispersibility in the resin, and the effect on the physical properties of the resin are considered. From the viewpoint of, for example, hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromogenyl, hexabromodiphenyloxide, octabromodiphenyloxide, decabromodiphenyloxide, pentabromocyclohexane, tetrabromobisphenol A and derivatives thereof (for example, Tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A-bis (2,3-dibromopropyl ether),
Tetrabromobisphenol A-bis (bromoethyl ether), tetrabromobisphenol A-bis (allyl ether), etc.], tetrabromobisphenol S and derivatives thereof [for example, tetrabromobisphenol S-
Bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether), etc.), tetrabromophthalic anhydride and derivatives thereof (eg, tetrabromophthalimide, ethylenebistetrabromophthalimide, etc.), ethylene bis (5 , 6-Dibromonorbornene-2,3-dicarboximide), tris- (2,3-dibromopropyl-1) -isocyanurate, an adduct of the Diels-Alder reaction of hexachlorocyclopentadiene, tribromophenylglycidyl ether, Bromophenyl acrylate, ethylenebistribromophenylether, ethylenebispentabromophenylether, tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy Fat, brominated polycarbonate, poly pentabromobenzyl acrylate, octa-bromonaphthalene, hexabromocyclododecane, bis (tribromophenyl) fumaramide, the use of such N- methyl hexabromoiridium diphenylamine is preferred.

In particular, hexabromobenzene, hexabromodiphenyl oxide, octabromodiphenyl oxide, decabromodiphenyl oxide, tetrabromobisphenol S and its derivatives, tetrabromophthalic anhydride and its derivatives, ethylene bis (5,6-dibromonorbornene-2,3 -Dicarboximide), tris- (2,3
-Dibromopropyl-1) isocyanurate, adduct of Diels-Alder reaction of hexachlorocyclopentadiene, ethylenebistribromophenylether, ethylenebispentabromophenylether, tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, Brominated epoxy resin,
Brominated polycarbonate, polypentabromobenzyl acrylate, bis (tribromophenyl) fumaramide, N-methylhexabromodiphenylamine are preferred.

These halogen-based flame retardants [B] are preferably used in an amount of 3 to 50 parts by weight, preferably 5 to 40 parts by weight, per 100 parts by weight of the component [A].

In the flame-retardant cyclic olefin polymer composition of the present invention,
An antimony-based flame retardant [C] is blended as a flame-retardant aid for more effectively exhibiting the flame-retarding effect of the halogen-based flame retardant [B]. Examples of the antimony flame retardant [C] include antimony trioxide, antimony pentoxide, sodium antimonate, and antimony trichloride.

These antimony-based flame retardants [C] are composed of [A] component 100
It is preferable to mix 1 to 30 parts by weight, preferably 2 to 20 parts by weight with respect to parts by weight.

In the flame-retardant cyclic olefin polymer composition of the present invention,
In addition to the halogen-based flame retardant [B] and the antimony-based flame retardant [C], polytetrafluoroethylene [D] is used as an anti-dripping agent for preventing dripping of the molten resin during combustion and further improving flame retardancy. ] Is compounded.

Polytetrafluoroethylene [D] is the component (A) 100
It is preferable to add 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight based on parts by weight.

In the flame-retardant cyclic olefin polymer composition of the present invention,
A magnesium hydroxide [E] is added to the components [A] to [D]. The mixing amount of magnesium hydroxide [E] is 2 to 150 parts by weight, preferably 5 to 1 part by weight based on the component [A].
00 parts by weight. By adding magnesium hydroxide [E], the compounding amount of the component [B], the component [C] and the component [D], particularly the compounding amount of the component [B] and the component [C] can be reduced. .

Further, the flame-retardant cyclic olefin-based polymer composition of the present invention may further comprise, as a component (F), (a) an amorphous or low-crystalline α-olefin polymer formed from at least two kinds of α-olefins. And (b) one or more copolymers selected from amorphous or low-crystalline copolymers in which (b) styrene or a derivative thereof is one of the monomer components and at least one of the glass transition temperatures is 0 ° C. or lower. Can be added to the component (A) in an amount of 5 to 100 parts by weight, preferably 5 to 50 parts by weight.

 Hereinafter, the component (F) will be described in detail.

As the component (F), (a) an amorphous or low-crystalline α-olefin-based copolymer formed from at least two kinds of α-olefins (hereinafter sometimes referred to as an α-olefin-based copolymer) ), For example, ethylene / propylene copolymer, propylene / butene-1 copolymer, propylene / isobutylene copolymer,
A copolymer of ethylene and propylene with a diene, or a blend of these polymers, a graft polymer obtained by grafting an unsaturated carboxylic acid or a derivative thereof,
An amorphous or low-crystalline copolymer (hereinafter referred to as a styrene-based copolymer) having (b) styrene or a derivative thereof as one of the monomer components, and having at least one of the glass transition temperatures of 0 ° C. or less, such as a block copolymer. Coalescence), specifically, styrene
An isobutylene copolymer, a styrene / butadiene copolymer, or the like can be used.

With respect to the α-olefin-based copolymer (a), when one of the α-olefins is ethylene, ethylene and another α-olefin are used.
Molar ratio with olefin (ethylene / α-olefin)
Varies depending on the type of α-olefin, but generally
Preferably it is 50/50 to 95/5. The molar ratio is α
If the olefin is propylene, 50/50 to 95 /
It is preferably 10, and when the α-olefin has 4 or more carbon atoms, it is preferably 60/40 to 95/5.

Further, when one α-olefin is propylene, that is, in a propylene / α-olefin copolymer,
The molar ratio of propylene to α-olefins other than propylene (propylene / α-olefin) varies depending on the type of α-olefin, but is generally preferably 50/50 to 95/5.

Such an α-olefin copolymer has a crystallinity of 0 to 50%, preferably 0 to 25%, as measured by X-ray diffraction.
%, The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.2 to 10 dl / g, preferably 1 to 7 dl / g.

Examples of the α-olefin-diene copolymer used as the α-olefin-based copolymer (a) include ethylene-α-olefin-diene copolymer, propylene-
An α-olefin / diene copolymer can be preferably used.

The α-olefin constituting the ethylene / α-olefin / diene copolymer is usually an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1 -Pentene, 1-octene, 1-decene or a mixture thereof can be exemplified. Of these, α-olefins having 3 to 10 carbon atoms are particularly preferred.

The α-olefin constituting the propylene / α-olefin / diene copolymer is usually an α-olefin having 4 to 20 carbon atoms, for example, 1-butene, 1-pentene,
Examples include -hexene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. Of these, α-olefins having 4 to 10 carbon atoms are particularly preferred.

The diene component in the ethylene / α-olefin / diene copolymer or propylene / α-olefin / diene copolymer includes 1,4-hexadiene, 1,6-octadiene, and 2-methyl-1,5-hexadiene. Linear non-conjugated dienes such as, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-
Cyclic non-conjugated dienes such as vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylenyl-2-norbornene; 2 , 3-Diisopropylidene-5-norbornene; 2-
Examples include ethylidene-3-isopropylidene-5-norbornene; 2-propenyl-2,2-norbornadiene.

In the ethylene / α-olefin / diene copolymer as described above, the molar ratio between ethylene and α-olefin (ethylene / α-olefin) varies depending on the type of α-olefin, but is generally 50/50 to 50/50. Preferably it is 95/5. The content of the diene component in the copolymer rubber is usually 1 to 20 mol%, preferably 2 to 15 mol%.

In the propylene / α-olefin / diene copolymer rubber as described above, the molar ratio of propylene to α-olefin (propylene / α-olefin) varies depending on the type of α-olefin, but is generally 50/50. ~ 95/5
It is preferred that The content of the diene component in the copolymer is preferably 1 to 20 mol%, more preferably 2 to 15 mol%.

Styrene-based copolymers (b) include styrene-butadiene block copolymer rubber, styrene-butadiene-
Styrene block copolymer rubber, styrene / isoprene block copolymer rubber, styrene / isoprolene / styrene block copolymer rubber, hydrogenated styrene / butadiene / styrene block copolymer rubber, hydrogenated styrene / isoprene / styrene block copolymer Examples include coalesced rubber and styrene / butadiene random copolymer rubber.

In these copolymer rubbers, the molar ratio of styrene to conjugated diene (styrene / conjugated diene) is generally
It is preferably 10/90 to 70/30.

The hydrogenated styrene / butadiene / styrene block copolymer rubber is a copolymer rubber obtained by hydrogenating a part or all of the double bonds remaining in the styrene / butadiene / styrene block copolymer rubber.

The hydrogenated styrene / isoprene / styrene block copolymer rubber is a copolymer rubber obtained by hydrogenating a part or all of the double bonds remaining in the styrene / isoprene / styrene block copolymer rubber.

The above soft resin or rubber-like substance has a glass transition temperature (Tg) of 0 ° C. or lower, preferably -10 ° C. or lower, more preferably -20 ° C. or lower, and intrinsic viscosity measured in decalin at 135 ° C. (Η) is 0.01 to 10 dl / g, preferably 0.
A range of from 08 to 7 dl / g, and a degree of crystallinity measured by X-ray diffraction method of from 0 to 10%, preferably from 0 to 7%, particularly preferably from 0 to 5% are preferred.

Such a soft resin or rubbery component can be used alone or in combination of two or more.

In the present invention, the melt flow index (MFR; ASTM D 123) of the flame-retardant cyclic olefin polymer composition to which the component (F) is added.
8 The condition L) is preferably 0.1 to 100.

Further, in addition to the above copolymer, the following polymers (c) to (so) can be blended.

(C) Halogen-containing vinyl polymers, specifically, polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polychloroprene, chlorinated rubber, etc. (d) derived from α, β-unsaturated acids and their derivatives Polymers, specifically polyacrylates, polymethacrylates, polyacrylamides, polyacrylonitriles, or copolymers of the monomers constituting the above polymers with other copolymerizable monomers, specifically acrylonitrile butadiene. (E) Polymers derived from unsaturated alcohols and amines or their acyl derivatives or acetal, such as styrene copolymers, acrylonitrile-styrene copolymers, acrylonitrile-styrene-acrylate copolymers, specifically polyvinyl alcohol , Polyvinyl acetate, polystearic acid Vinyl, poly (vinyl benzoate), poly (vinyl maleate), polyvinyl butyral, polyallyl phthalate,
Polyallyl melamine, or a copolymer of a monomer constituting the polymer and another copolymerizable monomer, specifically, ethylene.
(F) polymers derived from epoxides, specifically, polymers derived from polyethylene oxide or bisglycidyl ether, (g) polyacetals, specifically polyoxymethylene, (H) polyphenylene oxide, (H) polyphenylene oxide, (H) polysulfone, (H) polyurethane and urea resins, (II) Diamine and dicarboxylic acid and / or Polyamides and copolyamides derived from aminocarboxylic acids or the corresponding lactams, in particular nylon 6,
Nylon 66, Nylon 11, Nylon 12, etc. (W) Polyesters derived from dicarboxylic acids and dialcohols and / or oxycarboxylic acids or the corresponding lactones, specifically polyethylene terephthalate, polybutylene terephthalate, poly 1,4- (F) Polymers having a crosslinked structure derived from aldehyde and phenol, urea or melamine, such as dimethylol / cyclohexane terephthalate, specifically phenol / formaldehyde resin, urea / formaldehyde resin, melamine / formaldehyde, etc. Natural polymers, specifically cellulose, rubber, proteins, or derivatives thereof, such as cellulose acetate, cellulose propionate, cellulose acetate, cellulose ether, etc .; (t) alkyd resins, specifically glycemic resins (H) unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and obtained using a vinyl compound as a cross-linking agent, and halogen-containing modified resins; (So) an addition copolymer of a cyclic olefin represented by the general formula [I] and ethylene, and an α-olefin other than ethylene and / or a cyclic olefin other than the general formula [I] used as desired. In addition, a rubber-like material having a glass transition temperature of 0 ° C. or less can be used.

In the present invention, the flame-retardant cyclic olefin-based polymer composition may be subjected to a crosslinking reaction in the presence of an organic peroxide. The cross-linking reaction can be performed after all the components have been blended, or a method of mixing the components (A) and (F), then performing a cross-linking reaction, and then blending the remaining components can be employed. .

Examples of the organic peroxide used in the crosslinking reaction include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; 1,1-bis (t-butylperoxy) cyclohexane, and 2,2-bis (t-butyl peroxide). Peroxyketals such as oxy) octane; t-butyl hydroperoxide, cumene hydroperoxide, 2,2
Hydroperoxides such as 5-dimethylhexane-2,5-dihydroxy peroxide, 1,1,3,3-tetramethylbutyl hydroperoxide; di-t-butyl peroxide, 2,5-dimethyl-2, 5-di (t-butylperoxy)
Dialkyl peroxides such as hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-3, diacyl peroxides such as lauroyl peroxide and benzoyl peroxide; t-butylperoxyacetate, t
-Butyl peroxybenzoate, 2,5-dimethyl-2,5
-Peroxyesters such as di (benzoylperoxy) hexane.

The compounding amount of the above organic peroxide is [A] component and [F]
It is 0.01 to 1 part by weight, preferably 0.05 to 0.5 part by weight, based on 100 parts by weight of the total amount of the components.

When a compound having two or more radically polymerizable functional groups in the molecule is blended for the purpose of increasing the crosslinking efficiency during the crosslinking reaction, a composition having excellent impact resistance, particularly low-temperature impact resistance, can be obtained. preferable.

Compounds having two or more radically polymerizable functional groups in the molecule include divinylbenzene, vinyl acrylate,
And vinyl methacrylate. These compounds can be used in an amount of 1 part by weight or less, preferably 0.1 to 0.5 part by weight, based on 100 parts by weight of the total of the components [A] and [F].

In addition, the flame-retardant cyclic olefin polymer composition of the present invention further comprises aluminum hydroxide, calcium hydroxide, zirconium hydroxide, magnesium carbonate, dawsonite, calcium aluminate, Inorganic flame retardants such as gypsum, zinc borate, barium metaborate and the like can be blended. These inorganic flame retardants are preferably blended in an amount of 5 to 100 parts by weight based on the component (A).

As a method for producing the flame-retardant cyclic olefin-based polymer composition of the present invention, known methods can be applied, and examples thereof include a method in which each component is melt-mixed using an extruder or the like.

In addition, the flame-retardant cyclic olefin polymer composition of the present invention includes a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a slip agent, an anti-blocking agent, and an anti-fog within a range that does not impair the object of the present invention. Agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers and the like can be compounded in appropriate amounts. For example, as a stabilizer blended as an optional component, specifically, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, β- (3,5-
Phenolic antioxidants such as alkyl di-t-butyl-4-hydroxyphenyl) propionate and 2,2'-oxamidobis [ethyl-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Agent: trisnonylphenyl phosphite, tris (2,4-di-
phosphite-based stabilizers such as t-butylphenyl) phosphite; zinc stearate, calcium stearate,
Fatty acid metal salts such as calcium 12-hydroxystearate; polyhydric alcohol fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate A synthetic hydrotalcite, an epoxy compound and the like. These may be blended alone, but may be blended together,
For example, a combination of tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane with zinc stearate and glycerin monostearate can be exemplified.

Further, as an organic or inorganic filler, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, basic magnesium carbonate, dowamite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, Talc, clay, mica, asbestos, glass fiber, glass flake, glass beads,
Calcium silicate, montmorillonite, bentonite,
Examples thereof include graphite, aluminum powder, molybdenum sulfide, boron fiber, silicon carbide fiber, polyethylene fiber, polypropylene fiber, polyester fiber, and polyamide fiber.

As a method for mixing the flame-retardant cyclic olefin polymer composition of the present invention with other components, known methods can be applied, and for example, each component can be mixed simultaneously.

The flame-retardant cyclic olefin-based polymer composition of the present invention can be easily molded by any molding method such as extrusion molding and injection molding, and can be used for resin molded articles and other applications similar to conventional ones. Electrical products, home appliances,
When used for housings and components of OA equipment, etc., it fully demonstrates its characteristics.

〔The invention's effect〕

According to the present invention, a polymer comprising a specific cyclic olefin component (component (A)) is added to a halogen-based flame retardant, an antimony-based flame retardant, polytetrafluoroethylene, magnesium hydroxide, and an α-olefin-based copolymer. Incorporates components such as coalesced copolymers and styrene-based copolymers, so that less halogen-based flame retardants and antimony-based flame retardants are used, with excellent flame retardancy and heat resistance, chemical resistance, solvent resistance, dielectric properties, A flame-retardant cyclic olefin polymer composition having excellent electrical properties, rigidity, impact resistance, dimensional stability, moldability, and mechanical properties such as flexural strength and flexural modulus is obtained.

〔Example〕

 Hereinafter, examples of the present invention will be described.

Example 1 Ethylene-tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-
Dodecene copolymer (ethylene content 70 mol%, load 2.16k
g, melt flow index measured at 260 ° C, 20 g / min,
100 parts by weight of decabromodiphenyl oxide (hereinafter may be abbreviated as E-TCD copolymer) (Marubishi Yuka Co., Ltd.)
15.2 parts by weight of antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd.), 4.5 parts by weight of magnesium hydroxide (manufactured by Kyowa Chemical Co., Ltd., trade name: Kisuma 5
A) 30 parts by weight and 1.5 parts by weight of polytetrafluoroethylene powder (trade name: Teflon 6J, manufactured by Du Pont-Mitsui Flour Chemical Co., Ltd.) were mixed and melt-mixed at 230 ° C. by a twin screw extruder having a screw diameter of 45 mm. Pelletized.

The pellet temperature is 230 ° C and the mold temperature is 60 ° C.
To obtain various evaluation test pieces. Table 2 shows the compositions obtained by measuring various physical properties using these test pieces, and Table 3 shows the results.

 Various physical properties were measured under the following conditions.

Flammability: Tested on a 1/16 inch thick test specimen according to UL-94 standard.

That is, ten test pieces of a predetermined size were prepared for each sample, and a vertical combustion test was performed as follows.

The upper end of the test piece is clamped, the test piece is set vertically, a predetermined flame is applied to the lower end for 10 seconds, and the test piece is released, and the burning time (first time) of the test piece is measured.

Immediately after the fire is extinguished, a predetermined flame is again applied to the lower end for 10 seconds and then released, and the burning time (second time) of the test piece is measured.

The same measurement is repeated for the five pieces, and a total of ten pieces of data including five pieces of first burning time data and five pieces of second burning time data are collected.

Let T be the total of the ten data, and M be the maximum value of the ten data.

If T is 50 seconds or less, M is 10 seconds or less, and the flame does not burn up to the clamp, the flamed melt falls and the cotton 12 inches below does not ignite, V-0, T is 250 seconds or less, and M is 30 or less. In seconds or less, if the same conditions as those for the evaluation of V-0 are satisfied, V-1, T is 250 seconds or less, and M is 30 seconds or less. V-2 was evaluated when cotton under 12 inches ignited, and V-2 was rejected when the above evaluation criteria were not satisfied.

Melt flow index: ASTM D 1238 Izod impact strength (notched): ASTM D 256 Flexural strength, flexural modulus: ASTM D 790 Thermal deformation temperature: ASTM D 648 Example 2 Ethylene-tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10 ] -3-
Dodecene copolymer (ethylene content 70 mol%, load 2.16k
g, melt flow index measured at 260 ° C 20g / min)
80 parts by weight, 20 parts by weight of ethylene / propylene copolymer (ethylene content 80 mol%, load 2.16 kg, melt flow index 0.4 g / min measured at 190 ° C.), 15.2 parts by weight of decabromodiphenyl oxide, 4.5 of antimony trioxide Parts by weight, 30 parts by weight of magnesium hydroxide, and 1.5 parts by weight of polytetrafluoroethylene powder were mixed, melt-mixed at 230 ° C. by a twin screw extruder having a screw diameter of 45 mm, and pelletized.

The same test as in Example 1 was performed from this pellet. The composition is shown in Table 2 and the results are shown in Table 3.

Example 3 Ethylene-tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10] -3-
Dodecene copolymer (ethylene content 70 mol%, load 2.16k
g, melt flow index measured at 260 ° C 20g / min)
80 parts by weight, ethylene / propylene copolymer (ethylene content 80 mol%, load 2.16 kg, melt flow index measured at 190 ° C. 0.4 g / min) 20 parts by weight, divinylbenzene
0.3 parts by weight, and 0.1 part by weight of 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 were mixed and melt-mixed at 230 ° C. by a twin-screw extruder having a screw diameter of 45 mm, and pelletized. It has become.

Next, 100 parts by weight of the pellets, 15.2 parts by weight of decabromodiphenyl oxide, 4.5 parts by weight of antimony trioxide, 30 parts by weight of magnesium hydroxide, and 1.5 parts by weight of polytetrafluoroethylene powder were mixed and melt-mixed again under the above conditions. And pelletized.

The same test as in Example 1 was performed from this pellet. The composition is shown in Table 2 and the results are shown in Table 3.

Example 4 The same test as in Example 2 except that a styrene / ethylene / butadiene / styrene block copolymer (trade name: Kraton G1652, manufactured by Shell Chemical Co., Ltd.) was used instead of the ethylene / propylene copolymer. Was done. The composition is shown in Table 2 and the results are shown in Table 3.

Comparative Example 1 The same test as in Example 1 was performed without adding decabromodiphenyl oxide, antimony trioxide, magnesium hydroxide, and polytetrafluoroethylene. The composition is shown in Table 2 and the results are shown in Table 3.

Comparative Example 2 In Example 2, the same test was performed without adding decabromodiphenyl oxide, antimony trioxide, magnesium hydroxide, and polytetrafluoroethylene. The composition is shown in Table 2 and the results are shown in Table 3.

Comparative Example 3 In Example 3, the same test was performed without adding decabromodiphenyl oxide, antimony trioxide, magnesium hydroxide, and polytetrafluoroethylene. The composition is shown in Table 2 and the results are shown in Table 3.

Comparative Example 4 The same test was performed as in Example 3, except that polytetrafluoroethylene was not used, and the added amount of the other flame retardant components was changed to the amount shown in Table 2. The composition is shown in Table 2.
Table 3 shows the results.

Comparative Example 5 100 parts by weight of the E-TCD copolymer used in Example 1, 27.4 parts by weight of decabromodiphenyl oxide, and 9.6 parts by weight of antimony trioxide were mixed, and 2 parts having a screw diameter of 45 mm were mixed.
The mixture was melt-mixed at 230 ° C. and pelletized by a screw extruder.

The same test as in Example 1 was performed from this pellet. The composition is shown in Table 2 and the results are shown in Table 3.

Comparative Example 6 The same test was performed as in Example 3, except that magnesium hydroxide was not used, and the amount of other flame retardant components added was changed to the amount shown in Table 2. The composition is shown in Table 2 and the results are shown in Table 3.

Examples 5 and 6 In place of the E-TCD copolymer used in Examples 1 and 2, a resin obtained by hydrogenating a ring-opening polymer of a cyclic olefin (Zeonex 450 (registered trademark) manufactured by Zeon Corporation) And the same tests as in Examples 1 and 2 were conducted except that the melt mixing temperature in the twin screw extruder and the cylinder temperature in the injection molding machine were both set to 260 ° C. The composition is shown in Table 2 and the results are shown in Table 3.

Comparative Examples 7 and 8 The same tests as in Examples 5 and 6 were performed without adding decabromodiphenyl oxide, antimony trioxide, magnesium hydroxide, and polytetrafluoroethylene used in Examples 5 and 6. The composition is shown in Table 2 and the results are shown in Table 3.

From the results in Tables 2 and 3, decabromodiphenyl oxide (halogen flame retardant [B]), antimony trioxide (antimony flame retardant [C]), polytetrafluoroethylene [D] and magnesium hydroxide [ It can be seen that the addition of E] improves flame retardancy. In this case, it can be seen that the mixing amount of decabromodiphenyl oxide and antimony trioxide can be reduced by adding magnesium hydroxide [E].
Also, it can be seen that the impact strength is improved by blending the rubber component [F] as the polymer component.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 65/00 C08L 65/00 // (C08L 23/04 27:18) (C08K 13/02 3:22 3:16 3: 20 5:00) (C08L 65/00 27:18) (56) References JP-A-61-115916 (JP, A) JP-A-61-120816 (JP, A) JP-A-57-162734 (JP, A A) JP-A-63-110257 (JP, A) JP-A-63-135442 (JP, A) JP-B-51-39911 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) ) C08L 23/00-23/36 C08L 45/00 C08L 65/00 C08L 25/00-25/18 C08L 27/18

Claims (4)

(57) [Claims] 1. [A] The intrinsic viscosity [η] measured in decalin at 135 ° C. is 0.01 to 10 dl / g, and the softening temperature (TMA) is 70 ° C. or more. (A) a cyclic olefin-based random copolymer comprising an ethylene component and a cyclic olefin component represented by the following general formula [I], or (b) a ring opening weight of a cyclic olefin component represented by the following general formula [I]. Coalescence or its hydrogenated product, [Wherein, R ^{1 to} R ¹² are a hydrogen atom, a hydrocarbon group, or a halogen atom, and may be the same or different. R ⁹ and R ¹⁰ , or R ¹¹ and R ¹² may be integrated to form a divalent hydrocarbon group, and R ⁹ or R ¹⁰ and R ¹¹ or R ¹² may form a ring with each other. You may. n is 0 or a positive integer, and when R ^{5 to} R ⁸ are repeated a plurality of times, they may be the same or different. ] [B] a halogen-based flame retardant, [C] an antimony-based flame retardant, [D] polytetrafluoroethylene, and [E] magnesium hydroxide, and [B] component based on 100 parts by weight of [A] component. Is 3 to 50 parts by weight, [C] component is 1 to 30 parts by weight, [D] component is 0.01 to 5 parts by weight, and [E] component is 2 to 150 parts by weight. Cyclic olefin polymer composition. 2. [F] An amorphous or low-crystalline α-olefin copolymer formed from at least two kinds of α-olefins and styrene or a derivative thereof as one of the monomer components, and at least a glass. One or more copolymers selected from non-crystalline or low-crystalline copolymers, one of which has a transition temperature of 0 ° C. or lower, further containing 100 parts by weight of component (A).
The flame-retardant cyclic olefin polymer composition according to claim 1, wherein the component (F) is incorporated in an amount of 5 to 100 parts by weight. 3. The method according to claim 1, wherein the halogen-based flame retardant is hexabromobenzene, hexabromodiphenyl oxide, octabromodiphenyl oxide, decabromodiphenyl oxide, tetrabromobisphenol S and derivatives thereof,
Tetrabromophthalic anhydride and its derivatives, ethylenebis (5,6-dibromonorbornene-2,3-dicarboximide), tris- (2,3-dibromopropyl-1)-
Isocyanurate, adduct of Diels-Alder reaction of hexachlorocyclopentadiene, ethylene bistribromophenyl ether, ethylene bispentabromophenyl ether, tetradecabromodiphenoxybenzene, brominated polystyrene, brominated polyphenylene oxide, brominated epoxy resin, bromine Polycarbonate,
The flame-retardant cyclic olefin polymer composition according to claim 1 or 2, wherein the composition is polypentabromobenzyl acrylate, bis (tribromophenyl) fumaramide, or N-methylhexabromodiphenylamine. 4. An antimony-based flame retardant comprising antimony trioxide,
The flame-retardant cyclic olefin polymer composition according to any one of claims 1 to 3, which is antimony pentoxide, sodium antimonate, or antimony trichloride.