JPH11140282A - Flame resistant polymer composition and flame resistant resin molding product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame resistant polymer composition by improving the flame resistance of a thermoplastic ring-opening polymer of a thermoplastic norbornene-based monomer containing >=50 wt.% bicyclic or tricyclic norbornenes, or a hydrogenated product thereof, having excellent chemical resistance, heat resistance, impact resistance and flame resistance, and further to obtain a flame resistant molding product therefrom. SOLUTION: This polymer composition comprising a thermoplastic ring- opening polymer of a thermoplastic norbornene-based monomer containing >=50 wt.% bicyclic or tricyclic norbornenes, or a hydrogenated product thereof contains a halogen-containing flame retardant added thereto. The halogen- containing flame retardant is exemplified by bis(pentabromophenyl)ethane, bis(pentabromophenyl)methane, bis(tetrabromophenyl)ethane, bis(tribromophenoxy) ethane, a chlorinated polystyrene, an iodinated polystyrene and a brominated polystyrene.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polymer composition and a flame-retardant resin molded product, and more particularly, to a compound having excellent chemical resistance, heat resistance, impact resistance and flame resistance. The present invention relates to a ring-opened polymer of a norbornene-based monomer containing 50% by weight or more of bicyclic or tricyclic norbornenes or a hydrogenated product thereof.

[0002]

2. Description of the Related Art As a resin molded article having excellent chemical resistance, heat resistance and impact resistance and small molding shrinkage, a composition comprising a ring-opening polymer of norbornenes is formed into a predetermined shape by injection molding or blow molding. Resin molded articles have been proposed, and are expected to be used in various applications because of their excellent properties such as heat resistance and low moisture absorption.

[0003] A resin molded article molded using such a ring-opened polymer of norbornenes is excellent in various properties, but has a disadvantage of poor flame retardancy.

[0004] Therefore, compositions in which various flame retardants are blended with a thermoplastic ring-opening polymer of norbornenes or a hydrogenated product thereof have been studied. However, in order to improve the flame retardancy, it is usually necessary to add at least 10% by weight or more of a flame retardant. Therefore, the mechanical strength and the mechanical strength of the thermoplastic ring-opened polymer or the hydrogenated product thereof as a substrate are required. Features such as chemical properties are often impaired. Alternatively, in order to maintain these features to some extent, it was necessary to reduce the amount of the flame retardant to sacrifice the flame retardancy.

[0005]

SUMMARY OF THE INVENTION In some cases, a high degree of flame retardancy is required while maintaining characteristics such as mechanical strength and chemical resistance of a thermoplastic ring-opened polymer of a norbornene or a hydrogenated product thereof.

The present invention has been made in view of such circumstances, and contains 50% by weight or more of bicyclic or tricyclic norbornenes having excellent chemical resistance, heat resistance, impact resistance and flame retardancy. An object of the present invention is to provide a flame-retardant polymer composition and a flame-retardant resin molded product that can improve flame retardancy in a thermoplastic ring-opened polymer of a norbornene-based monomer or a hydrogenated product thereof. .

[0007]

In order to achieve the above object, a flame-retardant polymer composition according to the present invention comprises a norbornene-based monomer containing 50% by weight or more of bicyclic or tricyclic norbornenes. A halogenated flame retardant is added to a polymer composition comprising a thermoplastic ring-opened polymer or a hydrogenated product thereof.

The flame-retardant resin molded article according to the present invention is characterized by being obtained by molding a flame-retardant polymer composition into a predetermined shape.

(Thermoplastic norbornene ring-opening polymer or hydrogenated product thereof) In the present invention, the thermoplastic ring-opening weight of the norbornene monomer containing 50% by weight or more of bicyclic or tricyclic norbornenes is used. Coalescence or its hydrogenated product is used. Specifically, JP-A-63-26464
No. 6, JP-A-64-1705, JP-A-1-1-1
No. 68724, JP-A-1-168725, etc., among the norbornene-based thermoplastic ring-opening polymers and hydrogenated products thereof, the norbornene-based monomer as a raw material is a bicyclic or It contains 50% by weight or more of tricyclic norbornenes.

In general, ring-opening polymerization involves reacting a norbornene-based monomer (a monomer having a norbornene ring structure in the molecule as a main component) in the presence of a metathesis ring-opening polymerization catalyst system. Let it. In the present invention, a norbornene-based monomer (referred to as a monomer having a norbornene ring) containing 50% by weight or more of a bicyclic or tricyclic compound (here, carbonized in the molecule) is used. A monomer having n hydrogen rings is referred to as an n-ring monomer). Many norbornenes are known to be polycyclic having two or more rings, but in the present invention, a norbornene-based monomer containing 50% by weight or more of bicyclic or tricyclic norbornenes is used. Bicyclic or tricyclic norbornenes are added to 50
High impact resistance can be achieved only by using a norbornene-based monomer containing not less than% by weight.

The bicyclic norbornenes are adducts of substituted or unsubstituted non-cyclic olefins or non-cyclic dienes with cyclopentadiene, and specifically, bicyclo [2.2.1] hept-2. -Ene (common name norbornene), 5-methyl-bicyclo [2.2.1] hepta-
2-ene, 5,5-dimethyl-bicyclo [2.2.1]
Hept-2-ene, 5-ethyl-bicyclo [2.2.
1] Hept-2-ene, 5-butyl-bicyclo [2.
2.1] Hept-2-ene, 5-hexyl-bicyclo [2.2.1] hept-2-ene, 5-octyl-bicyclo [2.2.1] hept-2-ene, 5-octadecyl- Bicyclo [2.2.1] hepta-2-ene, 5-ethylidene-bicyclo [2.2.1] hepta-2-ene,
5-methylidene-bicyclo [2.2.1] hepta-2-
Ene, 5-vinyl-bicyclo [2.2.1] hepta-2
Norbornene derivatives such as -ene, 5-propenyl-bicyclo [2.2.1] hepta-2-ene, and halogens, hydroxyl groups, ester groups, alkoxy groups, cyano groups, amide groups, imide groups, and the like of these norbornene derivatives. Substitutes substituted with a polar group such as a silyl group (for example,
5-methoxy-carbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyano-bicyclo [2.2.1]
Hepta-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo [2.2.1] hepta-2-ene, etc.). Among these, a norbornene derivative having no polar group is preferable from the viewpoint of chemical resistance and ease of washing.

The tricyclic norbornenes are adducts of substituted or unsubstituted cyclic olefins or cyclic dienes with cyclopentadiene.
Tricyclo [4.3.0.1 ^2,6 ] deca
3,7-diene (commonly known as dicyclopentadiene), and its partially hydrogenated product (or adduct of cyclopentadiene and cyclopentene), tricyclo [4.3.0.1
^2,5 ] dec-3-ene; tricyclo [4.4. Which is an adduct of cyclopentadiene and cyclohexadiene.
1 ^2,5 ] undeca-3,7-diene or tricyclo [4.4.0.1 ^2,5 . 0 ^1,6] undec-3,8-diene, or a partially hydrogenated product (or an adduct of cyclopentadiene and cyclohexene) tricyclo [4.4.0.1 ^{2, 5]} undec-3-ene; 5-cyclopentyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyl-bicyclo [2.2.1], which is an adduct of cyclopentadiene and a vinyl compound having an alicyclic or aromatic ring group Hept-2-ene, 5-cyclohexenylbicyclo [2.2.1] hept-2-ene, 5-phenyl-bicyclo [2.2.1] hept-2
Tricyclic norbornenes such as -ene; and the like. Further, a substituted product of these norbornenes substituted with a polar group such as a halogen, a hydroxyl group, an ester group, an alkoxy group, a cyano group, an amide group, an imide group, and a silyl group may be used. Among them, those having no polar group are preferable from the viewpoint of chemical resistance and ease of cleaning, and tricyclo [4.3.1 ^2,5] is preferable in that the balance between impact resistance and heat resistance is excellent. . 0 ^1,6 ] Deca
3,7-diene is particularly preferred.

These bicyclic norbornenes and tricyclic norbornenes are used alone or in combination of two or more. The amount of the tricyclic norbornenes in the total amount of the bicyclic or tricyclic norbornenes is preferably 50% by weight or more, and more preferably 60% by weight.
As described above, the content is particularly preferably 70% by weight or more and 100% by weight or less. The properties such as impact resistance and heat resistance of the molded article molded in such a range are highly balanced and excellent.

The components other than these bicyclic or tricyclic norbornenes in the norbornene-based monomer are not particularly limited as long as they are copolymerizable monomer components. Norbornenes can be used.

As norbornenes having four or more rings, tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-Dodeca-
3-ene (also simply referred to as tetracyclododecene), 8-
Methyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
Dodeca-3-ene, 8-ethyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methylidenetetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-ethylidenetetracyclo [4.
4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-vinyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-propenyl-tetracyclo [4.
4.0.1 ^2,5 . 4-cyclonordenes having a tetracyclododecene (tetracyclic) structure such as 1 ^7,10 ] -dode-3-ene; 8-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene,
8-cyclohexyl-tetracyclo [4.4.0.1
^2,5 . 1 ^{7, 10]} - dodeca-3-ene, 8-cyclohexenyl - tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] −
Dodeca-3-ene, 8-phenyl-cyclopentyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ]-Dodeca-
Norbornenes 3-ene tetracyclododecene ring and alicyclic or 5 ring member having an aromatic ring such as; tetracyclo [7.4.0.1 ^10,13. 0 ^2,7 ] trideca-2,
4,6,11-tetraene (1,4-methano-1,4,4)
4a, also referred 9a- tetrahydrofluorene), tetracyclo [8.4.0.1 ^11,14. 0 ^3,8 ] tetradeca-3,5,7,12-tetraene (1,4-methano-
Pentacyclic norbornenes having a norbornene ring structure other than a tetracyclododecene ring and an aromatic ring, such as 1,4,4a, 5,10,10a-hexahydroanthracene); Pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0
^{9, 13]} pentadeca-3,10-diene and pentacyclo [7.4.0.1 ^3,6. 1 ^{10,1 3} . 0 ^2,7 ] pentadeca-4,11-diene; cyclopentadiene tetramer or higher adduct; and the like.

The norbornenes having four or more rings are the same as those described above
Derivatives having a cyclic group or more of norbornenes having a polar group (for example, 8-methoxycarbonyltetracyclo [4.4.
0.1 ^2,5 . 1 ^7,10 ] -dodec-3-ene, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.
^12.5 . 1 ^7,10 ] -dodec-3-ene, 8-hydroxymethyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] −
Dodeca-3-ene, 8-carboxytetracyclo [4.
4.0.1 ^2,5 . And a tetracyclododecene derivative having a substituent containing an oxygen atom such as [ ^17,10 ] -dode-3-ene. Among these tetracyclic or more norbornenes, those having no polar group are preferable from the viewpoint of chemical resistance and ease of washing.

Norbornenes (total of bicyclic or tricyclic norbornenes and tetracyclic or higher norbornenes)
Among them, bicyclic or tricyclic norbornenes are 50
% By weight or more, preferably 60% by weight or more, particularly preferably 70% by weight or more and 100% by weight or less. The properties such as impact resistance and heat resistance of the molded article molded in such a range are highly balanced and excellent.

Of the norbornene-based monomers (total of monomers), norbornenes (total amount of bicyclic or tricyclic and tetracyclic or more) are 70% by weight or more, preferably 80% by weight or more.
% By weight, particularly preferably 90% by weight or more.
00% by weight or less. When it is in such a range, the activity of the ring-opening polymerization reaction is high, which is preferable.

Other copolymerizable monomers include α-olefins having 2 to 12 carbon atoms such as ethylene, propylene, 1-butene and 4-methyl-1-pentene; styrene and α-methylstyrene. , P-methylstyrene, p
Styrenes such as -chlorostyrene; linear or branched dienes such as 1,3-butadiene, 1,4-butadiene and isoprene; vinyl ethers such as ethyl vinyl ether and isobutyl vinyl ether; cyclobutene;
Cyclopentene, cyclohexene, cycloheptene, cyclooctene monocyclic cycloolefin monomer: 1,3-
Cyclopentadiene, 1,3-cyclohexadiene,
Examples thereof include conjugated and non-conjugated cyclic diene monomers such as 1,3-cycloheptadiene and 1,3-cyclooctadiene.

The above norbornene-based monomer is subjected to ring-opening polymerization by a known method using a metathesis ring-opening polymerization catalyst system. The metathesis ring-opening polymerization catalyst system comprises a main catalyst and an activator, and is used in combination with a reaction modifier as required.

Since the thermoplastic norbornene ring-opening polymer obtained as a result of the ring-opening polymerization has an unsaturated bond remaining in the molecule, the unsaturated bond causes the thermoplastic norbornene ring-opening polymer to have weather resistance and thermal stability. Stability may decrease. For the purpose of improving this, it is preferable that 80% or more, preferably 90% or more of the unsaturated bond is saturated and used by hydrogenation. By using such a hydrogenation rate, weather discoloration when used for a long time is small, and excellent washing properties are obtained, which is preferable. The hydrogenation method and the hydrogenation catalyst can be performed by a known method.

The molecular weight of the thermoplastic norbornene-based ring-opening polymer and its hydrogenated product (hereinafter referred to as thermoplastic norbornene-based ring-opening polymer and the like) is appropriately selected, but the cyclohexane solution (thermoplastic norbornene-based ring-opening polymer) can be used. And the like are not dissolved, the number average molecular weight (in terms of polyisoprene) is usually 3,000 to 200,000, preferably 5,000 to 100,000, in particular, as measured by gel permeation chromatography of a toluene solution. Preferably it is in the range of 10,000 to 80,000. When the number average molecular weight of the thermoplastic norbornene-based ring-opening polymer or the like is in this range, it is preferable because mechanical strength such as impact resistance and molding processability are excellent.

The glass transition temperature (Tg) of the thermoplastic norbornene-based ring-opening polymer or the like may be selected as appropriate, but it is preferable that the molded product does not deform at the environmental temperature of use and has high heat resistance. It is preferable that the temperature is higher, and if the temperature is higher than the appropriate range, the resin becomes hard and the mechanical strength such as impact resistance is lowered. Tg is in the range of usually 30 to 140C, preferably 50 to 120C. When Tg is in this range, the molded product is suitable for long-term use without deformation or breakage.

The thermoplastic norbornene ring-opening polymer and the like include
They can be used alone or in combination of two or more.

(Other polymer components) In addition to the thermoplastic norbornene-based ring-opening polymer, other polymer components can be added to the molding material of the polymer composition according to the present invention, if necessary. Examples of other polymer components include rubbery polymers and thermoplastic resins other than thermoplastic norbornene-based ring-opening polymers.

The rubbery polymer is preferably a rubbery polymer having a glass transition temperature of around room temperature or lower, specifically 40 ° C. or lower. In addition, there are cases where the glass transition temperature of a rubbery polymer or the like obtained by block copolymerization has two or more points, in which case,
If the lowest glass transition temperature is 40 ° C. or lower, the rubbery polymer of the present invention having a glass transition temperature of 40 ° C. or lower can be used. Examples of preferred rubbery polymers include
Natural rubber, polybutadiene rubber, polyisoprene rubber,
Its hydrogenated products; chloroprene rubber, its hydrogenated products;
Saturated polyolefin rubbers such as ethylene / α-olefin copolymers such as ethylene / propylene copolymers and propylene / other α-olefin copolymers; ethylene / propylene / diene copolymers and α-olefin / diene copolymers Α-olefin / diene-based polymers such as union, isobutylene / isoprene copolymer, isobutylene / diene copolymer, and halides thereof; acrylonitrile /
Butadiene copolymer, hydrogenated product thereof; vinylidene fluoride / ethylene trifluoride copolymer, vinylidene fluoride / propylene hexafluoride copolymer, vinylidene fluoride / propylene hexafluoride / ethylene tetrafluoride copolymer And special rubbers such as urethane rubber, silicone rubber, polyether rubber, acrylic rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, propylene oxide rubber, and ethylene acrylic rubber; Norbornene-based rubbery polymers such as a copolymer of norbornene and ethylene or α-olefin, a terpolymer of norbornene and ethylene and α-olefin; styrene / butadiene copolymer rubber, styrene / isoprene copolymer Rubber, styrene
Random copolymers of aromatic vinyl monomers and conjugated dienes such as butadiene / isoprene terpolymer rubber and hydrogenated products thereof, styrene / butadiene / styrene block copolymer rubber, styrene / isoprene / styrene block copolymer Styrene-based thermoplastic elastomers such as linear or radial block copolymers of aromatic vinyl-based monomers and conjugated dienes such as polymer rubbers, and hydrogenated products thereof; urethane-based thermoplastic elastomers; polyamide-based thermoplastic elastomers; Examples thereof include thermoplastic elastomers such as 1,2-polybutadiene-based thermoplastic elastomer, vinyl chloride-based thermoplastic elastomer, and fluorine-based thermoplastic elastomer.

Rubbery polymers are those having a small difference in refractive index from thermoplastic norbornene-based ring-opening polymers and the like, and those which easily disperse by taking microdomains when mixed with thermoplastic norbornene-based ring-opening polymers. However, these selections are made in combination with the thermoplastic norbornene-based ring-opening polymer to be used.

Among the above rubbery polymers, a copolymer of an aromatic vinyl monomer and a conjugated diene monomer, a hydrogenated product thereof, and a norbornene rubbery polymer are used as a copolymer of a norbornene ring-opening polymer and the like. It is preferable because of good dispersibility. Here, the copolymer of the aromatic vinyl monomer and the conjugated diene monomer may be a block copolymer or a random copolymer. Preferred specific examples include styrene / butadiene block copolymer, styrene / butadiene / styrene / block copolymer, styrene / isoprene / block copolymer, styrene / isoprene / styrene / block copolymer, styrene / butadiene -A random copolymer and a hydrogenated product thereof are exemplified.
Among these, those obtained by hydrogenating some or all of the carbon-carbon unsaturated bonds other than the aromatic ring are more preferable, from the viewpoint that the weather resistance when the molded article is used for a long period of time is small, and styrene is preferred. Hydrogenated butadiene block copolymer, hydrogenated styrene / butadiene / styrene / block copolymer, hydrogenated styrene / isoprene / block copolymer, styrene / isoprene / styrene / block copolymer Particularly preferred are hydrogenated products and hydrogenated products of styrene / butadiene / random copolymer.

These rubbery polymers can be used alone or in combination. The compounding amount of the rubbery polymer is 100 or less such as norbornene-based ring-opening polymer.
The amount of the rubbery polymer is usually 0.01 to 100 parts by weight, preferably 0.05 to 50 parts by weight, more preferably 0.10 to 40 parts by weight with respect to parts by weight.

A thermoplastic resin other than the thermoplastic norbornene ring-opening polymer and the like can be used in combination.
Examples of such thermoplastic resins include polyolefins such as low-density polyethylene, high-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, polypropylene, syndiotactic polypropylene, polybutene, and polypentene; polyethylene terephthalate, polybutylene Polyesters such as terephthalate;
Polyamides such as nylon 6 and nylon 66; ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, polystyrene, syndiotactic polystyrene, polyphenylene sulfide, polyphenylene ether, polyamide, polyester, polycarbonate and the like. These other thermoplastic resins can be used alone or in combination of two or more, and the blending amount is appropriately selected within a range not to impair the object of the present invention.

(Blending agent) The molding material used in the present invention may be blended with a blending agent generally used for synthetic resins as long as the object of the present invention is not impaired.

For the purpose of improving the moldability at the time of molding, an etherified product of a polyhydric alcohol or an esterified product of a polyhydric alcohol may be added to a norbornene-based ring-opened polymer or the like. Specifically, for example, Japanese Patent Application Laid-Open No. 63-275
No. 654, glycerin monostearate, glycerin monolaurate, glycerin monobehenate, diglycerin monostearate, glycerin distearate, glycerin dilaurate, pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol monobehate Ethers of polyhydric alcohols such as pentaerythritol distearate, pentaerythritol dilaurate, pentaerythritol tristearate, dipentaerythritol distearate; 3- (octyloxy) -1,2
-Propanediol, 3- (decyloxy) -1,2-
Propanediol, 3- (lauryloxy) -1,2-
Propanediol, 3- (4-nonylphenyloxy) -1,2-propanediol, 1,6-dihydroxy-2,2-di (hydroxymethyl) -7- (4-nonylphenyloxy) -4-oxo Heptane, ether compound obtained by reaction of condensate of p-nonylphenol and formaldehyde with glycidol, ether compound obtained by reaction of condensate of p-octylphenol and formaldehyde and glycidol, condensate of p-octylphenol and dicyclopentadiene and glycidol And esterified products of polyhydric alcohols such as ether compounds obtained by the above reaction.

The molecular weight of the etherified product or esterified product of these polyhydric alcohols is not particularly limited.
Those having a number of from 00 to 2000, preferably from 800 to 1500 are preferred because they are difficult to elute. These etherified or esterified polyhydric alcohols may be used alone or in combination of two or more. The compounding amount is usually 0.01 part by weight based on 100 parts by weight of a norbornene-based ring-opened polymer or the like.
To 5 parts by weight, preferably 0.05 to 2 parts by weight, particularly preferably 0.1 to 1.0 part by weight. When the amount is within this range, the effects of improving moldability and reducing elution can be highly balanced.

It is also preferable to use a rubbery polymer in combination with an etherified or esterified product of a polyhydric alcohol.

A lubricant may be used for the purpose of improving moldability such as mold release. As the lubricant, for example, inorganic fine particles can be used. Here, the inorganic fine particles refer to the first, second, fourth, sixth, seventh, and seventh groups of the long period table.
Oxides, hydroxides, sulfides, nitrides, halides, carbonates, sulfates, acetates, phosphates, phosphites of Group 8 to 10, Group 11, Group 12, Group 13 and Group 14 elements; Organic carboxylate, silicate, titanate, particulates such as borate, these compounds and particulates of hydrous compounds of salts,
Particles of complex compounds having these salt centers or particles of natural minerals containing these salts as main components are shown. The amount of the lubricant to be added is appropriately selected according to the purpose of use, but is usually 0.001 to 5 parts by weight, preferably 0.005 parts by weight, per 100 parts by weight of the norbornene-based ring-opened polymer or the like.
When the amount is in this range, the moldability during molding is good.

Further, according to the present invention, oxidation or preservation during molding,
It is preferable to use an antioxidant for the purpose of preventing oxidative deterioration and aging deterioration during long-term use. Examples of the antioxidant include a phenolic antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. Among them, a phenol-based antioxidant is preferable, and an alkyl-substituted phenol-based antioxidant is preferable. Particularly preferred.

As the phenolic antioxidant, conventionally known phenolic antioxidants, for example, 2,6-di-t-butyl-
4-methylphenol, 2,6-di-t-butyl-4-
Ethylphenol, octadecyl-3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate, 2,2'-methylene-bis (4-methyl-6-t-
Butylphenol), 4,4'-butylidene-bis (6
-T-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-t-butylphenol), bis (3
-Cyclohexyl-2-hydroxy-5-methylphenyl) methane and the like.

The phosphorus-based antioxidant is not particularly limited as long as it is commonly used in the general resin industry. For example, triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris (Nonylphenyl) phosphite and the like can be mentioned. Examples of the sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3 ' -Thiodipropionate, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,
5] undecane and the like.

Each of these antioxidants is used alone.
Alternatively, two or more kinds can be used in combination.
The compounding amount of the antioxidant is 1 such as a norbornene-based ring-opening polymer.
It is usually in the range of 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight based on 00 parts by weight.

An ultraviolet inhibitor may be added for the purpose of improving weather resistance and the like. An antistatic agent can be used for the purpose of preventing dust and static electricity. In addition, for example, pigments and dyes for coloring;
Antiblocking agents; lubricants such as natural oils, synthetic oils and waxes may be added. These compounding agents can be used alone or in combination of two or more, and the compounding amount is appropriately selected within a range not to impair the object of the present invention.

(Halogen-Containing Flame Retardant) The halogen-containing flame retardant used in the present invention is not particularly limited, but a halogen-containing organic flame retardant is preferable in that it can prevent the molded article from decay. Examples of halogen-containing organic flame retardants include carbon tetrachloride, chloroform, 1,1,2,2-tetrabromoethane,
1,2,3,4-tetrabromoethane, 1,2,3-tribromopropane, hexabromobenzene, decabromodiphenyl oxide, bis (pentabromophenyl) ethane, bis (pentabromophenyl) methane, bis (tetra Bromophenyl) ethane, bis (tribromophenoxy) ethane, tetrabromobisphenol S, tetradecabromodiphenoxybenzene, 2,2-bis (4-
Hydroxy-3,5-dibromophenylpropane), pentabromotoluene, pentabromodiphenyl oxide, hexabromodiphenyl ether, octabromophenol ether, octabromodiphenyl ether,
Low molecular weight halogen-containing organic compounds such as octabromodiphenyl oxide and decabromodiphenyl ether; average molecular weight of about 350 to 550 and halogen content of 40 to 70
Weight percent normal paraffinic, average molecular weight about 500
A halogenated paraffin such as a paraffin wax system having a halogen content of 40 to 70% by weight and a halogenated elastomer; a halogenated polystyrene such as chlorinated polystyrene, iodine polystyrene, and brominated polystyrene; a halogen content of 50% by weight Halogenated polyolefins such as the above-mentioned high chlorinated polyethylene, high chlorinated polypropylene and chlorosulfonated polyethylene; halogenated polyvinyl chlorides such as chlorinated polyvinyl chloride;

Among these, brominated polystyrene, bis (pentabromophenyl) ethane, bis (pentabromo), and the like have a great effect of imparting flame retardancy and are excellent in compatibility with a thermoplastic norbornene-based ring-opening polymer and the like. Organic compounds having a brominated phenyl group such as phenyl) methane and bis (tetrabromophenyl) ethane are preferred.

The amounts of these halogen-containing flame retardants used are:
It is determined from the viewpoint of the degree of flame retardation, ease of kneading, dispersibility, and the like, and is preferably 10 to 100 parts by weight, more preferably 10 to 80 parts by weight, based on 100 parts by weight of the norbornene-based ring-opening polymer or the like. Range. If the used amount of the flame retardant is too small, the flame retardancy is not sufficient, and if the used amount is too large, the dispersibility tends to deteriorate or the molding becomes difficult. Therefore, the above range is preferable.

When an organic compound having a brominated phenyl group is used as the halogen-containing flame retardant, the weight ratio of bromine in the organic compound is such that the total amount of the organic compound is 100%.
When it is used as a weight part, it is preferably 30 to 80 parts by weight. By brominating a polystyrene resin in such a range, it functions well as a flame retardant. Also,
The weight ratio of the brominated polystyrene in the molded product is preferably 15 to 40% by weight, more preferably 15 to 30% by weight, although it depends on the desired degree of flame retardancy. If the weight ratio is too small, the flame retardancy of the molded article tends to decrease, and if it is too large, molding tends to be difficult.
The molecular weight of the brominated polystyrene is preferably 1,000
~ 500,000, more preferably 2,000 ~ 30
It is 0000. This is because the balance between heat resistance and moldability is excellent.

In the present invention, when an organic compound having a bromophenyl group is used as the flame retardant, dioxin is less likely to be generated as compared with the case where another flame retardant is used.

The average particle size of the organic compound having a brominated phenyl group is preferably 1 to 10 μm, more preferably 2 to 5 μm. If the particle size is too large, it may settle in the composition before molding, and a molded article having uniform flame retardant properties may not be obtained.

(Halogen-Free Flame Retardant) In the present invention, a halogen-free flame retardant may be used in combination with a halogen-containing flame retardant. However, some flame retardants such as aluminum hydroxide and magnesium hydroxide can be used as a halogen active species trapping agent, but here, such a flame retardant is not exemplified as a halogen-free flame retardant. Omitted.

The halogen-free flame retardant is not particularly limited, and inorganic compound flame retardants such as antimony oxide (antimony trioxide, diantimony tetroxide, diantimony pentoxide), sodium antimonate and zinc borate; (Chloroethyl) phosphate, tris (monochloropropyl) phosphate, tris (dichloropropyl) phosphate, triallylphosphite, tris (3-hydroxypropyl) phosphine oxide, tetrakis (2-
Chloroethylene) phosphorus-based flame retardants such as ethylene diphosphite and red phosphorus-based flame retardants; and the like.

Among them, antimony oxide, antimony pentoxide, and red phosphorus-based flame retardants are particularly preferred in order to particularly improve the flame retardancy. The red phosphorus-based flame retardant is a flame retardant that uses red phosphorus as an active species, such as red phosphorus particles, red phosphorus coated with aluminum or a resin, kneaded in a resin, ammonium polyphosphate, or the like. Is exemplified.

The amount of the halogen-free flame retardant used is determined by the amount of the halogen-containing flame retardant, the degree of flame retardation, and the like.
5 to 10 parts by weight or more, preferably 15 parts by weight or more, more preferably 20 parts by weight or more and 150 parts by weight or less, preferably 120 parts by weight or less. If the amount is too small, the flame retardancy tends to be insufficient. If the amount is too large, the moldability and the strength of the molded article tend to decrease.

In the present invention, when antimony oxide is used as the halogen-free flame retardant, the particle size of antimony oxide is not particularly limited, but is preferably 10 μm or less, and more preferably 0.1 to 10 μm. When the particle size is in this range, the moldability, the strength of the molded article, and the uniform flame retardant properties are preferred because they are highly balanced. The weight ratio of antimony oxide in the molded article was determined so that the flame retardancy was maximized in combination with the organic compound having a brominated phenyl group, and 100 parts by weight of the organic compound having a brominated phenyl group. , Preferably 5 to 30 parts by weight, more preferably 6 to 20 parts by weight. When brominated polystyrene is used as a halogen-free flame retardant, bromine (Br) and antimony (S
The ratio (Br / Sb) to b) is preferably 1/3 to 4
/ 1, more preferably 1/1 to 3/1.

(Halogen Activated Species Scavenger) In the composition and the molded article according to the present invention, it is preferable to include a halogen active species scavenger together with the halogen-containing flame retardant. The halogen active species trapping agent has a function of neutralizing the hydrogen halide generated when the halogen-containing flame retardant is heated, and by the action, the mold corrosion at the time of molding tends to be suppressed. is there. Examples of the halogen active species trapping agent include inorganic compounds such as aluminum hydroxide, magnesium hydroxide, and calcium carbonate, and organic compounds such as tetrahydric or higher polyhydric alcohol, phenol, and pentaerythritol. Among these,
In terms of excellent heat resistance of the obtained molded article, an inorganic type such as aluminum hydroxide and magnesium hydroxide is preferably exemplified.

The amount of the halogen-active species capturing agent used is 300 parts by weight or more, preferably 500 parts by weight or more based on 100 parts by weight of the halogen-containing flame retardant in the case of the inorganic type.
More preferably 700 parts by weight or more and 2000 parts by weight or less, preferably 1500 parts by weight or less, more preferably 1 part by weight or less.
000 parts by weight or less. In the organic type, 0.5 parts by weight or more based on 100 parts by weight of the halogen-containing flame retardant,
It is preferably at least 1 part by weight, more preferably at least 2 parts by weight, up to 20 parts by weight, preferably up to 15 parts by weight, more preferably up to 10 parts by weight. If the amount is too small, the capture of the halogen active species is not sufficient. If the amount is too large, molding tends to be inhibited or the strength of the molded body tends to decrease.

In the present invention, when aluminum hydroxide (Al (OH) ₃ ) is used as the halogen active species scavenger, the particle size of the aluminum hydroxide is preferably 20 μm or less, more preferably 10 μm or less. It is. If the particle size is too large, the moldability tends to decrease.

The weight ratio of aluminum hydroxide is determined in combination with an organic compound having a brominated phenyl group, and is preferably from 70 to 150 parts by weight, based on 100 parts by weight of the organic compound having a brominated phenyl group.
More preferably, it is 80 to 120 parts by weight. By including aluminum hydroxide in such a range, flame retardancy can be improved.

(Polymer Composition) The flame-retardant polymer composition according to the present invention can be obtained by mixing the above components with a thermoplastic norbornene ring-opening polymer or the like. The method of mixing is not particularly limited as long as the norbornene-based ring-opening polymer and the like and other polymer components and compounding agents are sufficiently dispersed. For example, there are a method of kneading the resin in a molten state with a mixer, a twin-screw kneader, or the like, a method of dissolving and dispersing in an appropriate solvent to coagulate, a method of casting, or a method of removing the solvent by a direct drying method.

In the case of kneading, it is appropriate that the resin temperature is a temperature of the glass transition temperature of the resin + 50 ° C. to the glass transition temperature + 150 ° C., and a sufficient uniform mixing state is obtained by sufficiently applying the shear. be able to.
If the resin temperature is too low, the viscosity increases and kneading is difficult.If it is too high, the thermoplastic norbornene-based ring-opening polymer and other resins and rubbery polymers deteriorate, and both are well kneaded due to differences in viscosity and melting point. Can not. Kneading conditions, such as screw shape, should be appropriately set according to the type and shape of the kneader. Preliminary kneading by the combination of the resin used, the rubbery polymer, and the equipment used for kneading,
It is preferable to determine the number of rotations, residence time, and the like according to the combination. After kneading, it is usually extruded into a rod shape in a molten state, cut into an appropriate length by a strand cutter, and is often used as pellets.

(Molding Method) The molded article of the present invention is obtained by molding the above molding material. The molding method may be in accordance with a conventionally known molding method, and includes injection molding, extrusion blow molding, injection blow molding, multilayer blow molding, connection blow molding, double wall blow molding, stretch blow molding, vacuum molding, rotational molding, and the like. No. The melting temperature of the resin at the time of molding varies depending on the type of the thermoplastic norbornene-based ring-opening polymer and the like, but is usually preferably 150 to 350 ° C. Further, as known from Japanese Patent Application Laid-Open No. 4-276253, increasing the gas barrier property, weather resistance, light resistance, etc. by multi-layer molding with another resin or double-wall molding depends on the purpose. This is possible as long as the visibility of the object is not affected.

Further, in order to improve the mechanical strength against a drop impact or the like, a reinforcing material such as a wire mesh is previously set in a mold at the time of molding, and is subjected to insert molding or other reinforcement after molding or during molding. The material may be used by being laminated on the surface of the molded body.

(Molded Article) The size and shape of the molded article formed using the polymer composition of the present invention are not particularly limited, and can be any desired size and shape. The obtained molded body has excellent flame retardancy of V-0 or more in a flame resistance test by UL (Underwritters Laboratory) 94 in addition to the fact that the resin is not carbonized or deteriorated. The specific use of the molded article obtained by the method according to the present invention is not particularly limited. For example, a use requiring flame retardancy such as a rear cover of a CT scanner, a casing for a personal computer, a casing of an electric appliance, furniture, and a wall material. Can be used for all.

[0061]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to only these examples. In particular, as for the shape of the molded body, in the examples, a test piece having a simple structure is prepared and tested as a test piece for flame retardancy test, but the shape is not limited to this shape.

Example 1 Tricyclo [4.3.0.1 ^2,5 ] deca-3,7-diene (tricyclic norbornenes, common name dicyclopentadiene, manufactured by Nippon Zeon, purity 95%, under nitrogen atmosphere) %, Hereinafter abbreviated as DCP) of 100 parts by weight with a known metathesis ring-opening polymerization catalyst system, followed by hydrogenation in a known manner to give D
A CP thermoplastic ring-opened polymer or a hydrogenated product thereof was obtained.
This DCP thermoplastic ring-opened polymer or a hydrogenated product thereof had a number average molecular weight Mn of 13,000 measured by GPC (gel permeation chromatography) using cyclohexane as a solvent in terms of polyisoprene. . The DCP thermoplastic ring-opened polymer or its hydrogenated product was dried by a known method. The hydrogenation rate before and after the hydrogenation reaction was 99.8% or higher by proton NMR, and the Tg measured by DSC was 97230C and the refractive index at 25 ° C was 1.5230 (based on ASTM D542).

With respect to 100 parts by weight of pellets of the DCP thermoplastic ring-opened polymer or a hydrogenated product thereof, 0.2 part by weight of a phenolic antioxidant pentaerythrityl-tetrakis (3- (3,5-di- Tertiary butyl-4-
Hydroxyphenyl) propionate) and 0.4 parts by weight of a hydrogenated styrene / butadiene / styrene / block copolymer (Toughtec H1051, manufactured by Asahi Kasei Corporation)
Crumb), 16 parts by weight of brominated polystyrene, 3
4 parts by weight of Al (OH) ₃ and 13 parts by weight of Sb ₂ O ₃
Were mixed and kneaded with a biaxial kneader, and the strand (rod-shaped molten resin) was passed through a strand cutter to obtain a pellet (granular) polymer composition (molding material).

The bromination ratio of the brominated polystyrene used in this example was 66% by weight. The average molecular weight of the brominated polystyrene was about 8000 or less. The average particle size of Al (OH) ₃ was 5 [mu] m, and Higlylite H-34 (trade name) manufactured by Showa Denko KK was used. The average particle size of Sb ₂ O ₃ was 0.5 μm, and Sb ₂ O ₃ of FS grade (trade name) manufactured by Sumitomo Metal Mining Co., Ltd. was used.

Next, using the pellet-shaped molding material produced as described above, an injection molding machine with a clamping pressure of 85 tons was used to inject the resin at a molding temperature of 260 ° C. and a mold temperature of 60 ° C. Molded, thickness 3.0mm, length 90mm, width 55m
m plate test pieces were manufactured.

No carbonization (burn) or the like was observed in the obtained molded article. When a flame resistance test of UL94 was performed using this molded body, it was confirmed that the evaluation of V-0 was satisfied and the flame retardancy was sufficient.

Further, the glass transition temperature (T
g) was measured and found to be 111 ° C. as shown in Table 1.
And the heat distortion temperature (HDT) is 96 ° C (JIS K
−6911, load 18.5kg), specific gravity 1.39g /
cm ³ , flexural strength 820 kg / mm ² , flexural modulus 2
3800 kg / mm ² (JIS K-7203), Izod impact strength is 4.4 kg · cm / cm [JIS K
−7110 6.5 (with a notch)], and it was confirmed that it had rigidity and flexibility, was lightweight, and was excellent in heat resistance and impact resistance.

[0068]

[Table 1] Example 2 Instead of DCP, 8-ethyltetracyclo [4.4.
^12.5 . ^17,10 . 0] -dodec-3-ene (tetracyclic norbornenes, hereinafter abbreviated as ETCD), 15 parts by weight, and DC
P85 parts by weight (total 100 parts by weight) and ETCD / DCP as in Example 1 except that the hydrogenated styrene / butadiene / styrene / block copolymer was not used.
A hydrogenated ring-opening copolymer was obtained. When the copolymerization ratio of each norbornene in the polymer was calculated from the composition of the residual norbornene in the solution after polymerization (by gas chromatography), it was almost equal to the charged composition at ETCD / DCP = 15/85. The ETCD / DCP thermoplastic ring-opened polymer or a hydrogenated product thereof has Mn of 16500
And the Tg was 106% or more.
° C.

When a flame resistance test was performed on UL94 in the same manner as in Example 1, the evaluation of V-0 was satisfied, and it was confirmed that the flame retardancy was sufficient.

Further, the glass transition temperature (T
g) was measured, and as shown in Table 1, 118 ° C
And the heat distortion temperature (HDT) is 103 ° C (JIS
K-6911, load 18.5kg), specific gravity 1.39g
/ Cm ³ , flexural strength 830 kg / mm ² , flexural modulus 24100 kg / mm ² (JIS K-7203), Izod impact strength 4.3 kg · cm / cm [JIS
K-7110 6.5 (with a notch)], and it was confirmed that it was rigid, flexible, lightweight, and excellent in heat resistance and impact resistance.

Example 3 In Example 1, bis (pentabromophenyl) ethane was used in place of brominated polystyrene as a halogen-containing flame retardant, and 100 parts by weight of pellets of a DCP thermoplastic ring-opening polymer or a hydrogenated product thereof. , A test piece was produced in the same manner as in Example 1 except that 15 parts by weight was added. The average particle size of bis (pentabromophenyl) ethane in this example was 3 μm, and Cytex 8010 (trade name) manufactured by Albemare Asano Co. was used.

No carbonization or the like was observed in the obtained molded article (test piece). Using this molded product, UL
When the flame resistance test of No. 94 was conducted, the evaluation of V-0 was satisfied, and it was confirmed that the flame retardancy was sufficient. Since the evaluation of V-0 was satisfied, it was confirmed that the amount of generated smoke was reduced and glowing was improved.

Further, the glass transition temperature (T
g) was measured to be 92 ° C., and the heat distortion temperature (HDT) was 77 ° C. (JIS K-6911, load 1)
8.5 kg), specific gravity 1.50 g / cm ³ , flexural strength 810 kg / mm ² , flexural modulus 23000 kg / mm
² (JIS K-7203), Izod impact strength is 4.2 kg · cm / cm [JIS K-7110 6.
5 (with a notch)], and it was confirmed that it had rigidity and flexibility, was lightweight, and had excellent heat resistance and impact resistance.

Comparative Example 1 The procedure of Example 1 was repeated except that the brominated polystyrene, Sb ₂ O ₃ and Al (OH) ₃ were not added to the DCP thermoplastic ring-opened polymer or its hydrogenated product pellets. A test piece was manufactured in the same manner as in Example 1.

A UL94 flame resistance test was carried out using the obtained molded product (test piece). As a result, the product did not satisfy the evaluation of V-0 and was HB. The superiority in flame retardancy of Example 1 was confirmed.

Example 4 A molded article was produced in the same manner as in Example 1 except that chlorinated polystyrene was used instead of brominated polystyrene in Example 1. The amount of the chlorinated polystyrene was 20 parts by weight based on 100 parts by weight of the pellets of the DCP thermoplastic ring-opening polymer or a hydrogenated product thereof.

The molded article obtained in this example was subjected to the same test as in Example 1, and found to be V-0 in the flame resistance test of UL94.

Example 5 A molded article was produced in the same manner as in Example 1 except that iodized polystyrene was used instead of brominated polystyrene in Example 1. The amount of the iodinated polystyrene was 20 parts by weight based on 100 parts by weight of the pellets of the DCP thermoplastic ring-opened polymer or its hydrogenated product.

The molded article obtained in this example was subjected to the same test as in Example 1. As a result, it was V-0 in the flame resistance test of UL94.

Example 6 A molded product was produced in the same manner as in Example 3 except that decabromodiphenyl ether was used instead of bis (pentabromophenyl) ethane. The amount of decabromodiphenyl ether added was the same as the amount of bis (pentabromophenyl) ethane added.

The molded article obtained in this example was subjected to the same test as in Example 1 and found to be V-0 in the flame resistance test of UL94.

[0082]

As described above, according to the present invention, 50% by weight of bicyclic or tricyclic norbornenes having excellent chemical resistance, heat resistance, impact resistance and flame retardancy are used. In the ring-opened polymer of the thermoplastic norbornene-based monomer or the hydrogenated product thereof, and the resin composition and the resin molded product, the flame retardancy can be particularly improved.

Claims (2)

[Claims] 1. A halogen-containing flame retardant in a polymer composition comprising a thermoplastic ring-opened polymer of a norbornene-based monomer containing 50% by weight or more of bicyclic or tricyclic norbornenes or a hydrogenated product thereof. A flame-retardant polymer composition, characterized by having added thereto. 2. A flame-retardant resin molded product obtained by molding the flame-retardant polymer composition according to claim 1 into a predetermined shape.