JP2003183473A - Flame retardant polymer composition - Google Patents

Abstract

(57) [Summary] [PROBLEMS] To provide excellent flame retardancy, no generation of toxic gas such as halogen gas when burned, and excellent balance of mechanical properties. Provided is a flame-retardant polymer composition suitable for use in industrial materials such as electric wire covering materials and insulating tapes. SOLUTION: A modified block copolymer comprising a vinyl aromatic hydrocarbon having a specific functional group and a conjugated diene or a hydrogenated product thereof (1) (100 parts by mass) and an inorganic filler (2) 1
A flame-retardant polymer composition comprising 0 to 2000 parts by mass.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is excellent in flame retardancy, does not generate toxic gas such as halogen gas even when burned, and has excellent balance of mechanical properties, wiring in equipment and harness for automobile. The present invention relates to a flame-retardant polymer composition suitable for applications such as electric wire coating materials and industrial materials such as insulating tapes.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomers, which are rubber-like soft materials and do not require a vulcanization step and have the same moldability as thermoplastic resins, have been used in automobile parts, home electric appliances,
It is used in the fields of industrial materials, wire coatings, medical parts, sundries, footwear, etc. Among such thermoplastic elastomers, a block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene and / or a hydrogenated product thereof is, for example, an extrusion molding or an injection molding as a composition with an olefin polymer. Molded by various methods such as car parts, household products,
It is also used for industrial materials. However, since the composition of such a block copolymer composed of a vinyl aromatic hydrocarbon and a conjugated diene and / or its hydrogenated product and an olefin polymer is flammable, it is rendered flame-retardant. Various methods have been studied.

As the most general method, a method of blending a halogen-based organic flame retardant is known. But,
Although these flame retardants exhibit flame retardant effects with a small amount of compounding, they have a problem that they generate corrosive and toxic gas when they burn. Further, for example, JP-A-2-263851 discloses a flame-retardant propylene resin composition containing a phosphorus-based flame retardant. However, this composition is required to prevent bleeding due to the hygroscopicity of the phosphorus-based flame retardant, and in terms of bleeding prevention, although an improvement effect can be seen by blending the olefin-based synthetic rubber and the silane coupling agent, flexibility is high. It was not satisfactory in terms of physical properties such as flexibility and flexibility.

Further, Japanese Patent Application Laid-Open No. 61-183337 discloses a flame-retardant polypropylene composition using bis (2,3-dibromopropyl) ether of tetrabromobisphenol S as a flame retardant. This compound was suspected to be an endocrine disruptor and was problematic in terms of environmental harmony. Further, for example, in JP-A-63-172759, a functionalized and selectively hydrogenated monoalkenyl arene-conjugated diene block copolymer, polypropylene, and a hydrate of an inorganic metal compound are blended. Japanese Patent Application Laid-Open No. 10-279736 discloses a polybutene / polypropylene alloyed polymer, a polyolefin resin, and a hydrate of an inorganic metal compound such as aluminum hydroxide or magnesium hydroxide. A compounded composition and a method for producing the same are disclosed in JP-A-2001-200.
No. 106 publication discloses a composition in which a hydrogenated conjugated diene polymer and / or an ethylene-α-olefin random copolymer, an olefin resin, and an inorganic filler such as magnesium hydroxide or aluminum hydroxide are blended. However, in a flame-retardant composition containing this type of hydrated inorganic filler, a large amount of hydrated inorganic filler is mixed in order to obtain sufficient flame retardancy. There is a problem that mechanical strength such as strength is lowered.

[0005]

DISCLOSURE OF THE INVENTION The present invention is excellent in flame retardancy, does not generate toxic gas such as halogen gas even when burned, and is excellent in balance of mechanical properties. An object of the present invention is to provide a flame-retardant polymer composition suitable for applications such as electric wire coating materials such as harnesses and industrial materials such as insulating tapes.

[0006]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above problems, the present inventors have found that a block copolymer having a specific functional group, and further a block having a specific functional group. By combining a composition in which a cross-linking agent having a specific functional group is combined with a copolymer, an inorganic filler, and if necessary, an olefin polymer, it is excellent in flame retardancy and halogen gas etc. even when burned. The present invention has been completed by finding out that no toxic gas is generated and the mechanical properties are excellent in balance.

That is, the present invention is as follows. 1. A block copolymer comprising at least one polymer block H mainly containing vinyl aromatic hydrocarbon and at least one polymer block S mainly containing conjugated diene, obtained by using an organolithium compound as a polymerization catalyst. 100 parts by mass of a modified block copolymer or hydrogenated product component (1) thereof obtained by subjecting a living group terminal to a functional group-containing modifier.
1. A flame-retardant polymer composition containing 10 to 2000 parts by mass of an inorganic filler (2). A block copolymer comprising at least one polymer block H mainly containing vinyl aromatic hydrocarbon and at least one polymer block S mainly containing conjugated diene, obtained by using an organolithium compound as a polymerization catalyst. 100 parts by mass of a modified block copolymer or hydrogenated product component (1) thereof obtained by subjecting a living group terminal to a functional group-containing modifier.
10 to 2000 parts by mass of the inorganic filler (2) and a cross-linking agent (3) which has reactivity with the functional group portion of the component (1).
A flame-retardant polymer composition comprising 01 to 20 parts by mass.

3. At least 1 mainly composed of vinyl aromatic hydrocarbon obtained by using an organolithium compound as a polymerization catalyst
Block copolymer consisting of one polymer block H and at least one polymer block S mainly composed of a conjugated diene, and a modified block copolymer obtained by adding and reacting a functional group-containing modifier to the living end of the block copolymer. Hydrogenated component (1) 1
00 parts by mass, inorganic filler (2) 10 to 2000 parts by mass,
Crosslinking agent (3) having reactivity with the functional group part of component (1)
A flame-retardant polymer composition comprising 0.01 to 20 parts by mass and olefin polymer (4) 2 to 1000 parts by mass.

4. At least 1 mainly composed of vinyl aromatic hydrocarbon obtained by using an organolithium compound as a polymerization catalyst
Block copolymer consisting of one polymer block H and at least one polymer block S mainly composed of a conjugated diene, and a modified block copolymer obtained by adding and reacting a functional group-containing modifier to the living end of the block copolymer. 100 parts by mass of the secondary modified block copolymer (5) obtained by reacting the crosslinking agent (3) having reactivity with the functional group of the hydrogenated component (1) in an amount of 0.3 to 10 mol per equivalent of the functional group, And inorganic filler (2)
A flame-retardant polymer composition comprising 10 to 2000 parts by mass.

5. At least 1 mainly composed of vinyl aromatic hydrocarbon obtained by using an organolithium compound as a polymerization catalyst
Block copolymer consisting of one polymer block H and at least one polymer block S mainly composed of a conjugated diene, and a modified block copolymer obtained by adding and reacting a functional group-containing modifier to the living end of the block copolymer. 100 parts by mass of the secondary modified block copolymer (5) obtained by reacting the crosslinking agent (3) having reactivity with the functional group of the hydrogenated component (1) in an amount of 0.3 to 10 mol per equivalent of the functional group, Inorganic filler (2) 10-2
000 parts by mass and olefin polymer (4) 2-1
A flame-retardant polymer composition comprising 000 parts by mass.

6. A functional group-containing modifier is a hydroxyl group, an epoxy group, an amino group, a silanol group, in the block copolymer by an addition reaction with the living end of the block copolymer,
At least one functional group selected from alkoxysilane groups
The flame-retardant polymer composition according to any one of claims 1 to 5, which is a modifier having a functional group that forms a modified block copolymer having bonded atomic groups or a hydrogenated product thereof. 7. The cross-linking agent (3) is a cross-linking agent having a functional group selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group. Flammable polymer composition. 8. Modified block copolymer or hydrogenated component thereof (1)
Is a modified block copolymer in which at least one atomic group having at least one functional group selected from the following formulas (1) to (14) is bonded, or a hydrogenated product thereof.
The flame-retardant polymer composition according to any one of 1 to 7.

[0012]

[Chemical 2]

(In the above formula, R ^{1 to} R ⁴ are hydrogen or carbon atoms 1
A hydrocarbon group having 1 to 24 carbon atoms or a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. R ⁵ has 1 to 1 carbon atoms
A hydrocarbon chain having 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. Elements such as oxygen, nitrogen, and silicon are bound to the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ in a bonding mode other than hydroxyl group, epoxy group, silanol group, and alkoxysilane group. It may be. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms) 9. The flame-retardant polymer composition according to any one of claims 1 to 8, wherein the inorganic filler (2) is a hydrated inorganic filler.

The present invention will be specifically described below.
Modified block copolymer composed of vinyl aromatic hydrocarbon and conjugated diene used in the present invention or hydrogenated component thereof (1)
The vinyl aromatic hydrocarbon content of is preferably 5 to 95 wt%, more preferably 10 from the balance of rigidity and elongation.
˜90 wt%, more preferably 15 to 85 wt%. When the vinyl aromatic hydrocarbon content of the component (1) is 60 wt% or more, preferably 65 wt% or more, it has resin-like properties and is less than 60 wt%, preferably 5
When it is 5 wt% or less, it has elastic properties. The vinyl aromatic hydrocarbon content of the component (1) which is particularly preferable in the present invention is such that the vinyl aromatic hydrocarbon content is 5 wt% or more and less than 70 wt%, preferably 7 to 60 wt%, and more preferably 10 to 50 wt%. Is.

The block copolymer can be produced by, for example, JP-B-36-19286 and JP-B-43-17.
979, JP-B-46-32415, JP-B-49-36957, JP-B-48-2423, JP-B-48-4106, and JP-B-56-289.
25, JP-B-51-49567, JP-A-5
The methods described in JP-A No. 9-166518, JP-A No. 60-186577 and the like can be mentioned.

The functional group-containing block copolymer used in the present invention can be obtained by addition-reacting the modifying agent described below to the living terminal of the block copolymer obtained by these methods. It has a structure that (HS) _n- X, H- (SH) _n- X, S- (H
_{-S) n -X, X- (H} -S) n, X- (H-S) n -
X, X-H- (SH) _n- X, X-S- (HS) _n
-X, [(SH) _n ] _m- X, [(HS) _n ] _m- X,
[(SH) _n- S] _m- X, [(HS) _n- H] _m- X (In the above formula, H is a polymer block mainly composed of vinyl aromatic hydrocarbon, and S Is a polymer having a conjugated diene as a main component, the boundary between H block and S block does not necessarily need to be clearly distinguished, and n is an integer of 1 or more, preferably an integer of 1 to 5. m is an integer of 2 or more, preferably an integer of 2 to 11. X represents a residue of a modifier to which an atomic group having a functional group described later is bonded, and X is added by a metalation reaction described later. In that case, the side chains of the H block and / or S block are bonded to each other, and the polymer chains bonded to X may have the same structure or different structures.

In the above description, the polymer block H mainly containing vinyl aromatic hydrocarbon is preferably 50 wt% or more of vinyl aromatic hydrocarbon, more preferably 70%.
A copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene containing at least wt% and / or a vinyl aromatic hydrocarbon homopolymer block is shown, and the polymer block S mainly composed of the conjugated diene is a conjugated diene. Preferably 50 wt
%, More preferably 60 wt% or more, and a conjugated diene / vinyl aromatic hydrocarbon copolymer block and / or conjugated diene homopolymer block is shown.

The vinyl aromatic hydrocarbon in the copolymer block may be distributed uniformly or in a taper shape. Further, the copolymer portion may coexist with a plurality of portions in which vinyl aromatic hydrocarbons are uniformly distributed and / or a plurality of portions in which taper distribution is formed. The block copolymer used in the present invention may be any mixture of the block copolymers represented by the above general formula.
In the present invention, the microstructure (ratio of cis, trans, vinyl) of the conjugated diene portion in the block copolymer can be arbitrarily changed by using a polar compound described later, and 1,3-butadiene is used as the conjugated diene. 1,2-vinyl bond content is preferably 5 to 90
%, More preferably 10 to 80%, when isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used in combination, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds. Preferably 3-80%,
It is more preferably 5 to 70%.

However, the microstructure in the case of using a hydrogenated product as the block copolymer has a conjugated diene of 1,3-
When butadiene is used, the 1,2-vinyl bond content is preferably 10-80%, more preferably 25-75.
%, And when isoprene is used as the conjugated diene or when 1,3-butadiene and isoprene are used in combination, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is preferably 5 to 70. % Is recommended. In the present invention, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (however, when 1,3-butadiene is used as the conjugated diene, the 1,2-vinyl bond amount) is Hereinafter referred to as vinyl bond content.

In the present invention, the conjugated diene is a diolefin having a pair of conjugated double bonds, for example, 1,3
-Butadiene, 2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene, 1,3-hexadiene and the like, but particularly common ones are 1,3-butadiene,
Examples include isoprene. These may be used not only in one kind but also in two or more kinds in the production of one block copolymer. Further, as the vinyl aromatic polymer, styrene, o-methylstyrene, p-methylstyrene, pt
ert-butyl styrene, 1,3-dimethyl styrene,
There are α-methylstyrene, vinylnaphthalene, vinylanthracene and the like, but styrene is particularly common. These may be used not only in one kind but also in two or more kinds in the production of one block copolymer.

In the present invention, when isoprene and 1,3-butadiene are used together as the conjugated diene of the block copolymer, the mass ratio of isoprene and 1,3-butadiene is preferably 95/5 to 5/95, more preferably Is 90/1
0-10 / 90, more preferably 85 / 15-15 / 8
It is 5. In particular, when obtaining a pressure-sensitive adhesive composition excellent in low-temperature characteristics, the mass ratio of isoprene and 1,3-butadiene is preferably 49/51 to 5/95, more preferably 45.
/ 55 to 10/90, more preferably 40/60 to 15
/ 85 is recommended. Isoprene and 1,3-
When used together with butadiene, even in high temperature molding processing,
A composition having a good balance of appearance properties and mechanical properties can be obtained.

In the present invention, the ratio of the vinyl aromatic hydrocarbon polymer block incorporated in the block copolymer (called the block ratio of vinyl aromatic hydrocarbon) can be adjusted, and the vinyl aromatic hydrocarbon block ratio can be adjusted. Block rate is preferably 50 wt% or more, more preferably 50 wt%
The amount can be adjusted to ˜98 wt%, more preferably 60 to 97 wt%. The block ratio of the vinyl aromatic hydrocarbon incorporated in the block copolymer is measured by oxidative decomposition of the block copolymer with tertiary butyl hydroperoxide using osmium tetroxide as a catalyst (IM KOLTHOFF, et al., JP
olym. Sci. 1,429 (1946)) to obtain a vinyl aromatic hydrocarbon polymer block component (excluding the vinyl aromatic hydrocarbon polymer component having an average degree of polymerization of about 30 or less). , Can be obtained from the following formula. Block ratio of vinyl aromatic hydrocarbon (%) = (mass of vinyl aromatic hydrocarbon polymer block in block copolymer / mass of all vinyl aromatic hydrocarbon in block copolymer) × 100

In the present invention, as the solvent used for producing the block copolymer, butane, pentane, hexane, isopentane, heptane, octane, isooctane and other aliphatic hydrocarbons, cyclopentane, methylcyclopentane, cyclohexane, methyl are used. Alicyclic hydrocarbons such as cyclohexane and ethylcyclohexane, or hydrocarbon solvents such as aromatic hydrocarbons such as benzene, toluene, ethylbenzene and xylene can be used. These may be used alone or as a mixture of two or more.

The organolithium compound used in the production of the block copolymer is a compound having one or more lithium atoms bonded in the molecule, such as ethyllithium,
Examples thereof include n-propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butadienyldilithium, and isoprenyldilithium. These may be used alone or as a mixture of two or more.

Further, the organolithium compound may be added once or more during the polymerization in the production of the block copolymer. In the present invention, a polar compound or a random compound for the purpose of adjusting the polymerization rate during production of the block copolymer, changing the microstructure of the polymerized conjugated diene moiety, adjusting the reactivity ratio between the conjugated diene and the vinyl aromatic hydrocarbon, and the like. Agents can be used. Examples of the polar compound and the randomizing agent include ethers, amines, thioethers, phosphoramide, potassium salt or sodium salt of alkylbenzene sulfonic acid, potassium or sodium alkoxide, and the like.

Examples of suitable ethers are dimethyl ether, diethyl ether, diphenyl ether, tetrahydrofuran, diethylene glycol dimethyl ether,
It is diethylene glycol dibutyl ether. As amines, tertiary amine, trimethylamine, triethylamine, tetramethylethylenediamine, and other cyclic tertiary amines can be used. Examples of the phosphine and phosphoramide include triphenylphosphine and hexamethylphosphoramide.

In the present invention, the polymerization temperature for producing the block copolymer is preferably -10 ° C to 150 ° C.
More preferably, it is 30 ° C to 120 ° C. The time required for the polymerization varies depending on the conditions, but it is preferably within 48 hours, particularly preferably 0.5 to 10 hours. The polymerization atmosphere is preferably an inert gas atmosphere such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is within the range of the above-mentioned polymerization temperature and is a pressure sufficient to maintain the monomer and the solvent in the liquid phase. Further, it is preferable that impurities such as water, oxygen, carbon dioxide gas, etc. which inactivate the catalyst and the living polymer are not mixed in the polymerization system.

The modified block copolymer or its hydrogenated component (1) used in the present invention is a polymer block H containing at least one vinyl aromatic hydrocarbon as a main component, which is obtained by using an organolithium compound as a polymerization catalyst. And a functional group-containing modifier are added to the living end of a block copolymer composed of a polymer block S containing at least one conjugated diene as a main component, and a hydroxyl group, a carboxyl group or a carbonyl group is added to the block copolymer. Group, thiocarbonyl group, acid halide group, acid anhydride group, carboxylic acid group, thiocarboxylic acid group, aldehyde group, thioaldehyde group, carboxylic acid ester group, amide group, sulfonic acid group, sulfonic acid ester group, phosphoric acid Group, phosphate ester group, amino group, imino group, nitrile group, pyridyl group, quinoline group, epoxy group, thioepoxy group, sulfur An atomic group having at least one functional group selected from a fido group, an isocyanate group, an isothiocyanate group, a silanol group, an alkoxysilane group, a silicon halide group, a tin halide group, an alkoxytin group, a phenyltin group, etc. The modified block copolymer or hydrogenated product thereof.

A method for obtaining a block copolymer having an atomic group having such a functional group bonded thereto or a hydrogenated product thereof is as follows. A modifier having a functional group that forms a modified block copolymer having an atomic group having at least one functional group selected from the functional groups bonded thereto or a hydrogenated product thereof, or the functional group is protected by a known method. It can be obtained by a method in which a modifier having an atomic group bonded thereto is subjected to an addition reaction.

As another method, the block copolymer is reacted with an organic alkali metal compound such as an organic lithium compound (metalation reaction), and the above-mentioned modifier is added to the polymer obtained by adding the organic alkali metal to the block copolymer. The method of carrying out the addition reaction can be raised. In the latter case, the hydrogenation product of the block copolymer may be obtained and then a metalation reaction may be carried out to react the above-mentioned modifier. Depending on the type of modifier, the hydroxyl group, amino group, etc. may generally be an organic metal salt at the stage of reaction with the modifier, in which case it should be treated with a compound having active hydrogen such as water or alcohol. Thus, a hydroxyl group or an amino group can be obtained.

In the present invention, when the living terminal of the block copolymer is reacted with the modifier, a partially unmodified block copolymer is mixed in the modified block copolymer of the component (1). May be. The proportion of the unmodified block copolymer mixed in the modified block copolymer of the component (1) is preferably 70 wt% or less, more preferably 60% by weight or less.
It is recommended that the content is less than wt%, more preferably less than 50 wt%. In the flame-retardant polymer composition of the present invention, the atomic group bonded to the modified block copolymer or its hydrogenated component (1) has at least one functional group selected from the above functional groups. , High reactivity or affinity with the inorganic filler, the interaction is effectively expressed by physical affinity such as chemical bond with the inorganic filler or hydrogen bond between mutual functional groups, It is possible to obtain a flame-retardant polymer composition having excellent properties aimed at by the present invention by causing a chemical bond or a physical affinity with the crosslinking agent specified in the present invention.

The modified block copolymer used in the present invention or its hydrogenated component (1) is particularly preferably one having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group. It is a modified block copolymer or a hydrogenated product thereof in which the atomic groups have been bound. In the present invention, a preferable atomic group as an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is a general atomic group represented by the following formulas (1) to (14). The atomic groups selected from those represented by the formula are raised.

[0033]

[Chemical 3]

(In the above formula, R ^{1 to} R ⁴ are hydrogen or a carbon number of 1
A hydrocarbon group having 1 to 24 carbon atoms or a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. R ⁵ has 1 to 1 carbon atoms
A hydrocarbon chain having 48 carbon atoms, or a hydrocarbon chain having 1 to 48 carbon atoms having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group. Elements such as oxygen, nitrogen, and silicon are bound to the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ in a bonding mode other than hydroxyl group, epoxy group, silanol group, and alkoxysilane group. It may be. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms) In the present invention, at least one atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group and an alkoxysilane group is bonded. Examples of the modifying agent used to obtain the modified block copolymer or the hydrogenated product thereof include the following.

For example, tetraglycidyl metaxylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiaminodiphenylmethane,
Diglycidyl aniline, diglycidyl orthotoluidine, γ-glycidoxyethyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, γ-glycidoxybutyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, γ- Glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylethyldimethoxysilane, γ-glycidoxypropylethyldiethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyldipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-glycidoxypropyldisilane They are ethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxysilane, γ-glycidoxypropyldiethylmethoxysilane, and γ-glycidoxypropylmethyldiisopropeneoxysilane.

Also, bis (γ-glycidoxypropyl)
Dimethoxysilane, bis (γ-glycidoxypropyl)
Diethoxysilane, bis (γ-glycidoxypropyl)
Dipropoxysilane, bis (γ-glycidoxypropyl) dibutoxysilane, bis (γ-glycidoxypropyl) diphenoxysilane, bis (γ-glycidoxypropyl) methylmethoxysilane, bis (γ-glycidoxy) Propyl) methylethoxysilane, bis (γ-glycidoxypropyl) methylpropoxysilane, bis (γ-glycidoxypropyl) methylbutoxysilane, bis (γ
-Glycidoxypropyl) methylphenoxysilane, tris (γ-glycidoxypropyl) methoxysilane, γ
-Methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyltrimethoxysilane, γ-methacryloxyethyltriethoxysilane, bis (γ-methacryloxypropyl) dimethoxysilane, tris (γ- Methacryloxypropyl) methoxysilane.

Furthermore, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, β- (3,3
4-epoxycyclohexyl) ethyl-triethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tripropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-tributoxysilane, β- (3,3
4-epoxycyclohexyl) ethyl-triphenoxysilane, β- (3,4-epoxycyclohexyl) propyl-trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-ethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-ethyldiethoxysilane, β- (3,4-
Epoxycyclohexyl) ethyl-methyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldipropoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldibutoxysilane, β
-(3,4-epoxycyclohexyl) ethyl-methyldiphenoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylmethoxysilane, β- (3,3
4-epoxycyclohexyl) ethyl-diethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylpropoxysilane, β- (3,4- Epoxy cyclohexyl) ethyl-
Dimethylbutoxysilane, β- (3,4-epoxycyclohexyl) ethyl-dimethylphenoxysilane, β-
(3,4-epoxycyclohexyl) ethyl-diethylmethoxysilane, β- (3,4-epoxycyclohexyl) ethyl-methyldiisopropeneoxysilane, 1,
Examples thereof include 3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N, N′-dimethylpropyleneurea, N-methylpyrrolidone and the like.

By reacting the above-mentioned modifying agent, the residue of the modifying agent to which an atomic group having at least one functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group is bonded. A bonded modified block copolymer is obtained. When the functional group-containing modifier is added to the living end of the block copolymer, the living end of the block copolymer may be either the polymer block H or the polymer block S, but in order to increase the mechanical strength of the composition. Is preferably bound to the end of the polymer block H.

In the present invention, the hydrogenated product of the modified block copolymer is obtained by hydrogenating the modified block copolymer obtained above. The hydrogenation catalyst is not particularly limited and is conventionally known 1) Ni, Pt, P
A supported heterogeneous hydrogenation catalyst in which metals such as d and Ru are supported on carbon, silica, alumina, diatomaceous earth, etc., 2) N
So-called Ziegler-type hydrogenation catalysts using organic acid salts such as i, Co, Fe and Cr or transition metal salts such as acetylacetone salts and reducing agents such as organic aluminum, 3) Ti,
A homogeneous hydrogenation catalyst such as a so-called organometallic complex such as an organometallic compound such as Ru, Rh or Zr is used.

As a specific hydrogenation catalyst, Japanese Patent Publication No. 42-
8704, Japanese Patent Publication No. 43-6636, Japanese Patent Publication No. 63-4841, Japanese Patent Publication No. 1-39700,
The hydrogenation catalysts described in JP-B-1-53851 and JP-B-2-9041 can be used. Preferred hydrogenation catalysts include a mixture with a titanocene compound and / or a reducing organometallic compound. As the titanocene compound, compounds described in JP-A-8-109219 can be used, and specific examples thereof include (substituted) biscyclopentadienyl titanium dichloride, monopentamethylcyclopentadienyl titanium trichloride and the like. At least one ligand having a cyclopentadienyl skeleton, an indenyl skeleton or a fluorenyl skeleton
Compounds having one or more can be mentioned. Examples of the reducing organic metal compound include organic alkali metal compounds such as organic lithium, organic magnesium compounds, organic aluminum compounds, organic boron compounds and organic zinc compounds.

The hydrogenation reaction is preferably carried out in the temperature range of 0 to 200 ° C, more preferably 30 to 150 ° C. The pressure of hydrogen used in the hydrogenation reaction is preferably 0.1 to
15 MPa, more preferably 0.2 to 10 MPa, further preferably 0.3 to 5 MPa is recommended. The hydrogenation reaction time is preferably 3 minutes to 10 hours, more preferably 10 minutes to 5 hours. The hydrogenation reaction is a batch process,
Either a continuous process or a combination thereof can be used.

In the hydrogenated product of the modified block copolymer used in the present invention, the total hydrogenation rate of unsaturated double bonds based on the conjugated diene compound can be arbitrarily selected according to the purpose and is not particularly limited. From the viewpoint of the thermal stability of the hydrogenated product of the modified block copolymer and the compatibility with the olefin polymer, 50% or more of the unsaturated double bond based on the conjugated diene compound in the modified block copolymer, preferably Is 60%
As described above, more preferably 80% or more is hydrogenated, and further the hydrogenation rate of vinyl bond based on the conjugated diene before hydrogenation is preferably 85% or more, more preferably 90% or more, and further preferably Is preferably 95% or more. Here, the hydrogenation rate of vinyl bonds means the rate of hydrogenated vinyl bonds in the vinyl bonds based on the conjugated diene before hydrogenation incorporated in the block copolymer.

The hydrogenation rate of the aromatic double bond based on the vinyl aromatic hydrocarbon in the block copolymer is not particularly limited, but is preferably 50% or less, more preferably 30% or less, and further preferably. 20% or less is recommended. The hydrogenation rate can be known by a nuclear magnetic resonance apparatus (NMR). The weight average molecular weight of the modified block copolymer or hydrogenated product thereof used in the present invention is 30,000 or more from the viewpoint of maintaining mechanical strength of the composition, and 1,000,000 or less from the viewpoint of melt-kneading property and moldability. Is preferable, and more preferably 4
It is 10,000 to 500,000, more preferably 50,000 to 300,000.

In the present invention, the amount of vinyl bond based on the conjugated diene compound in the block copolymer can be known by using a nuclear magnetic resonance apparatus (NMR). The hydrogenation rate can also be known using the same device. The weight average molecular weight of the block copolymer or the hydrogenated product thereof is measured by gel permeation chromatography (GPC), and the molecular weight of the peak of the chromatogram is determined by measuring the standard curve of commercially available polystyrene (standard curve). (Prepared using the peak molecular weight of polystyrene).

The solution of the modified block copolymer or hydrogenated product thereof obtained as described above is separated from the solution by removing the catalyst residue, if necessary, and then removing the modified block copolymer or hydrogenated product thereof from the solution. be able to. As the method for separating the solvent, for example, a method in which a polar solvent which is a poor solvent for the polymer such as acetone or alcohol is added to a solution after polymerization or hydrogenation to precipitate and recover the polymer, a modified block copolymer Alternatively, the solution of the hydrogenated product is poured into hot water with stirring,
Examples thereof include a method of removing the solvent by steam stripping and recovery, a method of directly heating the polymer solution and distilling the solvent. The modified block copolymer used in the present invention or a hydrogenated product thereof may contain stabilizers such as various phenol-based stabilizers, phosphorus-based stabilizers, sulfur-based stabilizers and amine-based stabilizers. .

Next, the inorganic filler used as the component (2) in the present invention is not particularly limited, but for the purpose of obtaining a composition excellent in flame retardance, for example, aluminum hydroxide, magnesium hydroxide, etc. , Zirconium hydroxide,
Hydrated inorganic, such as hydrated aluminum silicate, hydrated magnesium silicate, basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium hydroxide, hydrate of tin oxide, hydrate of inorganic metal compounds such as borax Fillers are preferred,
Of these, magnesium hydroxide and aluminum hydroxide are more preferable. These inorganic fillers may be used alone or in combination.
A combination of two or more species can be used.

As other inorganic fillers, calcium carbonate, diatomaceous earth, synthetic silica, glass beads, glass balloons, glass flakes, calcium silicate, talc, mica, calcium sulfate, calcium sulfite, titanium oxide,
Potassium titanate, barium sulfate, barium carbonate, barium titanate, zinc oxide, asbestos, magnesium oxide, alumina, bentonite, zeolite, kaolin clay, iron oxide, carbon black, acetylene black, furnace black and the like can be added.

In the present invention, the surface of the inorganic filler is coated with a fatty acid such as stearic acid, oleic acid and palmitic acid or a metal salt thereof; paraffin, wax, polyethylene wax or a modified product thereof; organic borane, organic titanate. Organometallic compounds such as; and those surface-treated with a silane coupling agent or the like may be used. Further, in the present invention, in order to enhance the flame retardant effect of the inorganic filler (2), an ammonium polyphosphate flame retardant, a phosphorus flame retardant such as a phosphoric acid ester, a silicone compound, quartz glass, etc. are used as necessary. Alternatively, water glass, frit, or the like may be used as the flame retardant aid, and silicon nitride short fibers or the like may be used for preventing drip.

The blending amount of the inorganic filler (2) in the present invention is 1 with respect to 100 parts by mass of the modified block copolymer of the component (1) or the hydrogenated component of the component (1) in view of the flame retardant effect.
It is 0 parts by mass or more, and is 200 from the viewpoint of breaking strength and elongation.
It is 0 parts by mass or less, preferably 20 to 1000 parts by mass, and more preferably 25 to 500 parts by mass. In the present invention, a crosslinking agent having reactivity with the functional group moiety of component (1) can be used as component (3). The cross-linking agent of the component (3) is a cross-linking agent having a functional group reactive with the functional group of the modified block copolymer or its hydrogenated component (1), preferably a carboxyl group, an acid anhydride group, It is a crosslinking agent having a functional group selected from an isocyanate group, an epoxy group, a silanol group, and an alkoxysilane group. When the crosslinking agent (3) is used, the compounding amount is 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (1),
It is preferably 0.03 to 10 parts by mass, more preferably 0.
05 to 7 parts by mass.

When the crosslinking agent (3) is used in such a blending amount, a flame-retardant polymer composition having excellent mechanical strength can be obtained. In addition, in this invention, these crosslinking agents can be used individually by 1 type or in combination of 2 or more types. Specific examples of the cross-linking agent of the component (3) include, as the cross-linking agent having a carboxyl group, maleic acid, oxalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, carballylic acid, cyclohexanedicarboxylic acid. Acids, aliphatic carboxylic acids such as cyclopentanedicarboxylic acid, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, trimesic acid, trimellitic acid, and aromatic carboxylic acids such as pyromellitic acid. .

Examples of the crosslinking agent having an acid anhydride group include maleic anhydride, itaconic anhydride, pyromellitic dianhydride, cis-4-cyclohexane-1,2-dicarboxylic acid anhydride, 1,2,4,5- Benzenetetracarboxylic dianhydride, 5- (2,5-dioxytetrahydroxyfuryl)
Examples thereof include -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride. Examples of the crosslinking agent having an isocyanate group include toluylene diisocyanate, diphenylmethane diisocyanate, and polyfunctional aromatic isocyanate.

Examples of the cross-linking agent having an epoxy group are tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-m-xylenediamine, diglycidylaniline, ethylene glycol diglycidyl, propylene glycol diglycidyl, and diglycidyl terephthalate. Ester acrylate etc. are mentioned. Examples of the crosslinking agent having a silanol group include a hydrolyzate of an alkoxysilane compound described as a modifier used to obtain the block copolymer of the component (1). As a cross-linking agent having an alkoxysilane group, bis-
Examples include (3-triethoxysilylpropyl) -tetrasulfane, bis- (3-triethoxysilylpropyl) -disulfane, and ethoxysiloxane oligomer.

In the present invention, a particularly preferable crosslinking agent has a carboxylic acid having two or more carboxyl groups or an acid anhydride thereof, or two or more acid anhydride groups, isocyanate groups, epoxy groups, silanol groups, and alkoxysilane groups. Cross-linking agents such as maleic anhydride, pyromellitic dianhydride, 1,2,4,5-benzenetetracarboxylic dianhydride, toluylene diisocyanate, tetraglycidyl-1,3-bisaminomethylcyclohexane, bis −
(3-triethoxysilylpropyl) -tetrasulfane and the like.

In the present invention, a secondary modified block copolymer obtained by previously reacting the above component (1) with the component (3) (defined as component (5) in the present invention) is blended with the component (2). Or, it can be mixed with the component (2) and the component (4) to give a flame-retardant polymer composition. When the component (1) is reacted with the component (3) in advance, the component (3) is 0.3 to 10 mol, preferably 0.4 to 5 mol, per equivalent of the functional group bonded to the component (1). , And more preferably 0.5
~ 4 moles. Examples of the method of previously reacting the component (1) with the component (3) include a melt-kneading method described below and a method of dissolving or dispersing and mixing each component in a solvent and the like to react.

When the component (5) thus obtained is blended with the component (2) or with the component (2) and the component (4) to give a flame-retardant polymer composition, the component 100 parts by weight of the total amount of (5) and component (2), or component (5),
The component (3) may be further added in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the total amount of the components (2) and (4). In the present invention, the method of previously reacting the component (1) with the component (3) is not particularly limited,
Known methods can be used. For example, a melt kneading method using a general mixer such as a Banbury mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, a multi-screw extruder, etc., after melting or dispersing and mixing each component, heating the solvent A method of removing it is used. In the present invention, the melt-kneading method using an extruder is preferable from the viewpoint of productivity and good kneading property.

Next, in the present invention, an olefin polymer can be used as the component (4). The olefin polymer that can be used in the present invention is a crystalline olefin polymer obtained by polymerizing one or more monoolefins by either a high pressure method or a low pressure method,
Among them, polyethylene, polypropylene, polybutene-
1 is preferred. The olefin polymer may be a homopolymer or a copolymer formed by copolymerizing with another monomer.

Other copolymerizable monomers include, for example, ethylene (except when the main polymer is polyethylene), propylene (except when the main polymer is polypropylene), butene-1, (where the main polymer is Except for polybutene-1,) straight chain α-olefins such as pentene-1, hexene-1, heptene-1, octene-1;
4-methylpentene-1,2-methylpropene-1,3
-Methylpentene-1,5-methylhexene-1,4-
Examples include branched α-olefins such as methylhexene-1,4,4-dimethylpentene-1; and monomers copolymerizable with the α-olefins.

The blending amount of these copolymerizable monomer components is preferably 40 wt% or less, more preferably 20 wt%. There is no particular limitation on the form of the copolymer when these are copolymerized, and for example, any of a random type, a block type, a graft type and a mixed type thereof may be used. Particularly preferable copolymers used as the olefin polymer in the present invention include propylene-ethylene copolymer, propylene-butene-1 copolymer, butene-1-ethylene copolymer, propylene-ethylene-butene-1. Examples thereof include copolymers. These olefin polymers can be used alone or in combination of two or more.

Olefin-based polymer (4) in the present invention
The compounding amount of the component (1) with respect to 100 parts by mass is 2 parts by mass or more from the viewpoint of tensile strength and 1000 parts by mass or less from the viewpoint of tensile elongation, preferably 5 to 800 parts by mass, and more preferably 10 parts by mass. To 500 parts by mass. Further, in the flame-retardant polymer composition of the present invention, known naphthenic and paraffinic process oils and mixed oils thereof can be used as a softening agent. The addition of the softening agent lowers the viscosity of the composition and thus improves the processability. The blending amount of these softening agents is 0 to 2 with respect to 100 parts by mass of the component (1) from the viewpoint of mechanical strength and thermal stability of the composition.
The range of 00 parts by mass, preferably 0 to 100 parts by mass is preferred. If necessary, stabilizers such as antioxidants and light stabilizers may be added to the flame-retardant polymer composition of the present invention.

As the antioxidant, for example, 2,6-di-
t-Butyl-4-methylphenol, n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-t-butylphenyl) propionate, 2,2'-methylenebis (4-methyl-6-t) -Butylphenol), 2,2 '
-Methylenebis (4-ethyl-6-t-butylphenol), 2,4-bis [(octylthio) methyl] -0-
Cresol, 2-t-butyl-6- (3-t-butyl-
2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6-
[1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate, 2- [1- (2
-Hydroxy-3,5-di-tert-pentylphenyl)] acrylate and the like hindered phenolic antioxidants; dilauryl thiodipropionate, lauryl stearyl thiodipropionate pentaerythritol-tetrakis (β-lauryl thiopropio) And sulfur-based antioxidants such as tris (nonylphenyl) phosphite and tris (2,4-di-t-butylphenyl) phosphite. Examples of the light stabilizer include 2- (2'-
Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-di-t- Examples thereof include benzotriazole-based UV absorbers such as butylphenyl) -5-chlorobenzotriazole, benzophenone-based UV absorbers such as 2-hydroxy-4-methoxybenzophenone, and hindered amine-based light stabilizers.

In addition to the above-mentioned stabilizers, the flame-retardant polymer composition used in the present invention may optionally contain antibacterial and antifungal agents; dispersants; foaming agents; foaming aids; red iron oxide, titanium dioxide, carbon. Colorants such as black; metal powders such as ferrite;
Inorganic fibers such as glass fibers and metal fibers; organic fibers such as carbon fibers and aramid fibers; composite fibers, inorganic whiskers such as potassium titanate whiskers; filling of pumice, cotton, cork powder, fluororesin, polymer beads, cellulose powder, etc. Agents or mixtures thereof; waxes such as paraffin wax, microcrystalline wax, low molecular weight polyethylene wax, etc .; amorphous polyolefins, polyolefin-based thermoplastics such as ethylene-ethyl acrylate copolymer or low-molecular weight vinyl aromatic thermoplastics is there.

Natural rubber; polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber, chloroprene rubber, acrylic rubber, isoprene-isobutylene rubber, polypentenamer rubber, and styrene-isoprene rubber other than the present invention. A synthetic rubber such as a block copolymer may be added. Other,
Examples thereof include those described in “Rubber / Plastic Blended Chemicals” (edited by Rubber Digest).

The method for producing the flame-retardant polymer composition of the present invention is not particularly limited, and known methods can be used. For example, various kneaders such as various extruders, Banbury mixers, kneaders, rolls, and the like, a method of melt-kneading with a kneader combining them, a method of dry blending with an injection molding machine, and the like can be given. In order to produce the composition of the present invention, each component may be mixed at once, or any component may be premixed in advance and then the remaining components may be mixed. The flame-retardant polymer composition of the present invention,
Conventionally known methods, for example, extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding,
Vacuum molding, rotational molding, powder slush molding, foam molding, laminate molding, calender molding, blow molding and the like can be processed into practically useful molded products. Further, if necessary, processing such as foaming, powder, stretching, adhesion, printing, painting, and plating may be performed.

[0064]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. In the following examples, the properties of the block copolymer and its hydrogenated product were measured as follows. (1) Styrene content Using an ultraviolet spectrophotometer (Hitachi UV200), 262
It was calculated from the absorption intensity at nm.

(2) Vinyl bond amount and hydrogenation rate Nuclear magnetic resonance apparatus (BRPX, DPX-400)
Was measured using. (3) Molecular weight GPC (apparatus: Shimadzu LC10, column: Shimadzu Shimpac GPC805 + GPC80)
4 + GPC804 + GPC803). Tetrahydrofuran is used as the solvent, and the measurement condition is a temperature of 35 ° C.
I went there. The molecular weight is a weight average molecular weight obtained by using a calibration curve (prepared by using the peak molecular weight of standard polystyrene) obtained by measuring the standard polystyrene of the chromatogram.

(4) Ratio of unmodified block copolymer A sample containing a modified block copolymer and a low molecular weight internal standard polystyrene by applying the characteristic that the modified component is adsorbed on a GPC column having silica gel as a packing material. For the solution,
The ratio of the modified block copolymer to the standard polystyrene in the chromatogram measured in the above (3), and the modified block copolymer weight to the standard polystyrene in the chromatogram measured by the silica-based column GPC [equipment is manufactured by DuPont: Zorbax]. The ratios of coalescence were compared, and the amount adsorbed on the silica column was measured from the difference between them. The ratio of the unmodified block copolymer is the ratio of those that were not adsorbed on the silica column.

Various performances of the flame-retardant polymer composition were measured by the following methods. (1) Tensile property According to JIS K7210, the breaking strength and breaking elongation of the sample were measured. (2) Oxygen index (O.I.) The oxygen index was measured according to JIS K7201, and
Evaluation was made in three levels of Δ and X. ○: 28% or more △: 24% or more and less than 28% ×: less than 24% Oxygen index is the minimum in a mixed gas of oxygen and nitrogen required for the material to sustain combustion under predetermined test conditions. It is a numerical value of oxygen concentration, and the larger the numerical value, the better the flame retardancy.

The hydrogenation catalyst used in the hydrogenation reaction was prepared by the following method. 1) Hydrogenation catalyst I 1 liter of dried and purified cyclohexane was charged into a reaction vessel purged with nitrogen, 100 mmol of bis (η5-cyclopentadienyl) titanium dichloride was added, and 200 mmol of trimethylaluminum was added with sufficient stirring. An n-hexane solution was added and reacted at room temperature for about 3 days.

2) Hydrogenation catalyst II 2 liters of dried and purified cyclohexane was charged into a reaction vessel purged with nitrogen, and 40 mmol of bis (η5-cyclopentadienyl) titanium di- (p-tolyl) and a molecular weight of about 1, Of 1,2-polybutadiene (1,2-
After dissolving 150 grams of vinyl bond (about 85%), n
A cyclohexane solution containing 60 mmol of -butyllithium was added, and the mixture was reacted at room temperature for 5 minutes. Immediately, 40 mmol of n-butanol was added and stirred, and the mixture was stored at room temperature.

In the following examples, the following components were used as each component. (1) Block Copolymer The characteristics of the block copolymer used in the present invention or a hydrogenated product thereof (hereinafter referred to as a block copolymer) are shown in Table 1. (2) Inorganic flame retardant X-1: Magnesium hydroxide surface-treated with higher fatty acid (Kyowa Chemical Co., Ltd., trade name: Kisuma 5A) X-2: Untreated magnesium hydroxide (Kyowa Chemical Co., Ltd.)
(Product name: Kisuma 5) (3) Crosslinking agent D-1: Maleic anhydride D-2: Tetraglycidyl-1,3-bisaminomethylcyclohexane (4) Olefin polymer polypropylene (PM801A manufactured by Montel SDK)

[0071]

[Example 1] An autoclave equipped with a stirrer and a jacket
Styrene 1 which had been purified, pre-purified by washing, drying, and purging with nitrogen
Cyclohexane solution containing 5 parts by mass (concentration 20 wt%)
Was thrown in. Then, n-butyllithium and tetramethylethylenediamine were added and polymerized at 70 ° C. for 30 minutes, then a cyclohexane solution (concentration 20 wt%) containing 71 parts by mass of previously purified butadiene was added and polymerized at 70 ° C. for 1 hour, and further. A cyclohexane solution containing 14 parts by mass of styrene was added and polymerized at 70 ° C. for 30 minutes. Then, 1,3-dimethyl-2-imidazolidinone (hereinafter, modifier M1) as a modifier was reacted with the n-butyllithium used for the polymerization in equimolar amounts. The obtained block copolymer had a styrene content of 29 wt% and a polybutadiene portion vinyl bond content of 42%.

To the block copolymer obtained above, 100 ppm of hydrogenation catalyst I was added as Ti, and the hydrogen pressure was adjusted to 0.7.
The hydrogenation reaction was carried out for 1 hour at MPa and a temperature of 65 ° C. After that, methanol was added, and then octadecyl-
0.3 parts by mass of 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer. The properties of the obtained block copolymer (hereinafter referred to as block copolymer A) are shown in Table 1.
The ratio of the unmodified block copolymer mixed in the block copolymer A was 20 wt%. With respect to 100 parts by mass of the block copolymer A, X-1 as an inorganic flame retardant
300 parts by mass, 0.5 part by mass of D-1 as a crosslinking agent,
100 parts by weight of polypropylene and 2- as a stabilizer
t-amyl-6- [1- (3,5-di-t-amyl-2
-Hydroxyphenyl) ethyl] -4-t-aminophenyl acrylate was added in an amount of 0.3 part by mass, and 30 mmφ
Melt kneading at 220 ° C with an axial extruder to pelletize,
A test piece for physical property evaluation was produced by injection molding. The physical property evaluation results are shown in Table 2.

[0073]

Example 2 A composition was obtained in the same manner as in Example 1 except that 100 parts by mass of the inorganic flame retardant X-1 was used. The evaluation results of physical properties of the obtained composition are shown in Table 2.

[0074]

Example 3 A composition was obtained in the same manner as in Example 1 except that the inorganic flame retardant X-1 was changed to 600 parts by mass. The evaluation results of physical properties of the obtained composition are shown in Table 2.

[0075]

Example 4 A composition was obtained in the same manner as in Example 1 except that the crosslinking agent was not used. The evaluation results of physical properties of the obtained composition are shown in Table 2.

[0076]

[Comparative Example 1] A composition was obtained in the same manner as in Example 1 except that 5 parts by weight of the inorganic flame retardant X-1 was used. The evaluation results of physical properties of the obtained composition are shown in Table 2.

[0077]

Comparative Example 2 A block copolymer B was prepared in the same manner as the block copolymer A except that no modifier was added.
The block copolymer B had a styrene content of 29 wt% and a vinyl bond content of 42% in the polybutadiene portion before the hydrogenation reaction. A composition was obtained by using the block copolymer B in the same manner as in Example 1. The evaluation results of physical properties of the obtained composition are shown in Table 2.

[0078]

Example 5 A composition was obtained in the same manner as in Example 2 except that the crosslinking agent D-1 was 2.0 parts by mass. The evaluation results of physical properties of the obtained composition are shown in Table 2.

[0079]

Example 6 A block copolymer C was prepared in the same manner as the block copolymer A except that the hydrogenation rate was 80%. The block copolymer C has a styrene content of 29 wt.
%, The vinyl bond content of the polybutadiene portion before the hydrogenation reaction is 4
It was 2%. The ratio of the unmodified block copolymer mixed in the block copolymer C was 25 wt%.
With respect to 100 parts by mass of the block copolymer A, 300 parts by mass of X-2 as an inorganic flame retardant, 4.0 parts by mass of D-2 as a crosslinking agent, 100 parts by mass of polypropylene, and 2-t- as a stabilizer. Amyl-6- [1- (3,5-di-
t-amyl-2-hydroxyphenyl) ethyl] -4-
0.3 part by mass of t-aminophenyl acrylate was blended, melt-kneaded at 220 ° C. with a 30 mmφ biaxial extruder to pelletize, and a test piece for physical property evaluation was prepared by injection molding. The physical property evaluation results are shown in Table 2.

[0080]

[Example 7] Styrene 1 which had been preliminarily purified by washing, drying, and purging with nitrogen in an autoclave equipped with a stirrer and jacket
Cyclohexane solution containing 0 parts by mass (concentration 20 wt%)
Was thrown in. Then, n-butyllithium and tetramethylethylenediamine were added and polymerized at 70 ° C. for 30 minutes, then a cyclohexane solution containing 81 parts by mass of previously purified butadiene (concentration 20 wt%) was added and polymerized at 70 ° C. for 1 hour. A cyclohexane solution containing 9 parts by mass of styrene was added and polymerized at 70 ° C. for 30 minutes. Then, tetraglycidyl-1,3-bisaminomethylcyclohexane (hereinafter, modifier M2) as a modifier was reacted in a molar amount of 0.25 times with respect to n-butyllithium used for the polymerization. The block copolymer obtained had a styrene content of 19
The vinyl bond content in the polybutadiene part was 36% by weight.

To the block copolymer obtained above, 100 ppm of hydrogenation catalyst II as Ti was added, and the hydrogen pressure was adjusted to 0.
The hydrogenation reaction was carried out for 1 hour at 7 MPa and a temperature of 65 ° C. After that, methanol was added, and then 0.3 parts by mass of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate as a stabilizer was added to 100 parts by mass of the block copolymer. . The properties of the obtained block copolymer (hereinafter referred to as block copolymer D) are shown in Table 1. The ratio of the unmodified block copolymer mixed in the block copolymer D was 30 wt%. As the inorganic flame retardant, X- was added to 100 parts by mass of the block copolymer D.
1 is 300 parts by mass, D-3 is 1.0 part by mass as a crosslinking agent, polypropylene is 100 parts by mass, and 2-t-amyl-6- [1- (3,5-di-t-amyl) as a stabilizer. 2-Hydroxyphenyl) ethyl] -4-t-aminophenyl acrylate was added in an amount of 0.3 part by mass, and 30 mm
A test piece for physical property evaluation was produced by melt-kneading and pelletizing at 220 ° C. with a φ2 screw extruder and injection molding. The physical property evaluation results are shown in Table 2.

[0082]

Example 8 An autoclave equipped with a stirrer and a jacket was washed, dried, purged with nitrogen, and pre-purified styrene 2
Cyclohexane solution containing 2 parts by mass (concentration 20 wt%)
Was thrown in. Then, n-butyllithium and tetramethylethylenediamine were added and polymerized at 70 ° C. for 30 minutes, then a cyclohexane solution (concentration 20 wt%) containing 60 parts by mass of previously purified butadiene was added and polymerized at 70 ° C. for 1 hour. A cyclohexane solution containing 18 parts by mass of styrene was added and polymerized at 70 ° C. for 30 minutes. Then, γ-glycidoxypropyltrimethoxysilane (hereinafter, modifier M3) was used as a modifier in equimolar reaction with n-butyllithium used for the polymerization. The obtained block copolymer had a styrene content of 40 wt% and a vinyl bond content of 28% in the polybutadiene portion.

To the block copolymer obtained above, 100 ppm of hydrogenation catalyst I was added as Ti, and the hydrogen pressure was adjusted to 0.7.
The hydrogenation reaction was carried out for 1 hour at MPa and a temperature of 65 ° C. After that, methanol was added, and then octadecyl-
0.3 parts by mass of 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate was added to 100 parts by mass of the block copolymer. The properties of the obtained block copolymer (hereinafter referred to as block copolymer E) are shown in Table 1.
The ratio of the unmodified block copolymer mixed in the block copolymer E was 25 wt%. With respect to 100 parts by mass of the block copolymer E, 300 parts by mass of X-2 as an inorganic flame retardant, 2.5 parts by mass of D-3 as a crosslinking agent, 50 parts by mass of polypropylene, and 2-t- as a stabilizer.
0.3 parts by mass of amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] -4-t-aminophenyl acrylate was blended, and the mixture was heated at 220 ° C. with a 30 mmφ twin-screw extruder. Melt kneading, pelletizing, and injection molding were used to prepare test pieces for physical property evaluation. The physical property evaluation results are shown in Table 2.

[0084]

Comparative Example 3 A block copolymer having no functional group was prepared in the same manner as the block copolymer E, except that SiCl4 was used as a coupling agent in a 1/4 mol reaction with respect to n-butyllithium used for the polymerization. I got F. The block copolymer F had a styrene content of 40 wt% and a vinyl bond content of 28% in the polybutadiene portion before the hydrogenation reaction. A composition was obtained by using the block copolymer F in the same manner as in Example 8. The evaluation results of physical properties of the obtained composition are shown in Table 2.

[0085]

Example 9 In the block copolymer A, 2.1 mol of the crosslinking agent D was added per equivalent of the functional group bonded to the block copolymer.
1 was blended and melt-kneaded with a 30 mmφ twin-screw extruder at 230 ° C. and a screw rotation speed of 100 rpm to obtain a secondary modified block copolymer of the block copolymer A (secondary modified block copolymer a). . Table 3 shows the composition of the secondary modified block copolymer a. Secondary modified block copolymer a100
300 parts by weight of X-1 as an inorganic flame retardant, 100 parts by weight of polypropylene, and 2-t-amyl-6- [1- (3,5-di-t-amyl- 2-Hydroxyphenyl) ethyl] -4-t-aminophenyl acrylate was mixed in an amount of 0.3 part by mass, and 30 mm
A test piece for physical property evaluation was produced by melt-kneading and pelletizing at 220 ° C. with a φ2 screw extruder and injection molding. The physical property evaluation results are shown in Table 4.

[0086]

Comparative Example 4 Block copolymer B was mixed with 2.1 times the mole of crosslinking agent D1 with respect to the block copolymer, and
mmφ twin-screw extruder 230 ℃, screw rotation speed 100
The mixture was melt-kneaded at rpm to obtain a cross-linking agent-containing block copolymer (cross-linking agent-containing block copolymer d). The composition of the cross-linking agent-containing block copolymer d is shown in Table 3. A composition was obtained in the same manner as in Example 9 using the cross-linking agent-containing block copolymer d. Table 4 shows the evaluation results of physical properties of the obtained composition.

[0087]

Example 10 The block copolymer D was mixed with 0.9 mol of the cross-linking agent D2 per equivalent of the functional group bonded to the block copolymer, and the mixture was heated at 230 ° C. in a 30 mmφ twin screw extruder at a screw rotation speed. The mixture was melt-kneaded at 100 rpm to obtain a secondary modified block copolymer of the block copolymer D (secondary modified block copolymer b). Table 3 shows the composition of the secondary modified block copolymer b. Secondary modified block copolymer b10
To 0 parts by mass, 300 parts by mass of X-1 as an inorganic flame retardant, 100 parts by mass of polypropylene, and 2-t-amyl-6- [1- (3,5-di-t-amyl) as a stabilizer. 2-hydroxyphenyl) ethyl] -4-t-aminophenyl acrylate was added in an amount of 0.3 part by mass, and 30 m
A test piece for measuring physical properties was prepared by melt-kneading and pelletizing at 230 ° C. with an mφ twin-screw extruder and injection molding.
The physical property evaluation results are shown in Table 4.

[0088]

Example 11 50 parts by mass of block copolymer A, 50 parts by mass of block copolymer D, and block copolymer A
And a total amount of functional groups bonded to the block copolymer D, 3.5 mol of the cross-linking agent D2 per 1 equivalent is mixed, and 30 mmφ
230 ° C with a twin-screw extruder, screw rotation speed 100 rpm
Then, the mixture was melt-kneaded to obtain a secondary modified block copolymer (secondary modified block copolymer c). Table 3 shows the composition of the secondary modified block copolymer c. Secondary modified block copolymer c
30 parts of X-1 as an inorganic flame retardant with respect to 100 parts by mass.
0 parts by mass, 100 parts by mass of polypropylene, and 2-t-amyl-6- [1- (3,5-di-t- as a stabilizer.
Amyl-2-hydroxyphenyl) ethyl] -4-t-
Add 0.3 parts by weight of aminophenyl acrylate and mix 3
A 0 mmφ twin-screw extruder was used to melt-knead at 220 ° C. to form pellets, and injection molding was performed to prepare test pieces for measuring physical properties. The physical property evaluation results are shown in Table 4. From the results of Examples 1 to 11 and Comparative Examples 1 to 4, it can be seen that the flame-retardant polymer composition of the present invention is excellent in flame retardancy and is excellent in balance of mechanical properties.

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

[Table 4]

[0093]

The flame-retardant polymer composition of the present invention is excellent in flame retardancy, does not generate toxic gas such as halogen gas even when burned, and is excellent in balance of mechanical properties. It is suitable for applications such as in-device wiring, wire coating materials for automobile harnesses, and industrial materials such as insulating tape.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 BB00X BB02X BB11X BB17X                       BP01W DE066 DE076 DE086                       DE096 DE146 DE236 DE286                       DJ006 DK006 EF067 EF077                       EF117 EF127 EL027 EL137                       EL147 EN037 EN067 ER007                       EX047 FD016 FD147 GM00                       GN00 GQ00 GQ01                 4J100 AB00P AB02P AB03P AB04P                       AS01Q AS02Q AS03Q AS04Q                       BA03H BA03Q BA29H BA29Q                       BA71H BA77H BA77Q BA78H                       BA78Q BC54H BC54Q CA04                       CA31 HA61 HA62 HC47 HC57                       HC63 HC78 HC80 HC83 HG03

Claims (9)

[Claims] 1. At least one polymer block H containing a vinyl aromatic hydrocarbon as a main component and at least one polymer block S mainly containing a conjugated diene, which are obtained by using an organolithium compound as a polymerization catalyst. Modified block copolymer obtained by addition reaction of a functional group-containing modifier to the living terminal of the block copolymer, or hydrogenated component (1) 10 thereof
A flame-retardant polymer composition comprising 0 parts by mass and 10 to 2000 parts by mass of the inorganic filler (2). 2. A polymer block H containing an organolithium compound as a polymerization catalyst and containing vinyl aromatic hydrocarbon as a main component and at least one polymer block S containing a conjugated diene as a main component. Modified block copolymer obtained by addition reaction of a functional group-containing modifier to the living terminal of the block copolymer, or hydrogenated component (1) 10 thereof
Flame retardancy comprising 0 parts by mass, 10 to 2000 parts by mass of the inorganic filler (2), and 0.01 to 20 parts by mass of the crosslinking agent (3) having reactivity with the functional group part of the component (1). Polymer composition. 3. At least one polymer block H containing a vinyl aromatic hydrocarbon as a main component and at least one polymer block S mainly containing a conjugated diene, which are obtained by using an organolithium compound as a polymerization catalyst. Modified block copolymer obtained by addition reaction of a functional group-containing modifier to the living terminal of the block copolymer, or hydrogenated component (1) 10 thereof
0 parts by mass, 10 to 2000 parts by mass of the inorganic filler (2), and a cross-linking agent (3) having reactivity with the functional group part of the component (1).
A flame-retardant polymer composition comprising 0.01 to 20 parts by mass and olefin polymer (4) 2 to 1000 parts by mass. 4. At least one polymer block H containing a vinyl aromatic hydrocarbon as a main component and at least one polymer block S mainly containing a conjugated diene, which are obtained by using an organolithium compound as a polymerization catalyst. A cross-linking agent (3) having reactivity with a functional group of a modified block copolymer or a hydrogenated product component (1) thereof obtained by adding a functional group-containing modifier to the living end of the block copolymer is added to the functional group. 100 parts by mass of the secondary modified block copolymer (5) reacted with 0.3 to 10 mol per equivalent, and the inorganic filler (2) 1
A flame-retardant polymer composition comprising 0 to 2000 parts by mass. 5. At least one polymer block H containing a vinyl aromatic hydrocarbon as a main component and at least one polymer block S mainly containing a conjugated diene, which are obtained by using an organolithium compound as a polymerization catalyst. A cross-linking agent (3) having reactivity with a functional group of a modified block copolymer or a hydrogenated product component (1) thereof obtained by adding a functional group-containing modifier to the living end of the block copolymer is added to the functional group. 100 parts by mass of secondary modified block copolymer (5) reacted with 0.3 to 10 mol per equivalent, and inorganic filler (2) 10 to 20
00 parts by mass and olefin polymer (4) 2 to 10
A flame-retardant polymer composition containing 100 parts by mass. 6. A functional group-containing modifier is a functional group selected from a hydroxyl group, an epoxy group, an amino group, a silanol group, and an alkoxysilane group in the block copolymer by an addition reaction with the living terminal of the block copolymer. A flame-retardant polymer composition according to any one of claims 1 to 5, which is a modified block copolymer having at least one atomic group bonded thereto or a modifier having a functional group that forms a hydrogenated product thereof. object. 7. The cross-linking agent (3) is a cross-linking agent having a functional group selected from a carboxyl group, an acid anhydride group, an isocyanate group, an epoxy group, a silanol group and an alkoxysilane group. A flame-retardant polymer composition as described in 1. 8. The modified block copolymer or its hydrogenated component (1) is bound to at least one atomic group having at least one functional group selected from the following formulas (1) to (14). The flame-retardant polymer composition according to any one of claims 1 to 7, which is a modified block copolymer or a hydrogenated product thereof. [Chemical 1] (In the above formula, R ^{1 to} R ⁴ are hydrogen, a hydrocarbon group having 1 to 24 carbon atoms, a hydroxyl group, an epoxy group, a silanol group,
A hydrocarbon group having 1 to 24 carbon atoms having a functional group selected from alkoxysilane groups. R ⁵ is a hydrocarbon chain having 1 to 48 carbon atoms, or 1 carbon atom having a functional group selected from a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group.
~ 48 hydrocarbon chains. In the hydrocarbon groups of R ^{1 to} R ⁴ and the hydrocarbon chain of R ⁵ , oxygen, in a bonding mode other than a hydroxyl group, an epoxy group, a silanol group and an alkoxysilane group,
Elements such as nitrogen and silicon may be bonded. R ⁶ is hydrogen or an alkyl group having 1 to 8 carbon atoms) 9. The flame-retardant polymer composition according to claim 1, wherein the inorganic filler (2) is a hydrated inorganic filler.