JPH07224192A - Polymer composition - Google Patents

Abstract

PURPOSE:To obtain a polymer composition having excellent impact resistance, flame-retardancy, abrasion resistance, oil resistance and chemical resistance and useful as an industrial material by adding a specific hydrogenated block copolymer, a phosphorus-based flame retardant and a silicone polymer to a composition containing a polyolefin and a polyphenylene ether. CONSTITUTION:This polymer composition is composed of (A) a polyolefin, (B) a polyphenylene ether, (C) a hydrogenated block copolymer of a vinyl aromatic compound and a conjugated diene (containing >45wt.% and <=95wt.% of bonded vinyl aromatic compound), (D) a hydrogenated block copolymer of a vinyl aromatic compound and a conjugated diene (containing 5-45wt.% of bonded vinyl aromatic compound), (E) phosphorus or a phosphorus compound and (F) a silicone polymer. The average amount of the bonded vinyl aromatic compound in the hydrogenated block copolymer is 20-65wt.% and the weight ratios of the components satisfy the formulas A/B=5/95 to 95/5, (A+B)/(C+D)=100/(1-100), (A+B+C+D)/E=100/(l-40) and (A+B+C+D+E)/F =100/(0.01-10).

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is excellent in oil resistance, chemical resistance, impact resistance, flame retardancy and abrasion resistance, and is a resin form which can be used in the fields of electric and electronic fields, automobile fields and various other industrial material fields. ~ It relates to an elastomeric polymer composition.

[0002]

2. Description of the Related Art Polyphenylene ether has a mechanical property, an electrical property, a heat resistance, a low temperature property, a low water absorption property and excellent dimensional stability, but has a drawback that it is inferior in moldability and impact resistance. By blending with high-impact polystyrene, these problems are improved, and it is widely used as a resin composition for, for example, electric / electronic parts, office equipment housings, automobile parts, precision parts, and various industrial parts. However, the classical polyphenylene ether resin composition composed of this polyphenylene ether and high-impact polystyrene (disclosed in U.S. Pat. No. 3,383,435) has improved impact resistance, but has poor chemical resistance. have.

For this reason, for example, US Pat.
In the specification of Japanese Laid-Open Patent Publication No. 51, it is proposed to blend polyphenylene ether with polyolefin to improve solvent resistance and impact resistance. US Pat. No. 3,994,485.
No. 6 describes improvement in impact resistance and solvent resistance by blending polyphenylene ether or polyphenylene ether and styrene resin with a hydrogenated block copolymer, and US Pat. No. 4,145,377.
In the specification, a polyphenylene ether or a polyphenylene ether and a styrene resin are used as a polyolefin / hydrogenated block copolymer = 20 to 80 parts by weight / 80 to 2
There is a description on improvement of impact resistance and solvent resistance by blending with 0 parts by weight of a premixture and a hydrogenated block copolymer, and further, there is a description about US Pat. No. 4,166,055.
U.S. Pat. No. 4,239,673 and U.S. Pat. No. 4,239,673 describe improving impact resistance by blending polyphenylene ether with hydrogenated block copolymers and polyolefins. And US Pat. No. 43830
82 and European Published Patent No. 115712.
In the specification, impact resistance is improved by blending polyphenylene ether with polyolefin and hydrogenated block copolymer.

Further, in JP-A-63-113058, JP-A-63-225642 and US Pat. No. 4,863,997, a specific water is used for modifying a resin composition composed of a polyolefin resin and a polyphenylene ether resin. There has been proposed a resin composition containing an additional block copolymer and having excellent chemical resistance and processability. In addition, the applicant of the present invention has filed Japanese Patent Application Laid-Open Nos. 62-20551 and 62-2.
5149, JP-A-62-48757, JP-A-62-48758, JP-A-62-199637.
U.S. Pat. No. 4,772,657 and U.S. Pat. No. 4,772,657 propose a rubber composition comprising a polyphenylene ether, a polyolefin and a hydrogenated block copolymer, which is excellent in rubber elasticity. And compatibility with a specific hydrogenated block copolymer, excellent in rigidity and heat resistance,
A resin composition having excellent solvent resistance was proposed.

[0005]

However, the prior art disclosed herein provides a resin composition having dramatically improved solvent resistance as compared with a classical polyphenylene ether resin composition, and has a high heat resistance. Although it provides a composition of a rubber-like elastic material having excellent properties, especially in a composition containing a large amount of a polyolefin component, the compatibility between the polyphenylene ether and the polyolefin is insufficient and the delamination phenomenon occurs remarkably at present. . Therefore, although it was possible to simultaneously improve the impact resistance, flame retardancy, and wear resistance to a certain level, it was not at a sufficient level.

[0006]

In view of the above situation, the present inventors have proposed a hydrogenated block co-polymer used as an admixture in order to impart a high level of miscibility to a composition containing polyolefin and polyphenylene ether. As a result of repeated intensive studies on the combination (hydrogenated product of vinyl aromatic compound-conjugated diene compound block copolymer), at least one kind of hydrogenated block copolymers in two specific ranges is selected from within each specific range. The hydrogenated block copolymer is selected from at least two types of hydrogenated block copolymers, and the average amount of bound vinyl aromatic compounds in all the selected hydrogenated block copolymers is limited to a specific range. By using a block copolymer, the miscibility of a composition containing a polyolefin and a polyphenylene ether is improved, and phosphorus and a phosphorus compound system are further added. Using a flame retardant, and further, the combined use of silicone polymers, impact resistance, flame retardancy,
It has been found that it provides a resin composition having excellent wear resistance, oil resistance, and chemical resistance, and a rubber-like elastic material composition having excellent heat resistance.

That is, according to the present invention, the amount of (a) polyolefin (b) polyphenylene ether (c) bound vinyl aromatic compound exceeds 45% by weight.
95% by weight of at least one hydrogenated product of vinyl aromatic compound-conjugated diene compound block copolymer (d) vinyl aromatic compound-conjugated diene compound having an amount of bonded vinyl aromatic compound of 5% by weight to 45% by weight At least one hydrogenated product of the block copolymer is composed of (e) phosphorus and a phosphorus compound (f) silicon polymer, and with respect to the total amount of the components (a) and (b),
The component (a) is 5 to 95% by weight, the component (b) is 95 to 5% by weight, and the component (c) and the component (d) are based on 100 parts by weight of the total amount of the components (a) and (b). The total amount of 1-100
Wt% and

[0008]

[Equation 2]

To 100 parts by weight of the total amount of the components (a) to (d), 1 to 40 parts by weight of the component (e) is added to 100 parts by weight of the total amount of the components (a) to (e).
The polymer composition is characterized in that the component (f) is 0.01 to 10 parts by weight. The polyolefin used as the component (a) in the present invention is a polyolefin having a weight average molecular weight of 30,000 or more, which is used as a general molding material, and examples thereof include isotactic polypropylene, ultrahigh molecular weight isotactic polypropylene, and poly (4-methyl). -1-Pentene), polybutene-1, high density polyethylene, ultra high molecular weight high density polyethylene, low density polyethylene, linear low density polyethylene,
Ultra low density polyethylene having a density of less than 0.90, a copolymer of two or more compounds selected from ethylene, propylene, other α-olefins, unsaturated carboxylic acids or their derivatives, for example, ethylene / 1-butene. Copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer, propylene / ethylene (random, block) copolymer, propylene / 1-
Examples include hexene copolymers and propylene / 4-methyl-1-pentene copolymers. These polyolefins may be used alone or in combination of two or more. Among these polyolefins, isotactic polypropylene, propylene / ethylene block copolymer, propylene / ethylene random copolymer and polyethylene are preferable, and polyethylene is most preferable.

The polyolefin used in the present invention is
In addition to the above-mentioned polyolefin, the polyolefin and α, β-unsaturated carboxylic acid or a derivative thereof in a molten state or in a solution state in the presence or absence of a radical generator are used in the presence of a radical generator.
It may be a known modified (0.01 to 10% by weight of the α, β-unsaturated carboxylic acid or its derivative is grafted or added) polyolefin obtained by reacting at a temperature of 0 to 350 ° C., and It may be a mixture of the above-mentioned polyolefin and the modified polyolefin in an arbitrary ratio.

The polyphenylene ether (b), which is the component (b) used in the present invention, is an essential component for imparting heat resistance and flame retardancy to the polymer composition of the present invention. The PPE has a binding unit:

[0012]

[Chemical 1]

(Where R1, R2, R3, and R4
Are hydrogen, halogen, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, or at least two carbon atoms each being a halogen atom. Selected from the group consisting of halohydrocarbonoxy groups separating an oxygen atom, which may be the same or different.
A homopolymer having a reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) of preferably 0.15 to 0.70, more preferably 0.20 to 0.60. And / or a copolymer.

Specific examples of this PPE include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly ( 2-methyl-6-phenyl-
1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like, and further 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethyl). Also included are polyphenylene ether copolymers such as copolymers with phenol and 2-methyl-6-butylphenol). Among them, poly (2,6-dimethyl-1,4-phenylene ether),
A copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-diphenylphenol)
6-dimethyl-1,4-phenylene ether) is preferred.

The method for producing such PPE is not particularly limited as long as it can be obtained by a known method. For example, a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 is used as a catalyst. Can be easily prepared by oxidative polymerization of 2,6-xylenol, for example, and US Pat. No. 3,306,875.
No. 3,257,357 and No. 3257358.
No. 5, Japanese Patent Publication No. 52-18880 and Japanese Patent Laid-Open No. 50-51.
It can be easily produced by the method described in No. 197 and No. 63-152628.

The PPE used in the present invention is, in addition to the above-mentioned PPE, the PPE and the α, β-unsaturated carboxylic acid or its derivative in a molten state or in a solution in the presence or absence of a radical generator. 80 to 350 in the state and slurry state
It may be a known modified (0.01 to 10% by weight of the α, β-unsaturated carboxylic acid or its derivative is grafted or added) PPE obtained by reacting at a temperature of ° C, and the above-mentioned PPE. It may be a mixture of the modified PPE and the modified PPE in any ratio.

And further, 9,10-dihydro-9-
Oxa-10-phosphaphenanthrene was added to PPE10.
The phosphorus compound-treated PPE obtained by adding 0.2 to 5 parts by weight to 0 parts by weight and melt-kneading the PP was also excellent in color tone and fluidity.
It can be used as E. Further, P used in the present invention
As the PE, in addition to the above PPE, polystyrene or high-impact polystyrene added to 100 parts by weight of these PPE in an amount not exceeding 100 parts by weight can be preferably used.

Next, the hydrogenated product of the vinyl aromatic compound-conjugated diene compound (hereinafter abbreviated as hydrogenated block copolymer) used as the component (c) in the present invention comprises at least one vinyl aromatic compound. A hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polymer block A containing a main component and a polymer block B containing at least one conjugated diene compound as a main component, such as AB,
A-B-A, B-A-B-A, (A-B-) _4- Si,
It is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as ABA-BAA. The hydrogenated block copolymer as the component (c) contains more than 45% by weight to 95% by weight, preferably 50 to 80% by weight of the vinyl aromatic compound bonded to the block copolymer before hydrogenation. Also, referring to the block structure, a polymer block A containing a vinyl aromatic compound as a main component
Is a vinyl aromatic compound homopolymer block, or
More than 50% by weight of vinyl aromatic compound, preferably 70
It has a structure of a copolymer block of a vinyl aromatic compound and a conjugated diene compound, which is contained by weight% or more, and the polymer block mainly containing the conjugated diene compound is a homopolymer block of the conjugated diene compound. Alternatively, it has a structure of a copolymer block of a conjugated diene compound containing more than 50% by weight, preferably 70% by weight or more of a conjugated diene compound and a vinyl aromatic compound.

Further, the polymer block A mainly containing these vinyl aromatic compounds and the polymer block B mainly containing these conjugated diene compounds are the conjugated diene compound or vinyl aromatic compound in the molecular chain of each polymer block. The distribution of the compound may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof. When there are two or more polymer blocks mainly composed of the merged block and the conjugated diene compound, the polymer blocks may have the same structure or different structures.

The vinyl aromatic compound constituting the block copolymer is, for example, one or more of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like. It can be selected, and styrene is particularly preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3.
One or more selected from butadiene and the like, and among them, butadiene, isoprene and combinations thereof are preferable. The polymer block mainly composed of the conjugated diene compound can have a microstructure in the block arbitrarily selected. For example, in the polymer block mainly composed of butadiene, the 1,2-vinyl bond has 2 to 85%. %, Preferably 10-75%, more preferably 25-55%.

The number average molecular weight of the block copolymer having the above structure is 5,000 to 1,000,000,
It is preferably in the range of 10,000 to 800,000, more preferably 30,000 to 500,000, and has a molecular weight distribution [weight average molecular weight (Mw) measured by gel permeation chromatography and number average molecular weight (M
The ratio of n)] is 10 or less. Further, the molecular structure of this block copolymer may be linear, branched, radial, or any combination thereof.

The block copolymer having such a structure is a hydrogenated block copolymer obtained by hydrogenating the aliphatic double bond of the polymer block B containing the conjugated diene compound of the above block copolymer as a main component. (Vinyl aromatic compound-conjugated diene compound block copolymer hydrogenated product) can be used as the component (c) of the present invention. The hydrogenation rate of such aliphatic double bonds is at least over 20%, preferably 50% or more, more preferably 80% or more.

The hydrogenated block copolymer of the above-mentioned component (c) may be obtained by any production method as long as it has the above-mentioned structure.
Examples of known manufacturing methods include, for example, JP-A-47-1.
No. 1486, No. 49-66743, No. 50-75651, No. 54-126255.
JP-A-56-10542, JP-A-56-
62847, JP-A-56-100840,
British Patent No. 1130770 and US Patent No. 3281
383 and 3639517, as well as British Patent No. 1020720 and US Patent No. 333.
3024 and 4501857.

The hydrogenated block copolymer of the component (c) used in the present invention is, in addition to the above-mentioned hydrogenated block copolymer, the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid. Or a derivative thereof in the presence or absence of a radical generator in a molten state, a solution state, or a slurry state at 80 to 3
Even a known modified (copolymerized with 0.01 to 10% by weight of the α, β-unsaturated carboxylic acid or its derivative) hydrogenated block copolymer obtained by reaction at a temperature of 50 ° C. Of course, a mixture of the above-mentioned hydrogenated block copolymer and the modified hydrogenated block copolymer may be used in any ratio.

Next, the hydrogenated product of the vinyl aromatic compound-conjugated diene compound (hereinafter abbreviated as hydrogenated block copolymer) used as the component (d) in the present invention comprises at least one vinyl aromatic compound. A hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polymer block A containing a main component and a polymer block B containing at least one conjugated diene compound as a main component, such as AB,
A-B-A, B-A-B-A, (A-B-) _4- Si,
It is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as ABA-BAA. The hydrogenated block copolymer of the component (d) contains 5% by weight to 45% by weight, preferably 15% by weight, of the vinyl aromatic compound bonded to the block copolymer before hydrogenation.
40% by weight, and referring to the block structure, the polymer block A mainly composed of a vinyl aromatic compound is a homopolymer block of a vinyl aromatic compound or a vinyl aromatic compound exceeding 50% by weight, preferably 70% by weight. Having a structure of a copolymer block of a vinyl aromatic compound and a conjugated diene compound, which is contained in an amount of not less than wt%, and further,
A polymer block mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a conjugated diene compound containing more than 50% by weight, preferably 70% by weight or more of a conjugated diene compound and a vinyl aromatic compound. It has a structure of a copolymer block.

Further, the polymer block A mainly containing these vinyl aromatic compounds and the polymer block B mainly containing these conjugated diene compounds are the conjugated diene compound or vinyl aromatic compound in the molecular chain of each polymer block. The distribution of the compound may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof. When there are two or more polymer blocks mainly composed of the merged block and the conjugated diene compound, the polymer blocks may have the same structure or different structures.

The vinyl aromatic compound constituting the block copolymer is, for example, one or more of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like. It can be selected, and styrene is particularly preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3.
One or more selected from butadiene and the like, and among them, butadiene, isoprene and combinations thereof are preferable. The polymer block mainly composed of the conjugated diene compound can have a microstructure in the block arbitrarily selected. For example, in the polymer block mainly composed of butadiene, the 1,2-vinyl bond has 2 to 85%. %, Preferably 10 to 75%, more preferably 25 to 55%.

The number average molecular weight of the block copolymer having the above structure is 5,000 to 1,000,000,
It is preferably in the range of 10,000 to 800,000, more preferably 30,000 to 500,000, and has a molecular weight distribution [weight average molecular weight (Mw) measured by gel permeation chromatography and number average molecular weight (M
The ratio of n)] is 10 or less. Further, the molecular structure of this block copolymer may be linear, branched, radial, or any combination thereof.

The block copolymer having such a structure is a hydrogenated block copolymer obtained by hydrogenating the aliphatic double bond of the polymer block B mainly composed of the conjugated diene compound of the above block copolymer. (Vinyl aromatic compound-conjugated diene compound block copolymer hydrogenated product) can be used as the component (d) of the present invention. The hydrogenation rate of such aliphatic double bonds is at least over 20%, preferably 50% or more, more preferably 80% or more.

These hydrogenated block copolymers of the above-mentioned component (d) may be obtained by any production method as long as they have the above-mentioned structure.
Examples of known manufacturing methods include, for example, JP-A-47-1.
No. 1486, No. 49-66743, No. 50-75651, No. 54-126255.
JP-A-56-10542, JP-A-56-
62847, JP-A-56-100840,
British Patent No. 1130770 and US Patent No. 3281
383 and 3639517, as well as British Patent No. 1020720 and US Patent No. 333.
3024 and 4501857.

Further, the hydrogenated block copolymer of the component (d) used in the present invention includes, in addition to the above-mentioned hydrogenated block copolymer, the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid. Or a derivative thereof in the presence or absence of a radical generator in a molten state, a solution state, or a slurry state at 80 to 3
Even a known modified (copolymerized with 0.01 to 10% by weight of the α, β-unsaturated carboxylic acid or its derivative) hydrogenated block copolymer obtained by reaction at a temperature of 50 ° C. Of course, a mixture of the above-mentioned hydrogenated block copolymer and the modified hydrogenated block copolymer may be used in any ratio.

Examples of phosphorus and phosphorus compounds used as component (e) in the present invention include organic phosphorus compounds, red phosphorus, and inorganic phosphorus compounds. Examples of the organic phosphorus compound include phosphoric acid ester, phosphorous acid ester, phosphine,
Phosphine oxide, biphosphine, phosphonium salt,
Examples thereof include phosphinic acid salts.

As an example of the above-mentioned red phosphorus, in addition to general red phosphorus, the surface thereof is previously coated with a film of a metal hydroxide selected from aluminum hydroxide, magnesium hydroxide, zinc hydroxide and titanium hydroxide. Treated, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, treated with a coating consisting of a metal hydroxide selected from titanium hydroxide and a thermosetting resin, aluminum hydroxide, magnesium hydroxide, It is also possible to preferably use a metal hydroxide selected from zinc hydroxide and titanium hydroxide, which is doubly coated with a film of a thermosetting resin on a film of a metal hydroxide.

Examples of the above inorganic phosphorus compounds include inorganic phosphates represented by ammonium polyphosphate and the like. Furthermore, among the above phosphoric acid esters, an aromatic phosphoric acid ester-based flame retardant is particularly preferable.
Aromatic phosphate ester compounds obtained by reacting a monovalent, divalent or trivalent phenol compound alone or with a phosphorus halide may be obtained by any method, for example, 2,2-bis. -{4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, aromatic condensed phosphate ester , Bisphenol A polyphosphate, and similar derivatives thereof. These flame retardants may be used alone or in combination of two or more. Among these flame retardants, 2,2-bis- {4- [bis (methylphenoxy) phosphoryl] represented by the following formula is shown from the viewpoints of volatility during processing, bleed-out to the surface of molded articles and thermal stability. Luoxy] phenyl}
Propane is more preferably used.

[0035]

[Chemical 2]

Further, the silicone polymer of the component (f) used in the present invention is a polydimethylsiloxane or a part of the methyl group thereof is hydrogen, phenyl group, halogenated phenyl group, halogenated alkyl group, fluoroester group, etc.
And those substituted with two or more species.
From the viewpoint of bleed-out on the surface of molded products, the viscosity is 1
A polymer having a high molecular weight of 0,000 cSt (25 ° C.) or higher is preferable.

The polymer composition of the present invention comprises the above-mentioned components (a) to (f) as basic components, and (a)
The blending amount of the polyolefin of the component (a) is 5 to 95% by weight, preferably 35% with respect to the total amount of the component and the component (b).
Is about 75% by weight, and the amount of the polyphenylene ether as the component (b) is 95 to 5% by weight, preferably 65 to 25%.
% By weight.

The total blending amount of the hydrogenated block copolymer of the component (c) and the component (d) is 1 to 100 parts by weight based on 100 parts by weight of the total amount of the components (a) and (b). It is preferably 5 to 55 parts by weight, more preferably 15 to 55 parts by weight. Further, the blending amount of the component (e) is from the component (a) to
The total amount of the component (d) is 1 to 40 parts by weight, preferably 5 to 20 parts by weight, and the amount of the component (f) is the total of the components (a) to (e). Quantity 100
0.01 to 10 parts by weight, preferably 0.
It is 1 to 3 parts by weight.

By the way, this hydrogenated block copolymer is changed from a hard resinous hydrogenated block copolymer to a soft elastomeric hydrogenated block copolymer by changing the content ratio of the vinyl aromatic compound and the hydrogenated conjugated diene compound. It is known that it can change in a wide range to coalescence. In addition, since polyolefin and polyphenylene ether are not inherently compatible and the layer peeling cannot be practically used only by simple mixing, a hydrogenated block copolymer is used as a compatibilizer for polymerizing polyolefin and polyphenylene ether. It is known.

However, regarding the performance of these hydrogenated block copolymers as a compatibilizer, those having a large hydrogenated conjugated diene compound content have a high affinity with polyolefins, and those having a large vinyl aromatic compound content. Although there is a qualitative knowledge that the compound has a high affinity with polyphenylene ether, it is no exaggeration to say that a preferred compatibilizer for both components of polyolefin and polyphenylene ether is not within the scope of the prior art.

A feature of the present invention is that when selecting a hydrogenated block copolymer that acts as a compatibilizer for polyolefins and polyphenylene ethers, the hydrogenated block has two specific ranges of bound vinyl aromatic compound content. In the copolymer, at least one hydrogenated block copolymer is selected from the individual specific ranges, and the hydrogenated block copolymer is composed of at least two or more hydrogenated block copolymers and the whole hydrogenated block copolymer is used. Using a hydrogenated block copolymer so that the average amount of bound vinyl aromatic compound of is in a specific range,
Further, the combined use of phosphorus, a phosphorus compound, and a silicon polymer is a point that excellent flame retardancy, impact resistance, and abrasion resistance are simultaneously satisfied.

According to this method, a mixture of a hydrogenated block copolymer containing a small amount of a bound vinyl aromatic compound having a high affinity with a polyolefin and a polyolefin and a hydrogenated product containing a large amount of a bound vinyl aromatic compound having a high affinity with a polyphenylene ether. A mixture of the block copolymer and the polyphenylene ether produces a polymer alloy with higher miscibility through both hydrogenated block copolymers. That is, in the present invention, the (c) component and (d) used
The ratio of the components is the total hydrogenated block copolymer [component (c) +
The average amount (% by weight) of the bound vinyl aromatic compound of (d) component] is blended in such a proportion that the following formula is satisfied.

[0043]

[Equation 3]

Usually, in order to obtain a composition in which the polyolefin as the component (a) serves as a matrix to form a continuous phase, the average amount of bound vinyl aromatic compounds in such a fully hydrogenated block copolymer is 20 to 55% by weight. In order to obtain a composition in which the polyphenylene ether of the component (b) serves as a matrix and forms a continuous phase, the average amount of the vinyl aromatic compound bonded with the all hydrogenated block copolymer is 30
% By weight to 65% by weight. If the average amount of the bound vinyl aromatic compound in the all hydrogenated block copolymer is less than 20% by weight or exceeds 65% by weight, the compatibility between the polyolefin and the polyphenylene ether is significantly deteriorated, which is not preferable.

In the present invention, in addition to the above-mentioned components, other optional components, such as the above-mentioned non-hydrogenated block copolymer of the component (c), may be added as necessary within the range not impairing the characteristics and effects of the present invention. , (D) non-hydrogenated block copolymers, antioxidants, flame retardants other than phosphorus and phosphorus compounds (metal hydroxides, metal oxides, melamine compounds, aromatic halogen flame retardants, etc.), plastic Agents (oil, low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids, weather (light) resistance improvers, nucleating agents for polyolefins, slip agents, inorganic or organic fillers And reinforcing materials (glass fiber, carbon fiber, whiskers, mica, talc, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite, conductive metal fibers, conductive Over carbon black, etc.), various types of coloring agents,
A release agent or the like may be added.

The polymer composition of the present invention can be produced by various methods using the above-mentioned components. For example, a heat-melting and kneading method using a single-screw extruder, a twin-screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer and the like can be mentioned. Among them, the melt-kneading method using a twin-screw extruder is most preferable. The melt-kneading temperature at this time is not particularly limited, but is usually 150 to 3
It can be arbitrarily selected from 50 ° C.

The polymer composition of the present invention thus obtained becomes a resin-like to elastomer-like polymer composition, and various known methods such as injection molding,
It can be molded as a molded body of various parts by extrusion molding or hollow molding. Examples of these various parts include automobile parts.Specifically, exterior parts such as bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, and installation parts. Suitable for interior parts such as instrument panel, console box and trim. Further, it can be suitably used as an interior / exterior component of an electric device, specifically, suitable for various computer and its peripheral devices, other office automation equipment, televisions, videos, cabinets such as various disc players, parts such as refrigerators, Further, it is suitable for various gaskets, flexible tubes, hose coatings, weather strips, flexible bumpers, air intake hoses, cushion panels, and other parts.

[0048]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting.

[0049]

[Reference Example 1: Preparation of polyolefin as component (a)] High-density polyethylene (Suntech-HDS360; manufactured by Asahi Kasei Kogyo) was designated as (a-1), and high-density polyethylene (Suntech-HDJ320; manufactured by Asahi Kasei Kogyo) was used ( a-2)
And In addition, low-density polyethylene (Suntech-LD
M1804; manufactured by Asahi Chemical Industry Co., Ltd.) was used as (a-3).

[0050]

[Reference Example 2: Preparation of PPE as component (b)] After fully replacing the inside of a stainless reactor having an oxygen blowing port at the bottom of the reactor with a cooling coil and stirring blades with nitrogen,
Cupric bromide 53.6 g, di-n-butylamine 1110
g, 20 liters of toluene, 16 n-butanol
2,6-in a mixed solvent of liter and 4 liters of methanol
8.75 kg of xylenol was dissolved and charged into a reactor. Continue to blow oxygen into the reactor while stirring, 1
Polymerization was carried out for 80 minutes. In addition, in order to maintain the internal temperature at 40 ° C., water was circulated through the cooling coil during the polymerization. After the completion of the polymerization, the precipitated polymer was filtered off, a methanol / hydrochloric acid mixture was added to decompose the residual catalyst in the polymer, and the polymer was thoroughly washed with methanol and dried to give a white powder PPE (reduced viscosity 0.54) was obtained. Let this polymer be (b-1). Furthermore, except that the amount of catalyst used was changed, the reduced viscosity was 0.3.
A PPE of 1 was obtained. Let this polymer be (b-2).

[0051]

[Reference Example 3: Preparation of hydrogenated block copolymer of component (c)] Polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene amount 62%, number average molecular weight 108,000, molecular weight distribution 1 0.08, the polybutadiene before hydrogenation has a 1,2-vinyl bond content of 38.
%, The hydrogenation rate of the polybutadiene part was 99.9%, and a hydrogenated block copolymer was synthesized.
And

Similarly, it has the structure of polystyrene-hydrogenated polybutadiene-polystyrene, the bound styrene content is 75%, the number average molecular weight is 133,000, the molecular weight distribution is 1.05, and the polybutadiene before hydrogenation is 1,2- The vinyl bond content is 36% and the hydrogenation rate of the polybutadiene part is 9
A 9.9% hydrogenated block copolymer was synthesized, and this polymer was designated as (c-2).

[0053]

[Reference Example 4: Preparation of hydrogenated block copolymer of component (d)] It has a structure of hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene and has a bound styrene content of 31% and a number average molecular weight of 91. , 00
0, molecular weight distribution 1.04, 1,2-vinyl bond content of polybutadiene before hydrogenation 36%, hydrogenation rate of the polybutadiene portion 99.8% was synthesized a hydrogenated block copolymer, this polymer (D-1).

Similarly, it has a structure of (polystyrene-hydrogenated polybutadiene-) _4- Si, and has a bound styrene content of 20%, a number average molecular weight of 523,000, a molecular weight distribution of 2.4, and polybutadiene before hydrogenation. The 1,2-vinyl bond content is 46% and the hydrogenation rate of the polybutadiene part is 9%.
A 9.4% hydrogenated block copolymer was synthesized, and this polymer was designated as (d-2).

[0055]

[Reference Example 5: Preparation of phosphate ester type flame retardant as component (e)] 2,2-bis- {4- [bis (methylphenoxy)]
Phosphoryloxy] phenyl} propane (CR-7
41C; manufactured by Daihachi Chemical Co., Ltd.) was designated as (e-1).

[0056]

Reference Example 6: Preparation of Silicon Polymer as Component (f) Master batch of high molecular weight polydimethylsiloxane oil / polypropylene (50/50 weight ratio) (BY27-0
01; manufactured by Toray Dow Corning Silicone Co., Ltd. (f-
1). The physical properties of each composition were evaluated according to the following methods. (1) Presence or absence of layer peeling Using an injection molding machine [Auto Shot 50D (manufactured by FANUC)] at a mold temperature of 40 to 70 ° C. and a cylinder set temperature of 250 to 270 ° C., a test piece conforming to ASTM-D638 Molded, universal testing machine [Autograph 500
0 (manufactured by Shimadzu Corporation)] was pulled at a pulling speed of 30 mm / min to break, and the fracture surface was observed, and it was determined whether the fracture surface was peeled into layers. (2) Impact resistance A test piece for Izod impact test was molded using an injection molding machine in the same manner as in (1), and Izod (notched) impact strength (ASTM-D256: 23 ° C) was measured. (3) Flame retardance A film (thickness: 0.1 mm) is formed by a heat press (set temperature: 260 ° C.), and 0.1 mm × 3 mm × 20
It was cut to 0 mm, fixed at the upper end with a clamp, hung vertically, and indirectly fired at the lower end with a gas burner for 3 seconds, and then the flame was removed. (4) Wear resistance As in (1), using an injection molding machine, JIS-K721
Outer diameter based on 8- (A) 25.6 mm x inner diameter 20 mm
× By forming into a cylindrical sample having a height of 15 mm and a contact area of 2 cm ² , and using a thrust type abrasion tester (manufactured by Toyo Seiki Co., Ltd.),
Atmospheric temperature 23 ℃, non-lubricated, steel S4 as friction mating material
5C is selected, the surface pressure at the time of measurement is 5 kg / cm ² , the sliding linear velocity is 60 cm / sec, and the total travel distance is 500 km continuously, and the wear amount per unit distance (weight change before and after the wear test The value obtained by dividing by the test travel distance) was calculated and compared.

[0057]

Examples 1 to 8 and Comparative Examples 1 to 8 Polyolefin (a-1 to 3), polyphenylene ether (b-1 to 1)
2), hydrogenated block copolymers (c-1 and 2), hydrogenated block copolymers (d-1 and 2), phosphate ester flame retardant (e-1), silicone polymer / polypropylene masterbatch ( f-1) was blended with the composition shown in Tables 1 and 2, and a twin-screw extruder with a vent port (ZSK-25; WERNER & PFLEIDERER) set at 280 ° C.
(Manufactured by Germany, Germany) and melt-kneaded to obtain pellets.

Using these pellets, the pellets were molded by the above-mentioned methods and the physical properties were evaluated. These results are also shown in Table 1.
I put it on ~ 2. From these results, as a compatibilizer of polyolefin and polyphenylene ether,
A composition in which at least one hydrogenated block copolymer having a different amount of bound styrene is used together does not cause delamination. on the other hand,
The composition using only the hydrogenated block copolymer having a fixed amount of bound styrene shows remarkable delamination.

Furthermore, the composition in which at least one hydrogenated block copolymer having a different amount of bound styrene is used in combination is capable of exhibiting excellent levels of impact resistance, flame retardancy and abrasion resistance at the same time. , Is superior to a composition using only a hydrogenated block copolymer having a fixed amount of bound styrene. It can be seen that the level of wear resistance was greatly improved by adding the silicon polymer.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

Example 9 Polypropylene (Asahi Kasei Polypro E420
1; Asahi Chemical Industry Co., Ltd.) 46 parts by weight, PPE having a reduced viscosity of 0.31 54 parts by weight, hydrogenated block copolymer (polystyrene-hydrogenated polybutadiene-polystyrene) structure, bound styrene amount 75% , Number average molecular weight 14
2000, molecular weight distribution 1.05, 11 parts of 1,2-vinyl bond content of polybutadiene before hydrogenation of 40%, hydrogenation rate of polybutadiene part is 99.9%, hydrogenated block copolymer (polystyrene- It has a structure of hydrogenated polybutadiene-polystyrene and has a bound styrene content of 33.
%, Number average molecular weight 172,000, molecular weight distribution 1.05,
(The 1,2-vinyl bond content of polybutadiene before hydrogenation is 40%, the hydrogenation rate of polybutadiene part is 99.9%)
16 parts, paraffin oil (Diana Process Oil PW-380; manufactured by Idemitsu Kosan Co., Ltd.) 8 parts, and 2,2-
12 parts of bis- {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane (CR741-C; manufactured by Daihachi Chemical Co., Ltd.), silicone polymer / polypropylene masterbatch (50/50 weight ratio) (BY27-00)
1; Toray Dow Corning Silicone Co., Ltd.) 1.5 parts of components are mixed and blended with a Henschel mixer,
Twin screw extruder with vent port set to 280 ° C (ZS
K-25; Werner & Pfleiderer Co.,
(Germany) and melt-kneaded to obtain pellets.

Using these pellets, the pellets were molded by the above-mentioned method and the physical properties were evaluated. The Izod impact strength was 14 (kg · cm / cm notch). The flammability test was self-extinguishing. As the wear resistance, the wear amount per unit distance was 2.31 × 10 ⁻⁷ (g / km). In the confirmation of the layer delamination by observing the fracture surface after the tensile test, no delamination phenomenon was observed.

[0064]

Example 10 Polypropylene (Asahi Kasei Polypro M16
00; manufactured by Asahi Kasei Kogyo Co., Ltd.) 50 parts by weight, reduced viscosity 0.31
50 parts by weight of PPE, hydrogenated block copolymer (polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene amount 75%, number average molecular weight 1
42,000, molecular weight distribution 1.05, 12 parts of 1,2-vinyl bond amount of polybutadiene before hydrogenation 81%, hydrogenation rate of polybutadiene part 99.9%, hydrogenated block copolymer (polystyrene- It has the structure of hydrogenated polybutadiene-polystyrene and the amount of bound styrene is 3
3%, number average molecular weight 172,000, molecular weight distribution 1.0
5, 1,2-vinyl bond amount of polybutadiene before hydrogenation is 40%, hydrogenation rate of polybutadiene part is 99.9
%) 50 parts, paraffin oil (Diana Process Oil PW-380; manufactured by Idemitsu Kosan Co., Ltd.) 50 parts, triphenyl phosphate (TPP; manufactured by Daihachi Chemical Co., Ltd.) 25 parts as a flame retardant, silicone polymer / polypropylene masterbatch ( (50/50 weight ratio) (BY27-001; Toray Dow Corning Silicone Co., Ltd.)
Twin screw extruder with a vent port set to ℃ (ZSK-2
5; melt-kneaded using WERNER & PFLEIDER, Germany) to obtain rubber-like pellets. At this time, there was a large amount of volatile substances from the extruder outlet, and when cooled and recovered, it was triphenyl phosphate.

Using the pellets, the pellets were molded by the above-mentioned methods and the physical properties were evaluated. When measured by Izod impact strength, the molded product was very soft and did not break. The flammability test was self-extinguishing. In the confirmation of the layer delamination by observing the fracture surface after the tensile test, no delamination phenomenon was observed. However, triphenyl phosphate bleeded out slightly on the surface of the molded product.

[0066]

Example 11 Example 11 except that 12 parts of 2,2-bis- {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane (CR741-C; manufactured by Daihachi Chemical Co., Ltd.) was used as a flame retardant. Twin screw extruder with vent port (ZSK-25; WERNER & P)
It was melt-kneaded using FLEIDERER (Germany) to obtain rubber-like pellets.

Using the pellets, the pellets were molded by the above-mentioned methods and their physical properties were evaluated. When measured by Izod impact strength, the molded product was very soft and did not break. The flammability test was self-extinguishing. In the confirmation of the layer delamination by observing the fracture surface after the tensile test, no delamination phenomenon was observed. Neither the volatilized component at the time of molding processing nor the bleed-out product appearing on the surface of the molded product as observed in Example 10 was observed.

[0068]

Comparative Example 9 Polypropylene (Asahi Kasei Polypro M160
0: Asahi Kasei Kogyo Co., Ltd.) 50 parts by weight, 50 parts by weight of PPE having a reduced viscosity of 0.31 and a hydrogenated block copolymer (polystyrene-hydrogenated polybutadiene-polystyrene) structure having a bound styrene content of 80%. , Number average molecular weight 99
000, molecular weight distribution of 1.04, 9 parts of 1,2-vinyl bond amount of polybutadiene before hydrogenation of 35%, hydrogenation rate of polybutadiene part of 99.9%, hydrogenated block copolymer (polystyrene- Having a structure of hydrogenated polybutadiene-polystyrene, the amount of bound styrene is 64%,
Number average molecular weight 105,000, molecular weight distribution 1.06, polybutadiene before hydrogenation has a 1,2-vinyl bond content of 38.
%, The hydrogenation rate of the polybutadiene part is 99.9%) 5
Part, and further 2,2-bis- {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane (CR
741-C; manufactured by Daihachi Chemical Co., Ltd.) 12 parts, silicon polymer / polypropylene masterbatch (50/50 weight ratio)
(BY27-001; manufactured by Toray Dow Corning Silicone Co., Ltd.) 1.5 parts of components are mixed and blended with a Henschel mixer, and a twin-screw extruder with a vent port (ZSK-25; WERNER & PFLEI) set at 280 ° C.
It was melt-kneaded using DERRER (Germany) to obtain rubber-like pellets.

The pellets were molded by the above-mentioned method and evaluated for physical properties. As a result, in the combustion test, it has self-extinguishing property, and the wear amount per unit distance is
It was 2.00 × 10 ⁻⁷ (g / km). However, as a compatibilizer for polyolefin and polyphenylene ether, two types of hydrogenated block copolymers having different amounts of bound styrene were used together, and the calculated average bound styrene amount of all hydrogenated block copolymers was about 74%. ,
It was confirmed that delamination occurred remarkably, and the Izod impact strength was as low as 3.1 kg · cm / cm.

[0070]

Example 12 Polypropylene (Asahi Kasei Polypro M16
00; manufactured by Asahi Kasei Kogyo Co., Ltd.) 50 parts by weight, reduced viscosity 0.31
50 parts by weight of PPE, a hydrogenated block copolymer (polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene content 80%, number average molecular weight 9
9000, molecular weight distribution 1.04, 4 parts of 1,2-vinyl bond amount of polybutadiene before hydrogenation of 35%, hydrogenation rate of polybutadiene part is 99.9%, hydrogenated block copolymer (polystyrene- It has a structure of hydrogenated polybutadiene-polystyrene and has a bound styrene content of 64.
%, Number average molecular weight 105,000, molecular weight distribution 1.06,
The amount of 1,2-vinyl bonds in the polybutadiene before hydrogenation is 38%, and the hydrogenation rate of the polybutadiene part is 99.9%)
4 parts, hydrogenated block copolymer (having a structure of polystyrene-hydrogenated polybutadiene-polystyrene,
Bound styrene content 40%, number average molecular weight 116000, molecular weight distribution 1.07, polybutadiene before hydrogenation 1,
2-vinyl bond amount is 41%, hydrogenation rate of polybutadiene part is 99.9%, 4 parts, hydrogenated block copolymer (polystyrene-hydrogenated polybutadiene-polystyrene structure), bound styrene amount 23%, number average molecular weight 184,000, molecular weight distribution 1.09, 1,2-vinyl bond amount of polybutadiene before hydrogenation is 34%, hydrogenation rate of polybutadiene part is 99.9%) 4 parts, and further 2, 2-bis- {4- [bis (methylphenoxy) phosphoryloxy] phenyl} propane (CR741-
C; manufactured by Daihachi Chemical Co., Ltd.) 12 parts, silicone polymer / polypropylene masterbatch (50/50 weight ratio) (BY2
7-001; manufactured by Toray Dow Corning Silicone Co., Ltd.)
A twin-screw extruder with a vent port (ZSK-25; WERNER & PFLEIDERE) set to 280 ° C by mixing and blending 1.5 parts of ingredients with a Henschel mixer.
Melt-kneading was carried out using R company, Germany) to obtain pellets.

The pellets were molded by the above-mentioned methods and evaluated for physical properties. The Izod impact strength was 11 (kg · cm / cm notch), and the combustion test showed self-extinguishing property. As the wear resistance, the amount of wear per unit distance was 0.67 × 10 ⁻⁷ (g / km). Further, as a compatibilizer of polyolefin and polyphenylene ether, two or more hydrogenated block copolymers having different amounts of bound styrene are used in combination, and the calculated average bound styrene amount of all hydrogenated block copolymers is about 52%.
It was confirmed that delamination did not occur.

[0072]

Industrial Applicability The polymer composition of the present invention has a hydrogenated block copolymer having a bound vinyl aromatic compound amount in two specific ranges, which acts as a compatibilizer of polyolefin and polyphenylene ether. In the combination, at least one hydrogenated block copolymer within each specific range is used, and at least two hydrogenated block copolymers are used, and the bound vinyl aroma of the entire hydrogenated block copolymer is used. Since the hydrogenated block copolymer is used so that the average amount of the group compound is within a specific range,
Improves the delamination phenomenon of polymer composition containing polyolefin and polyphenylene ether, which was difficult with conventional technology, and provides a polymer composition with excellent impact resistance, flame retardancy, abrasion resistance, oil resistance, and chemical resistance. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C08L 83/04 LRY

Claims (2)

[Claims] 1. The amount of (a) polyolefin (b) polyphenylene ether (c) bound vinyl aromatic compound exceeds 45% by weight.
95% by weight of at least one hydrogenated product of vinyl aromatic compound-conjugated diene compound block copolymer (d) vinyl aromatic compound-conjugated diene compound having an amount of bonded vinyl aromatic compound of 5% by weight to 45% by weight At least one hydrogenated product of the block copolymer is composed of (e) phosphorus and a phosphorus compound (f) silicon polymer, and with respect to the total amount of the components (a) and (b),
The component (a) is 5 to 95% by weight, the component (b) is 95 to 5% by weight, and the component (c) and the component (d) are based on 100 parts by weight of the total amount of the components (a) and (b). The total amount of 1-100
% By weight, and With respect to 100 parts by weight of the total amount of the components (a) to (d),
1 to 40 parts by weight of the component (e), relative to 100 parts by weight of the total amount of the components (a) to (e),
The polymer composition, wherein the component (f) is 0.01 to 10 parts by weight. 2. The polymer composition according to claim 1, wherein the component (a) is polyethylene.