JPH04108838A - Thermoplastic polymer composition - Google Patents

Abstract

PURPOSE:To provide a composition having largely improved Vicat softening point and impact resistant strength and having good heat resistance, elongation and abrasion resistance by compounding a vinyl aromatic compound polymer, a thermoplastic polyurethane elastomer, etc., with a functional group-containing vinyl aromatic compound, etc. CONSTITUTION:The composition comprises (A) 50-96wt.% of the homopolymer of a vinyl aromatic compound, a graft copolymer thereof with a cyanized vinyl compound, etc., (B) 2-40wt.% of a thermoplastic polyurethane elastomer, thermoplastic polyester elastomer, etc., (C) a block copolymer comprising a polymer block consisting mainly of a vinyl aromatic compound and a polymer block consisting mainly of a conjugated diene compound, etc., and (D) a (co)polymer having functional groups selected from hydroxyl groups, acid anhydride groups and epoxy groups in an amount of 1-50 pts.wt. per 100 pts.wt. of the sum of the components A, C and B.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a thermoplastic polymer composition having excellent compatibility, transparency, heat resistance, mechanical strength, abrasion resistance, and impact resistance. More specifically, in contrast to polymers mainly consisting of vinyl or aromatic compounds, elastomers such as thermoplastic polyurethane elastomers, and vinyl aromatic compound-conjugated diene compound copolymers, vinyl aromatic compounds or olefin compounds-unsaturated carbon acids, their derivatives, or α.

(Co) with glycidyl esters of β-unsaturated carboxylic acids
The present invention relates to a thermoplastic polymer composition containing a polymer.

[Prior Art] Styrenic polymers have good processability in injection molding, sheet molding, etc., and hot water resistance, but have the disadvantage of poor impact resistance and oil resistance. In addition, thermoplastic elastomers such as thermoplastic polyurethane elastomer, thermoplastic polyester elastomer, and thermoplastic polyamide elastomer,
It has good processability such as injection molding and extrusion molding, heat resistance, oil resistance, impact resistance, and abrasion resistance, but it has a drawback of hot water resistance. However, since styrenic polymers and these thermoplastic elastomers are incompatible, it is not possible to overcome the drawbacks of both polymers simply by mixing them.

[Problems to be Solved by the Invention] The present invention was developed as a result of intensive studies aimed at improving the compatibility between costicine-based polymers and thermoplastic polyurethane elastomers, and developing compositions that are more beneficial in terms of physical properties. be.

[Means for Solving the Problems] That is, the present invention provides (a) (a-1) a homopolymer of a vinyl aromatic compound, and (a-2) a vinyl aromatic compound, a vinyl cyanide compound, and a conjugated diene. 50 to 96% by weight of a random or graft copolymer (hereinafter referred to as "vinyl aromatic polymer") with at least one selected from compounds and monoolefin hydrocarbon compounds, (b) (b-1) Thermoplastic Polyurethane elastomer (b-2) 2 to 40% by weight of at least 11 selected from thermoplastic polyester elastomer and (b-3) thermoplastic polyamide elastomer, (c) (c-1) vinyl A block copolymer (hereinafter referred to as [copolymer (
c-1) J), and (c-2) a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene compound (hereinafter referred to as "copolymer (c-2) J"). 2 to 30% by weight of at least one type, and (d) at least one functional group selected from hydroxyl group, carboxyl group, acid anhydride group, and epoxy group (
At least one selected from co)polymers, 1. (a)
) component, (b) component and (c') component total amount 100
The object of the present invention is to provide a thermoplastic polymer composition characterized in that it contains 1 to 50 parts by weight.

The present invention will be explained in detail below.

The vinyl aromatic compounds used in component (a) include styrene, α-methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene,
Examples include fluorostyrene, p-tert-butylstyrene, ethylstyrene, and vinylnaphthalene, and one or more of these may be used. Among these, styrene is particularly preferred. In addition, vinyl cyanide compounds include acrylonitrile and metacyclonitrile, and conjugated diene compounds include 1,3-butadiene and 2-butadiene.
-Methyl-1,3-butadiene, 2,3-dimethyl-1
, 3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro1,3-butadiene, 2-cyano-1
, 3-butadiene, substituted linear conjugated pentagenes, linear and side chain conjugated hexadiene, and the like. Among these, use of 1,3-butadiene and 2-methyl-1-23-butadiene is particularly preferred. Examples of the monoolefin hydrocarbon compound include ethylene and propylene.

Here, the vinyl aromatic polymer preferably contains 50% by weight or more of a vinyl aromatic compound component such as styrene, more preferably 60% by weight or more, particularly preferably 70% by weight or more. For example, (
a-1) Homopolymers of vinyl aromatic compounds include polystyrene, impact-resistant polystyrene, etc. (a-2)
Random or graft copolymers containing vinyl aromatic compounds include styrene-acrylonitrile copolymers (
AS), acrylonitrile-butadiene-stycine copolymer (ABS), acrylonitrile ethylene-propylene-styrene copolymer (AES), and the like.

As the vinyl aromatic polymer, those obtained by known radical polymerization methods, ionic polymerization methods, etc. can be suitably used. Its number average molecular weight is preferably 5°000 to 500,00
0, more preferably from 50°000 to 200,000, and the molecular weight distribution [weight average molecular weight (Mw
) and the number average molecular weight (Mn) (Mw/Mn)) is
It is preferably 5 or less.

Among the above, as component (a), a homopolymer of a vinyl aromatic compound is preferable.

In the present invention, polyphenylene ether may be added to the vinyl aromatic polymer.

The polyphenylene ether used in the present invention is a homopolymer or a copolymer obtained by oxidative polymerization of one or more monocyclic phenols represented by the general formula (I), and a vinyl aromatic compound in the polyphenylene ether skeleton. Contains a graft copolymer grafted with.

R, R2 (wherein R1-R5 are selected from hydrogen, halogenated hydrocarbons, hydrocarbon groups, or substituted hydrocarbon groups) Polyphenylene obtained by polycondensation of one or more of these phenols Examples of ether include poly(2,
6-dimethyl-1,4-phenylene)ether, poly(
2,6-danityl-1,4-phenylene) ether, poly(2,6-diprobyl-1,4-)unisine) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, -Methyl-6-propyl-1゜4
-) unicin) ether, poly(2-ethyl-6-broby-1,4-)unicin) ether, 2,6-dimethylphenol/2,3.6-dimethylphenol copolymer, 2,6-dimethylphenol Methylphenol/2.3.6-)ruethylphenol copolymer, 2,6-dimethylphenol/2.3°6-dolimethylphenol copolymer, 2,
6-diprobylphenol/2,3.64-limethylphenol copolymer, graft copolymer of styrene grafted onto poly(2,6-dimethyl-1°4-phenylene) ether, 2,6-dimethylphenol /2.3.
6-) A graft copolymer obtained by graft-polymerizing styrene onto a trimethylphenol copolymer may be mentioned. especially,
Poly(2,6-dimethyl-1,4-phenylene) ether, 2゜6-dimethylphenol/2,3.6-drimethylphenol copolymer, and a graft copolymer in which styrene was grafted onto each of the former two. Includes merging.

There are no particular restrictions on the polyphenylene ether used in the present invention;
-0.70 is used, and from the mechanical strength and moldability (fluidity) of the resulting composition, the range is 0.30 to 0.60.
is more preferable. Note that polyphenylene ether can be added to component (a) preferably in an amount of 60% by weight or less, more preferably up to 50% by weight.

Among the components (b) of the present invention, the thermoplastic polyurethane elastomer (b-1) is produced by a polyaddition reaction using long-chain polyols, short-chain glycols, diisocyanates, etc. as raw materials through urethane bonds in the molecule. This is a polymer obtained by

Here, the polyol component including long chain polyol and short chain polyol and the diisocyanate compound are diisocyanate compound/polyol component (mole ratio) usually 0.
React at a ratio of 95 to 1.1.

The long-chain polyols that are the raw materials for this thermoplastic polyurethane elastomer include poly(1,4-butylene adipate), poly(1,6-hexane adipate), polycaprolactone, polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol. and so on. In addition, short chain glycols include ethylene glycol,
Examples of diisocyanates include 1,4-butanediol and 1,6-hexanediol, and examples of diisocyanates include tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. be. A soft segment is formed by a long chain polyol and a diisocyanate, and a hard segment is formed by a short chain glycol and a diisocyanate.

The preferred molecular weight of the thermoplastic polyurethane elastomer is preferably 5,000 to 500,000, more preferably 10,000 to 300,000.

The thermoplastic polyester elastomer (b-2) of the present invention is a polyester block copolymer, and in its polymer chain, a high melting point crystalline segment (D) mainly consisting of aromatic polyester units and an aliphatic polyether unit (F) and/or aliphatic polyester unit (G
) and a low melting point polymer segment (E) mainly consisting of.

The aromatic polyester unit of the high melting point crystalline segment (D), which is the hard segment used above, is formed from an acid component and a glycol component, and this acid component includes terephthalic acid, isophthalic acid, phthalic acid, 2, 6- and 1,5-naphthalenedicarboxylic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4.
4'-diphenyl ether dicarboxylic acid, 4.4'
- Aromatic dicarboxylic acids such as diphenylmethane dicarboxylic acid and phenylindane dicarboxylic acid, 1,4 cyclohexane dicarboxylic acid, cyclopencune dicarboxylic acid, 4
, 4'-dicyclohexyl dicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, and dimer acid. It is preferable to use aromatic dicarboxylic acid in an amount of at least 50 mol %, and use of terephthalic acid is particularly recommended.

Further, the glycol component forming the aromatic polyester unit is a glycol having 2 to 12 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-bentanediol, 1,6 -hexanediol, decamethylene glycol, cyclohexane dimetatool, bis(p-
Bisphenols such as hydroxy)diphenyl, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)propane, and mixtures thereof are used, but aliphatic or alicyclic diols having 2 to 8 carbon atoms are particularly preferably used. .

Furthermore, the aliphatic polyether unit (F) constituting the low melting point polymer segment (E), which is the soft segment, is formed from polyalkylene glycol having an average molecular weight in the range of about 200 to 6,000. However, the polyalkylene glycol is, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, or polyethylene glycol-polypropylene glycol block copolymer, with polytetramethylene glycol being particularly preferred. These are its carbon numbers:
As long as the oxygen number ratio is 2.0 to 4.5, they can be used alone or as a mixture.

The aliphatic polyester unit (G), which is another unit constituting the low melting point polymer segment (E), mainly consists of an aliphatic dicarboxylic acid and a glycol. succinic acid,
These are adipic acid, sepatic acid, and decanedicarboxylic acid.

In addition to the aliphatic dicarboxylic acids mentioned above, a small amount of aromatic dicarboxylic acids such as isophthalic acid may be used in combination.

Further, the glycol component forming the aliphatic polyester unit (G) is a glycol component having 2 to 12 carbon atoms, and is exemplified as the glycol component forming the aromatic polyester unit of the high melting point crystalline segment (D). It is similar to

The aliphatic polyester unit (G) is obtained by polycondensing the aliphatic dicarboxylic acid and the glycol component in a conventional manner, and may be a homopolyester or a copolyester, or may be obtained by ring-opening a cyclic lactone. It may also be a polylactone obtained by polymerization, such as polycaproate.

The composition ratio of the high melting point crystalline segment (D) as a hard segment and the low melting point polymer segment (E) as a soft segment in the thermoplastic polyester elastomer (b-2) used in the present invention is as follows: From 9515
Preferably it is 5/95, more preferably 70
/30 to 30/70.

The polyester block copolymer particularly preferably used as the thermoplastic polyester elastomer (b-2) of the present invention includes polytetramethylene terephthalate, polytrimethylene terephthalate (polytrimethylene terephthalate)-2, 6 naphthalate, and aliphatic polyester such as polytetramethylene glycol, polytetramethylene adipate, polycaproate, etc. as the low melting point polymer segment (E).

The thermoplastic polyamide elastomer (b-3) of the present invention is a polyamide block copolymer, and its polymer chain consists of a high melting point crystalline segment (H) mainly consisting of aliphatic polyamide units and an aliphatic polyether unit. It has a main low melting point polymer segment (I).

The aliphatic polyamide unit of the high melting point crystalline segment (H), which is the hard segment used above, is a lactam or amino acid whose hydrocarbon chain has 4 to 14 carbon atoms, or a condensation product of a dicarboxylic acid and a diamine. Formed from dicarboxylic acids, this lactam component includes caprolactam, lauryllactam, enantlactam,
These include dodecalactam, undecanolactam, and dodecalactam. The amino acid component includes 11-amino-undecanoic acid and 12-amino-dodecanoic acid, preferably caprolactam, lauryllactam, etc., and the dicarboxylic acid in the condensation product of the dicarboxylic acid and diamine includes adipic acid, azelain, etc. The acid, sebacic acid, 1,12-dodecanedioic acid, and diamine include hexamethylene diamine and nonamethylene diamine, preferably a condensation product of adipic acid and hexamethylene diamine. The above dicarboxylic acid is necessary to obtain a polyamide having carboxylic acid at the end, and has 4 to 20 carbon atoms.
aliphatic dicarboxylic acids such as succinic acid, adipic acid,
Speric acid, azelaic acid, sebacic acid, undecanoic acid and dodecanedic acid, preferably adipic acid.

The average molecular weight of aliphatic polyamide is usually 300 to 15,
000, preferably 800-5. It is 000.

The low melting point polymer segment (which is the soft segment above)
The aliphatic polyether units of I) have an average molecular weight of about 20
0 to 6,000, which polyalkylene glycols are, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol polypropylene glycol block copolymers, especially polytetra Methylene glycol is preferred. These have a ratio of carbon number to oxygen number of 2. 0 to 4.5, it can be used alone or as a mixture.

Two or more of the above components (b-1) to (b-3) can also be used in combination.

Among the components (b), it is particularly preferable to use the thermoplastic polyurethane elastomer (b-1) from the viewpoint of compatibility.

Among component (c), copolymer (c-1) preferably contains a vinyl aromatic compound in an amount of 2 to 30% by weight, more preferably 5 to 25% by weight, and has a linear structure. , may be branched or radial, and is not particularly limited.

Specifically, the general formula % formula % (wherein A is a polymer block mainly composed of an aromatic vinyl compound, B is a polymer block mainly composed of a conjugated diene compound, X is a coupling agent residue, n is an integer of 1 or more).

Here, the polymer block mainly composed of a vinyl aromatic compound is a vinyl aromatic compound homopolymer or a vinyl aromatic compound containing usually 60% by weight or more, preferably 80% by weight.
It has a structure consisting of a copolymer of a vinyl aromatic compound and a conjugated diene compound containing at least % by weight.

On the other hand, a polymer block mainly composed of a conjugated diene compound is a conjugated diene compound homopolymer, or a conjugated diene compound containing a conjugated diene compound in an amount of usually 60% by weight or more, preferably 80% by weight or more, and a vinyl aromatic compound. It may have a structure consisting of a copolymer of , and may have one or more so-called tapered blocks in which vinyl aromatic compounds are randomly bonded or gradually increased.

As vinyl aromatic compounds and conjugated diene compounds,
The same ones as above can be mentioned.

The weight average molecular weight of the entire copolymer (c-1) is preferably 10,000 to 500,000, more preferably 2
0,000 to 300,000.

The copolymer (c-1) has not only one type but also different structures,
It is also possible to combine materials with different vinyl aromatic compound contents.

The copolymer (c-2) is a random or block copolymer of a vinyl aromatic compound and a conjugated diene compound,
The content of the vinyl aromatic compound is usually 50% by weight or less, preferably 40 to 5% by weight.

Specifically, the general formula % formula % (4) A-B1-B+ (B+ vinyl bond is preferably 20% or more, B2 vinyl bond is preferably 20%
less than) (5) A/B, T6) A-A/B,
(7) A-A/B-C, (8) A-A/B-A.

(9) B2-BT-B2, (10) c-B,
(11) C-B-C1 (12) C-A/B
-C1(13) C-A-B (wherein A and B are the same blocks as above, A/B is a block consisting of a random copolymer of a vinyl aromatic compound and a conjugated diene compound, and C is a vinyl aromatic It is a copolymer of a group compound and a conjugated diene compound, and is a tapered block in which the vinyl aromatic compound gradually increases. Examples include water additives of copolymers such as polymers (hereinafter referred to as "diene copolymers").

Regarding A-B and -82 in (4) above, patent application No. 6328
No. 5774, regarding A/H of (5), JP-A-63-1
No. 27400. (6) AA/B, (7
), preferably the ratio of vinyl aromatic compound/conjugated diene is 5 to 40/60 to 95% by weight, and the total amount of vinyl aromatic compounds of A or A and C is the same. 3 to 25% by weight of the polymer, the vinyl bond content of the conjugated diene moiety in A/B is 15% or more, particularly preferably 3
It is 0-80%.

The vinyl aromatic compounds and conjugated diene compounds used to produce these diene copolymers include:
The same ones as above can be mentioned.

The hydrogenation rate of olefinic unsaturated bonds in diene polymers is 7
It is 0% or more, preferably 90% or more.

In addition, the microstructure of the diene polymer is 1,2-13.4
The amount of vinyl bonding metal such as - is preferably 10% or more, more preferably 20 to 80%, particularly preferably 30 to 6
The number average molecular weight of the diene polymer is preferably 5,000 to 1°000.000, more preferably 30,000 to 300,000.

Regarding the method of polymerizing the above-mentioned diene polymer and the method of hydrogenating the diene polymer, see, for example, Japanese Patent Application No. 6:3-10.
The method shown in No. 4256 can be used.

(d) Components include (d-1) a vinyl aromatic (co)polymer having a functional group (hereinafter referred to as "copolymer d-1"), and (d-2) an olefin having a functional group. elastomer (hereinafter referred to as "copolymer d-2").

The copolymer (d-1) contains at least one selected from unsaturated carboxylic acids, derivatives thereof, hydroxyalkyl esters of α,β-unsaturated carboxylic acids, and glycidyl esters of α,β-unsaturated carboxylic acids. A copolymer containing a vinyl aromatic compound, and examples of the vinyl aromatic compound include those mentioned above.

In addition, unsaturated carboxylic acids or their derivatives include maleic acid, maleic anhydride, fumaric acid, itaconic acid, (
meth)acrylic acid, crotonic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, etc., and their anhydrides,
Further examples include imidides, among which maleic anhydride is preferred. Examples of the glycidyl ester of α,β-unsaturated carboxylic acid include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate, and among these, glycidyl methacrylate is preferred.

Examples of the hydroxyalkyl ester of α,β-unsaturated carboxylic acid include hydroxyethyl methacrylate and hydroxyethyl acrylate.

In addition, during copolymerization, vinyl compounds other than vinyl aromatic compounds such as (meth)acrylonitrile, acrolein, N-vinylpyrrolidone, and N-vinylcaprolactam, methyl (meth)acrylate, butyl (meth)acrylate, (
(meth)acrylic acid ester compounds such as hexyl meth)acrylate, or ethylene, propylene, butene-
Olefin compounds such as 1 and N-phenylmaleimide,
Other radically polymerizable monomers such as vinyl chloride, vinylidene chloride, (meth)acrylamide, allyl glycidyl ether, and chloromethylstyrene can be used alone or in copolymers containing two or more of them.

There are various methods for producing the copolymer, and the copolymer can be obtained by known methods such as solution polymerization, bulk polymerization, and bulk-suspension polymerization. or a graft copolymer.

The graft copolymer can be prepared by the following method, for example: (i) suspending a high molecular weight monomer having a carbon-carbon double bond at the molecular end (hereinafter referred to as "r high molecular weight monomer") and a vinyl monomer in an aqueous system; It is produced by a method of graft copolymerization by polymerization, or a method of graft copolymerization of a prepolymer mainly composed of α-olefin and α,β-unsaturated carboxylic acid glycidyl ester and a vinyl aromatic compound by aqueous suspension polymerization. be able to.

The high molecular weight monomers used in the method (2) above include the vinyl aromatic compounds, unsaturated carboxylic acids or derivatives thereof, glycidyl esters of α, β-unsaturated carboxylic acids, and other radically polymerizable monomers. A (meth)acroyloxy group introduced into at least one end of a prepolymer having a number average molecular weight of about 1,000 to 5,000 obtained by radical polymerization or ionic polymerization of at least one compound selected from It is. Furthermore, the vinyl monomer is preferably a compound that can dissolve a high molecular weight monomer, and examples thereof include the same monomers as the vinyl compounds used for producing the high molecular weight monomer.

Polymerization of high molecular weight monomers and vinyl monomers is performed using water, dispersants such as polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxymethyl cellulose, flame retardant metal phosphates, etc., and surfactants such as sodium dodecylbenzenesulfonate. The polymerization can be carried out using an organic peroxide such as benzoyl peroxide or lauroyl peroxide or an azo compound such as azobisisobutyronitrile as a polymerization initiator.

The α-olefins used in the above method (1) include ethylene, propylene, 1-butene, isobutyne, 1-pentene, 1-hexene, 1-decene, 4-methyl-1-
Examples include butene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, etc., and examples of the α,β-unsaturated carboxylic acid glycidyl ester include those mentioned above. The number average molecular weight of the prepolymer mainly composed of α-olefin and α,β-unsaturated carboxylic acid glycidyl ester is about 5,000 to 50°, ooo.

This prepolymer, aromatic vinyl compound, and vinyl monomer can be graft copolymerized by aqueous suspension polymerization in the presence of a radically polymerizable organic peroxide and a radical polymerization initiator.

Among the copolymers (d-1), preferred are random copolymers of a vinyl aromatic compound and maleic anhydride, random copolymers of a vinyl aromatic compound and glycidyl methacrylate, and random copolymers of a vinyl aromatic compound and glycidyl methacrylate. Examples include graft copolymers consisting of glycidyl methacrylate.

The composition of the copolymer (d-1) is usually 5 to 97% by weight, preferably 5 to 95% by weight of a vinyl aromatic compound, an unsaturated carboxylic acid, a derivative thereof, and a hydroxyalkyl of an α,β unsaturated carboxylic acid. At least one selected from esters and glycidyl esters of α,β-unsaturated carboxylic acids
The amount of the species is usually 1 to 70% by weight, preferably 3 to 45% by weight, and the amount of other radically polymerizable monomers is usually 0 to 95% by weight, preferably 0 to 90% by weight.

In addition, among the components (d), the polymer (d-2) is, for example,
Copolymerizing an olefin compound and a monomer compound having at least one functional group selected from hydroxyl group, carboxyl group, acid anhydride group, and epoxy group (hereinafter referred to as "specific functional group-containing monomer compound"). Alternatively, it can be produced by a polymer reaction between a polymer of an olefin compound and a monomer compound containing a specific functional group.

Here, as the olefin compound, the same compound as the above-mentioned α-olefin is used, as the monomer compound having a carboxyl group or an acid anhydride group, the same compound as the above-mentioned unsaturated carboxylic acid and its derivative, and as the monomer compound having a carboxyl group or an acid anhydride group, the same compound as the above-mentioned unsaturated carboxylic acid and its derivative, Examples of the monomeric compounds include the same compounds as the glycidyl ester of α,β-unsaturated carboxylic acid mentioned above.

The copolymer (d-2) may further be copolymerized with a radically polymerizable compound other than the olefin compound or the specific functional group-containing monomer compound.

In addition, the specific functional group-containing monomer compound is usually 0.01 to 20% by weight in all the monomers constituting the copolymer (d-2).
, preferably 0.05 to 15% by weight.

Among the copolymers (d-2), preferred are maleic anhydride-modified ethylene-1-butene copolymer elastomer, maleic anhydride-modified ethylene-propylene copolymer elastomer, and glycidyl methacrylate-modified ethylene-1-butene copolymer elastomer.
Examples include propylene copolymer elastomer and (meth)acrylic acid-modified ethylene propylene copolymer elastomer.

The weight average molecular weight of the copolymer of component (d) is not particularly limited, but is usually 1,000 to 1゜ooo, oo
o, preferably from 3,000 to 800°,000, more preferably from 5,000 to 500°,000. When the weight average molecular weight is less than 1,000, component (a) and (b)
Although the effect of compatibilizing the components can be obtained, this is not preferable because the interfacial strength of the composite is low and the fracture properties are inferior. In addition, when the weight average molecular weight exceeds 1,000,000,
This is not preferable because the compatibilizing effect is deteriorated.

Further, the copolymer of component (d) may be modified by blending rubber during production. Examples of such rubber include polybutadiene rubber, butyl rubber, styrene-butadiene rubber, styrene-butadiene block copolymer, acrylic rubber, nitrile rubber, ethylene-propylene rubber, natural rubber, hydrogenated styrene-butadiene copolymer, and water. These include butadiene polymers.

In the composition of the present invention, component (a) is 50 to 96% by weight, preferably 60 to 96% by weight, more preferably 6% by weight.
5 to 95% by weight, component (b) 2 to 40% by weight, preferably 2 to 30% by weight, more preferably 2 to 25% by weight
, component (c) is 2 to 30% by weight, preferably 5 to 30% by weight, more preferably 5 to 25% by weight, component (cl) is composed of two components (a), (b) and (c). The amount is preferably 1 to 50 parts by weight, preferably 2 to 30 parts by weight, based on a total of 100 parts by weight. If it is less than 1 part by weight, the compatibility effect will not be exhibited, and if it exceeds 150 parts by weight, the original flexibility, rubber elasticity, and processability of component (b) and CC) will deteriorate, which is undesirable.

Note that the kneading method may be any method described below. For example, a method of kneading each component all at once or a method of kneading each component one after another may be used, but first the (b) component and (d)
A method in which the components are kneaded and then the components (a) and (c) are added and kneaded is preferred from the viewpoint of further improving compatibility.

In addition, the composition of the present invention can be modified by conventionally known methods, such as maleation, carboxylation, hydroxylation, epoxidation, halogenation, and sulfonation, as well as sulfur crosslinking, peroxide crosslinking, and metal ion. Crosslinking such as crosslinking, electron beam crosslinking, and silane crosslinking can also be performed.

The thermoplastic polymer composition of the present invention can be subjected to conventional thermal techniques. For example, plasticizers such as phthalate esters,
Fillers or reinforcing agents such as silica, talc, glass fiber, etc., antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, lubricants, foaming agents, colorants, pigments, core materials, crosslinking agents, crosslinking aids etc., or a mixture of these.

Other rubber-like polymers as necessary, such as SBR, NB
RSBR, EPT, EPRXNR, IR.

1.2-Polybutadiene, ARSCR, I IR.

H8R etc. can be added.

In addition, other thermoplastic resins other than the components (a) to <c> above, such as polyethylene resins, polyethylene resins, polypropylene resins, diene resins, polyvinyl chloride resins, and polyvinyl acetate resins, may be added as necessary. , polycarbonate resin, polyacetal resin, polyamide resin, polyester resin, polyether resin, polysulfone, polyphenylene sulfide, etc. can also be blended.

Further, the composition of the present invention can be processed into a practically useful molded article by conventionally known methods such as extrusion molding, injection molding, blow molding, compression molding, and calendering. Furthermore, processing such as painting and plating can be applied as necessary.

The composition of the present invention has excellent heat resistance, abrasion resistance, impact resistance, processability, flexibility, low temperature properties, temperature dependence, compatibility, paintability, printability, hot stampability, adhesion, and depth. By taking advantage of its drawability, hot water resistance, rubber elasticity, rubber feel, flexibility, slip resistance, stress crack resistance, etc., it can be used as adhesive/pressure-sensitive adhesive materials, asphalt modification materials, and vulcanized rubber modification materials. It can be used for etc. For example, ■Sheet applications such as tray fruit and vegetable packs for meat and fresh fish, frozen dessert foods, and containers, ■Food packaging, daily miscellaneous goods packaging, industrial material packaging, laminates for various rubber products, resin products, fabrics, leather products, etc., and paper diapers. ■Film applications such as elastic tapes used in applications such as hoses, tubes, and belts; ■Footwear applications such as sports shoes, leisure shoes, fashion sandals, and leather shoes; ■Home appliance applications such as televisions, stereos, and vacuum cleaners. ■Applications for automotive interior and exterior parts such as bumper parts, body panels, and sight shields; ■Material applications such as hot melt adhesives/adhesives, contact adhesives, and spray adhesives; ■Road paving materials, waterproofing Asphalt blend material applications such as sheets and piping coatings,
■It can be used for a wide range of other purposes, including daily necessities, leisure goods, toys, and industrial goods.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the Examples unless the gist of the present invention is exceeded.

Component (c) (Preparation of block copolymer ASB) In a washed and dried autoclave equipped with a stirrer and a jacket, 4.500 g of cyclohexane and 1 g of tetrahydrofuran were charged under a nitrogen atmosphere, and the internal temperature was then brought to 70°C. Next, after adding a hexane solution containing 0.4 g of n-butyllithium, 120 g of styrene was added and polymerized for 60 minutes. Next, 360 g of butadiene was added and polymerized for 60 minutes. Furthermore, 120 g of styrene was added and polymerized for 60 minutes. Note that during the polymerization, the temperature was adjusted to 70°C. After completion of polymerization, 2,6-di-tert-butyl-
After adding p-cresol, cyclohexane was removed by heating to obtain a linear block copolymer. The bound styrene content in this block copolymer was 40%, and the weight average molecular weight was 180,000. This is block copolymer A
shall be.

A linear block copolymer having a bound styrene content of 15% and a weight average molecular weight of 180,000 was obtained in the same manner as above. This is referred to as block copolymer B.

(Adjustment of block copolymer C) In the same autoclave as above, cyclohexane 4,5
After adding 00g and 1g of tetrahydrofuran, the internal temperature was 7.
The temperature was 0°C. Next, after adding a hexane solution containing 0.8 g of n-butyllithium, 420 g of styrene was added, and 60 g of styrene was added.
Polymerized for minutes. Next, 180 g of butadiene was added and 6
Polymerization was carried out for 0 minutes. Next, add 0.5g of tetrachlorosilane.
was added and left for 30 minutes. In addition, the temperature was kept at 70° during the polymerization.
Adjusted to be C. After the polymerization was completed, 2,6-ditertiary-butyl-p-cresol was added, and then cyclohexane was removed by heating to obtain a radial block copolymer. The bound styrene content of this block copolymer is 70%
The weight average molecular weight was 220,000. This will be referred to as block copolymer C.

(Examples and Comparative Examples) Using the following vinyl aromatic polymer, thermoplastic elastomer, and copolymer, and using a 190°C plastomill (newly manufactured by Toyo Seiki Seisakusho) with the composition shown in Table 1, 50°C was used at 60 rpm.
These compression molded products were obtained by kneading for a minute and their physical properties were measured.

In addition, the following materials were used as shown in Tables 1 and 2.

(a) Ingredients: Styrene resin TOPOLEX 525 (Mitsui Toatsu Chemical) ABS, JS
RABS12 (manufactured by Japan Synthetic Rubber Co., Ltd.) ・Polyphenylene ether noryl 731J (manufactured by GE Plastics) (b) component ・Thermoplastic polyurethane nylastmark Ramilon 1190 (manufactured by Kuraray) ・Thermoplastic polyester elastomer PIBIF (EX46CM) (manufactured by Japan Synthetic Rubber Co., Ltd.) ) ・Thermoplastic polyamide elastomer FEBAX 4033 (manufactured by Atochem) (c) component ・Hydrogenated block copolymer Kraton G1650 (shell chemical type) (hydrogenated block copolymer A) Kraton G1657 (shell chemical type) (hydrogenated Block copolymer B) Styrene-isoprene-styrene copolymer SIS
5000 (Nippon Synthetic Rubber) Component (d) Styrene-maleic anhydride copolymer Moremax-UG830 (Idemitsu Petrochemical System) (Copolymer I) M n = 220,000 styrene/maleic anhydride-86/14M5X -200
0 (manufactured by Sanyo Chemical Industries) (copolymer ■) M n = 10,000 styrene/maleic anhydride-9515 styrene-glycidyl methacrylic ester copolymer (
Copolymer ■) KZ-731 (manufactured by Arayo Kagaku Kogyo Co., Ltd.) M n = 40,000 styrene/glycidyl methacrylic ester = 90/10 - Polymer obtained by graft copolymerizing styrene and acrylonitrile to an ethylene-glycidyl methacrylic ester copolymer ( Graft copolymer weight) Modiper A-4400 (NOF) Ethylene/glycidyl methacrylic ester/styrene/acrylonitrile-59°5/10.5/9/21 - Graft copolymerization of styrene to ethylene-glycidyl methacrylic ester copolymer Polymer (graft copolymer ■) Modiper-A-4100 (NOF) Ethylene/glycidyl methacrylate ester/styrene-59,5/10
．． 5/ ・Polymer obtained by graft copolymerizing styrene to glycidyl methacrylic ester-styrene copolymer (graft copolymer ■) Rezeta GP500 (Toagosei Chemical Industry Co., Ltd.) ・Maleic anhydride modified ethylene-propylene rubber (graft copolymer ■ ) T7741P (manufactured by JSR) In addition, each physical property was measured by the following method.

・Vicat softening point ASTM D1525 (load 1kg) O Tensile property according to JIS K2SO3 ・Taper wear ASTM D1044 (wearing wheel H-22) ・Hot water resistance: After immersing the tensile test piece in hot water at 70℃ for 10 days, JIS K2SO3 Evaluation based on retention rate (%) under tension.

・Oil resistance JIS No. 2 cm square rectangular body with 2 mm thickness at 70℃
After being immersed in 1 oil for 1 day, the volume change rate (%) was evaluated according to JIS K2SO3.

O Impact resistance: Measured according to the notched Izot impact strength of OIS K7110).

Examples 1 to 22 are compositions of the present invention, which are excellent in impact resistance, heat resistance, tensile properties, abrasion resistance, hot water resistance, and oil resistance, and the objective compositions of the present invention can be obtained. It is being

Comparative Examples 1 and 2 that do not use component (d) of the present invention are (a)
The components (b) and (c) are not sufficiently compatible;
Poor tensile properties, abrasion resistance, hot water resistance, oil resistance, and impact resistance.

In Comparative Example 3, component (d) exceeds the scope of the present invention, and although heat resistance is improved, oil resistance, moldability, and impact resistance are poor.

Comparative Examples 4 to 6 are (a) component or (b) component, (c)
Comparative Example 7, in which the components were below the range of the present invention and had poor hot water resistance, while the component (a) was beyond the range of the present invention,
Poor heat resistance, impact resistance, abrasion resistance, and oil resistance.

Blank space below [Effects of the invention] Mixtures of conventional vinyl aromatic copolymers and polyurethane elastomers, polyamide elastomers, or polyester elastomers have low Vicat softening points, low tensile strength, low impact resistance, low elongation, and low wear. It is not large enough to be of practical use.

Furthermore, the transparency was poor, and the two were not compatible.

However, as in the present invention, a vinyl aromatic polymer or a mixture of the same and polyphenylene ether, a diene copolymer, and a thermoplastic polyester elastomer, a thermoplastic polyamide elastomer, or a thermoplastic polyurethane elastomer further has a functional group. Those blended with a polymer of a compound or an olefin elastomer having a functional group are found to have significantly improved Vicat softening point and impact strength, and are highly heat resistant compositions. Furthermore, tensile strength and elongation are improved, and an improvement in wear value is also observed. Furthermore, a composition with excellent oil resistance can be obtained.

The composition of the present invention is a material with excellent properties as described above, and is useful for hoses, tubes, footwear, industrial parts, automobile interior and exterior parts, toys, daily necessities, films, medical products, adhesives, paints, etc. It can be suitably used and is an industrially valuable material.

Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] (1) (a) At least one member selected from (a-1) a homopolymer of a vinyl aromatic compound, and (a-2) a vinyl aromatic compound and a vinyl cyanide compound, a conjugated diene compound, and a monoolefin hydrocarbon compound 50-96% by weight of random or graft copolymer with seeds, (b) (b-1) thermoplastic polyurethane elastomer,
(b-2) 2 to 40% by weight of at least one selected from thermoplastic polyester elastomers and (b-3) thermoplastic polyamide elastomers; (c) (c-1) polymers mainly composed of vinyl aromatic compounds; At least one selected from a block copolymer consisting of a combined block and a polymer block mainly composed of a conjugated diene compound, and (c-2) a hydrogenated product of a copolymer of a vinyl aromatic compound and a conjugated diene compound. Seeds 2-30% by weight,
and (d) having at least one functional group selected from a hydroxyl group, a carboxyl group, an acid anhydride group, and an epoxy group (
The co)polymer is combined with the above components (a), (b) and (c).
) A thermoplastic polymer composition containing 1 to 50 parts by weight based on 100 parts by weight of the total amount of components.