JP2001011141A - Graft copolymer and thermoplastic resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a graft copolymer capable of giving a thermoplastic resin composition with its mechanical properties maintained while improving its flowability, and also capable of giving molded products with good surface appearance from the above resin composition. SOLUTION: This graft copolymer is composed of (A) segment consisting of, as constituent, at least one polymer selected from (1) a thermoplastic elastomer, (2) a polymer and/or copolymer made from a nonpolar α-olefin monomer and (3) a copolymer made from a nonpolar α-olefin monomer and a polar vinyl monomer and (B) another kind of segment consisting of, as constituent, a polymer or copolymer made from a monomer mixture comprising an unsaturated carboxylic acid 8-24C alkyl ester monomer, wherein the structure of this graft copolymer is such that one of two kinds of the segments forms a disperse phase as microparticles each 0.001-10 μm in size in the other segment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a graft copolymer useful as a fluidity improver for thermoplastic resins, especially thermoplastic elastomers, and a thermoplastic resin composition containing the same which is excellent in fluidity during molding and the like. It is about things.

[0002]

2. Description of the Related Art Thermoplastic resins, especially thermoplastic elastomers, are effective in a wide range of fields such as automobile parts, electric and electronic machine parts, and industrial parts as substitutes for soft PVC and rubber in place of recent environmental problems, recycling problems, and energy saving. Used and has greatly increased its demand. However, thermoplastic elastomers have drawbacks such as low fluidity and poor moldability. Therefore, plasticizers and process oils are generally used for the purpose of improving plasticization and flowability. However, although plasticization and flowability are improved, tensile strength,
There is a problem that various physical properties such as oil resistance are reduced. Generally, process oils used for the purpose of improving plasticization and fluidity improve plasticization and fluidity,
Since it is a low molecular weight compound, it bleeds out of the resin when used in large amounts, which limits the amount of addition and lowers various physical properties such as tensile strength and oil resistance.

In order to solve these problems, Japanese Patent Application Laid-Open No. Hei 6-136070 discloses that a thermoplastic resin such as polyphenylene ether or polycarbonate is added to a non-polar α-olefin monomer homopolymer or Copolymers of two or more non-polar α-olefin monomers, copolymers formed from non-polar α-olefin monomers and different polar vinyl monomers, and poly (C1 to C7) It is disclosed that by adding a graft polymer with a vinyl monomer such as (meth) acrylic acid ester or polystyrene as a fluidity improver and increasing the molecular weight, fluidity can be improved without bleeding out. Improvement was desired.

[0003] The present invention has been made in view of the above problems, and its object is to maintain mechanical properties while maintaining
It is an object of the present invention to provide a graft copolymer capable of exhibiting excellent fluidity during molding of a thermoplastic resin, particularly a thermoplastic elastomer, and a thermoplastic resin composition having improved fluidity due to the graft copolymer.

[0004]

In order to achieve the above object, the graft copolymer according to the first aspect of the present invention comprises a thermoplastic elastomer, a polymer formed from a non-polar α-olefin monomer, and / or a copolymer. Segment (A) having one or more of a polymer and a copolymer formed from a non-polar α-olefin monomer and a polar vinyl monomer as a constituent part, and an unsaturated carboxylic acid having 8 carbon atoms (B) comprising a polymer or copolymer as a constituent part, which is formed from a monomer mixture containing an alkyl ester of from 24 to 24, wherein one of the two segments is 0.00
It is characterized in that a dispersed phase is formed as fine particles of 1 to 10 μm.

[0005] A second aspect of the invention is characterized in that the thermoplastic resin contains the graft copolymer of the first aspect.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. The segment (A) constituting the graft copolymer of the present invention is a thermoplastic elastomer, an olefin polymer or a copolymer formed from a nonpolar α-olefin monomer, and a nonpolar α-olefin monomer. And one or more copolymers formed from a polar vinyl monomer.

The thermoplastic elastomer of the segment (A) constituting the graft copolymer specifically includes a styrene elastomer, an olefin elastomer, a PVC elastomer, a urethane elastomer, a polyester elastomer, a nitrile elastomer, Polyamide elastomer, fluorine elastomer, urethane PVC elastomer, chlorinated polyethylene, trans1,
4 isoprene, silicone elastomers and the like. Among these resins, styrene-based elastomers, olefin-based elastomers, and urethane-based elastomers are particularly preferred because of their excellent fluidity improving effect.

The styrene-based elastomer is a block copolymer containing at least one polymer of a vinyl aromatic monomer and at least one polymer of a conjugated diene. It may be a type. Further, the polymer containing the conjugated diene may be a random copolymer with a small amount of a vinyl aromatic monomer, or a so-called taper type block in which the amount of the vinyl aromatic monomer gradually increases. No problem. The structure of the block copolymer is not particularly limited, and any of (AB) _n- type, (AB) _n- A type, and (A, B) _n- C type can be used. In the formula, A represents a polymer of a vinyl aromatic monomer, B represents a polymer of a conjugated diene, C represents a residue of a coupling agent, and n represents an integer of 1 or more. In the above block copolymer, it is also possible to use a block copolymer in which the conjugated diene portion has been hydrogenated.

Specific examples of the vinyl aromatic monomer constituting the styrene-based elastomer include styrene, α-styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and vinyl naphthalene. And styrene is particularly preferred. As the conjugated diene, 1,3-butadiene, isoprene, piperylene and the like are used.
-Butadiene, isoprene are particularly preferred.

The weight average molecular weight of the styrenic elastomer is preferably from 10,000 to 800,000, more preferably from 50,000 to 500,000. The content of the vinyl aromatic monomer in the block copolymer is 5-6.
It is preferably 0% by weight, more preferably 10 to 50% by weight.

Specific examples of such styrene-based elastomers include diblock copolymers such as styrene-styrene-butadiene rubber and styrene-styrene-isoprene rubber, and hydrogenated products thereof, styrene-butadiene-styrene, styrene-isoprene- rubber. Examples include triblock copolymers such as styrene and styrene-butadiene / isoprene-styrene, and hydrogenated products thereof.

The olefin-based elastomer is an elastomer containing, as constituents, an olefin-based copolymer rubber component and a crystalline olefin-based polymer, and it is preferable that these are bonded and crosslinked.

The olefin copolymer rubber constituting the olefin elastomer comprises a copolymer of at least one polyene (usually a diene) and two or more nonpolar α-olefin monomers. It is essentially an amorphous rubbery copolymer, with EPDM and EPR being preferred.

The above-mentioned crystalline olefin polymer constituting the olefin elastomer is obtained by polymerizing a non-polar α-olefin monomer such as ethylene, propylene, butene-1 or pentene-1 by a conventional method. It is a crystalline polymer obtained. Typically, polyethylene and its copolymer, polypropylene and its copolymer, polybutene and the like can be mentioned, but polypropylene and its copolymer are preferable.

The ratio of the olefin-based copolymer rubber to the crystalline olefin-based copolymer is usually 40 to 80% by weight of the olefin-based copolymer rubber and 6% for the crystalline olefin-based polymer.
0-20% by weight is preferred. Both components are kneaded at a temperature higher than the melting point to form an olefin-based elastomer.

In order to impart useful properties as an elastomer, it is preferable to vulcanize the olefin copolymer rubber. In this case, the kneading treatment is performed by vulcanizing a peroxide, a phenol resin, sulfur, or the like. It is performed in the presence of the agent.

Specifically, a propylene / ethylene propylene diene copolymer blend or a crosslinked product,
Ethylene propylene rubber copolymer blend or crosslinked product, ethylene / ethylene-vinyl acetate copolymer, ethylene
/ Ethylene-ethyl acrylate copolymer, ethylene / ethylene-glycidyl methacrylate copolymer and the like.

The olefin-based elastomer may contain other components as long as the rubber properties and the like are not impaired. Specific examples include oils, fillers, carbon black, stabilizers and the like.

The urethane-based elastomer is obtained through a urethane bond in a molecule by a polyaddition reaction using a long-chain polyol, a short-chain polyol, a short-chain glycol, diisocyanate or the like as a raw material. It is a polymer. Long-chain polyols, which are raw materials for this urethane-based elastomer, include poly (1,4-butylene adipate), poly (1,6-hexane adipate), polycaprolactone, polyethylene glycol, and polypropylene glycol. And polyoxytetramethylene glycol. Also, short-chain glyco-
Include ethylene glycol, 1,4-butanediol-
And 1,6-hexanediol, and the diisocyanate further includes tolylene diisocyanate,
4,4-diphenylmethanedisocionate, hexamethylenediisocyanate, isophoronediisocyanate and the like. A soft segment is formed by long-chain polyol and diisocyanate, and a hard segment is formed by short-chain glycol and diisocyanate.

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

The polymer or copolymer formed from the non-polar α-olefin monomer of the segment (A) forming the graft copolymer refers to a polymer or copolymer obtained by high-pressure radical polymerization, medium-low pressure ionic polymerization or the like. It refers to a homopolymer of a polar α-olefin monomer or a copolymer of two or more non-polar α-olefin monomers. Here, ethylene or propylene is preferable as the non-polar α-olefin monomer, and butene-1, hexene-1, octene-1, and 4-methylpentene-1 as other nonpolar α-olefin monomers. Is mentioned.

Specific examples of the non-polar α-olefin (co) polymer include low-density polyethylene, ultra-low-density polyethylene, ultra-low-density polyethylene, low-molecular-weight polyethylene, polypropylene, polybutene, and ethylene-propylene copolymer. Can be mentioned. These non-polar α-olefin (co) polymers can also be used as a mixture.

The polar vinyl monomer in the copolymer formed from the non-polar α-olefin monomer of the segment (A) forming the graft copolymer and the polar vinyl monomer is a non-polar α -A monomer having a vinyl group copolymerizable with an olefin monomer. Examples include acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1)-
Α, β-unsaturated carboxylic acids such as 5-heptene-2,3-dicarboxylic acid and metal salts thereof, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, acrylic 2-ethylhexyl acid, methyl methacrylate, ethyl methacrylate,
Α, β-unsaturated carboxylate esters such as n-butyl methacrylate and isobutyl methacrylate, vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl stearate and vinyl vinyl acetate Examples include esters, unsaturated glycidyl group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and monoglycidyl itaconate.

Specific examples of the copolymer comprising a non-polar α-olefin monomer and a polar vinyl monomer include ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-acrylic acid Ethyl copolymer, ethylene-isopropyl acrylate copolymer, ethylene-n-butyl acrylate copolymer, ethylene-isobutyl acrylate copolymer, ethylene-2-ethylhexyl acrylate copolymer, ethylene-methacrylic acid copolymer Polymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-isopropyl methacrylate copolymer, ethylene-n-butyl methacrylate copolymer, ethylene-isobutyl methacrylate copolymer,
Ethylene-2-ethylhexyl methacrylate copolymer,
Ethylene-vinyl acetate copolymer, ethylene-vinyl propionate copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer, ethylene-ethyl acrylate-glycidyl methacrylate copolymer, ethylene-vinyl acetate-methacrylic acid Glycidyl copolymer, ethylene-glycidyl methacrylate copolymer and the like can be mentioned. These resins can be appropriately selected and used according to the respective properties.

These thermoplastic elastomers, non-polar α-olefin (co) polymers, and copolymers formed from non-polar α-olefins and polar vinyl monomers may be used alone as a mixture. Can also. Also,
Thermoplastic elastomer, non-polar α-olefin (co)
A mixture of a polymer and a copolymer formed from a nonpolar α-olefin and a polar vinyl monomer can also be used.

Next, the segment (B) constituting the graft copolymer is a (co) polymer formed from a monomer mixture containing an alkyl ester of an unsaturated carboxylic acid having 8 to 24 carbon atoms. . Unsaturated carboxylic acid having 8 to 2 carbon atoms
Specific examples of the alkyl ester monomer of No. 4 include alkyl ester monomers having 8 to 24 carbon atoms of acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid and itaconic anhydride. More specifically, octyl-, ethylhexyl-, isooctyl-, decyl-, isodecyl-, undecyl-, dodecyl-, isododecyl-, butyloctyl-, tridecyl-, tetradecyl-, pentadecyl-, hexadecyl-, heptadecyl-, octadecyl-, Examples include alkyl ester monomers such as isostearyl-, hexyllauryl-, and behenyl-.

Specifically, octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, decyl acrylate, isodecyl acrylate, undecyl acrylate, dodecyl acrylate, isododecyl acrylate, butyl octyl acrylate, tridecyl acrylate, Acrylates such as tetradecyl acrylate, pentadecyl acrylate, hexadecyl acrylate, heptadecyl acrylate, octadecyl acrylate, isostearyl acrylate, hexyl lauryl acrylate, behenyl acrylate, octyl methacrylate, 2-ethylhexyl methacrylate, Isooctyl methacrylate, decyl methacrylate, isodecyl methacrylate,
Undecyl methacrylate, dodecyl methacrylate, isododecyl methacrylate, butyl octyl methacrylate,
Tridecyl methacrylate, tetradecyl methacrylate,
Methacrylates such as pentadecyl methacrylate, hexadecyl methacrylate, heptadecyl methacrylate, octadecyl methacrylate, isostearyl methacrylate, hexyl lauryl methacrylate, and behenyl methacrylate; fumaric esters such as octyl fumarate and 2-ethylhexyl fumarate Octyl itaconate,
Examples include itaconic esters such as 2-ethylhexyl itaconic acid.

These monomers can be used alone or as a mixture. Of these, alkyl methacrylates having 8 to 24 carbon atoms are particularly preferred because of their excellent fluidity.

Besides, vinyl aromatic monomers such as styrene, nuclear-substituted styrene such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, α-substituted styrene such as α-methylstyrene and α-ethylstyrene, Acrylic acid or methacrylic acid, carbon number 1 of acrylic acid or methacrylic acid
Alkyl esters of 7, for example, methyl-, ethyl-, propyl-, isopropyl-, butyl-, glycidyl-, 2-hydroxyethyl-, 2- (meth) acrylic acid
(Meth) acrylic acid ester monomers such as hydroxypropyl-, vinyl cyanide such as acrylonitrile or methacrylonitrile, vinyl esters such as vinyl acetate and vinyl propionate, (meth) acrylamides such as acrylamide and methacrylamide, and maleic anhydride One to two or more of maleimides such as acid, phenylmaleimide and cyclohexylmaleimide, and vinyl monomers such as mono- and di-esters of maleic acid may be used in an amount of 0 to 95% by weight.

The graft copolymer of the present invention contains the segment (A) or segment (B) matrix
Segment (A) or segment (B), which is a different component, is almost uniformly dispersed in fine particles, usually spherical.

The fine dispersed particle diameter is usually 0.001 to
It is 10 μm, preferably 0.01 to 5 μm. When the dispersed particle diameter is less than 0.001 μm or more than 10 μm, the dispersibility of the graft copolymer when blended with a thermoplastic resin, particularly a thermoplastic elastomer, becomes insufficient, and the appearance deteriorates, and the tensile strength and It is not preferable because mechanical properties such as elongation are reduced.

The vinyl (co) polymer of the segment (B) constituting the graft copolymer of the present invention has a number average degree of polymerization of 5 to 10,000, preferably 10 to 5,000. If the number average degree of polymerization is less than 5, the fluidity of the thermoplastic resin composition of the present invention can be improved, but heat resistance is lowered and appearance is deteriorated, which is not preferable. On the other hand, if the number average polymerization degree exceeds 10,000, the melt viscosity is high, and the moldability is lowered and the surface gloss is lowered.

In the graft copolymer of the present invention, the segment (A) preferably comprises 5 to 95% by weight, more preferably 20 to 90% by weight. Therefore, the vinyl (co) polymer portion of the segment (B) is preferably 95 to 5% by weight, more preferably 80 to 10% by weight.

When the content of the segment (A) is less than 5% by weight and 95%
If the amount is more than 10% by weight, the fluidity improving effect is insufficient, and the mechanical properties are undesirably reduced.

The grafting method for producing the graft copolymer of the present invention may be any of the well-known methods such as chain transfer method and ionizing radiation irradiation method. This is based on the method shown. This is because the grafting efficiency is high and secondary aggregation due to heat does not occur, so that the expression of performance is more effective and the production method is simple.

Hereinafter, the method for producing the graft copolymer of the present invention will be described in detail. That is, segment (A)
100 parts by weight are suspended in water. Then, at least one
5 to 400 parts by weight of a vinyl monomer of the following general formula 1
Or 0.1 to 10 parts by weight of the radical polymerizable organic peroxide represented by 2 with respect to 100 parts by weight of the vinyl monomer, and a half-life of 10 hours. A radical polymerization initiator having a decomposition temperature of 40 to 90 ° C. to obtain was obtained by dissolving 0.01 to 5 parts by weight based on 100 parts by weight of the total of the vinyl monomer and the radical polymerizable organic peroxide. Add solution.

Then, the segment (A) is impregnated with a vinyl monomer, a radically polymerizable organic peroxide and a radical polymerization initiator by heating under a condition that decomposition of the radical polymerization initiator does not substantially occur. The temperature of the aqueous suspension is raised, and the vinyl monomer and the radical polymerizable organic peroxide are copolymerized in the segment (A) to obtain a graft precursor.

This grafting precursor is also a thermoplastic resin having a multi-phase structure and serves as a fluidity improver. Therefore, the grafting precursor may be directly melt-mixed with a thermoplastic resin, especially a thermoplastic elastomer.

Further, the grafting precursor is used in an amount of 100 to 300.
The graft copolymer of the present invention can be obtained by kneading in a molten state at a temperature of ° C. At this time, a thermoplastic resin, particularly a thermoplastic elastomer or an olefin (co) polymer or a vinyl (co) is added to the grafting precursor.
Even if the polymers are mixed and kneaded while being melted, a graft copolymer can be obtained. Most preferred is a graft copolymer obtained by kneading a grafting precursor.

The radically polymerizable organic peroxide represented by the general formula 1 is the following compound.

[0041]

Embedded image In the formula, R ¹ is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms, R ² is a hydrogen atom or a methyl group, R ³ and R
⁴ represents an alkyl group having 1 to 4 carbon atoms, and R ⁵ represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. m is 1 or 2.

The radically polymerizable organic peroxide represented by the general formula 2 is the following compound.

[0043]

Embedded image In the formula, R ⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ⁷ is a hydrogen atom or a methyl group, R ⁸ and R ⁹ are each an alkyl group having 1 to 4 carbon atoms, and R ¹⁰ is 1 carbon atom.
And represents an alkyl group, a phenyl group, an alkyl-substituted phenyl group or a cycloalkyl group having 3 to 12 carbon atoms.
n is 0, 1 or 2.

Specific examples of the radical polymerizable organic peroxide represented by the general formula 1 include t-butylperoxyacryloyloxyethyl carbonate and t-amylperoxyacryloyloxyethyl carbonate. Tert-hexylperoxyacryloyloxyethyl carbonate;
1,1,3,3-tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate , T
-Butyl peroxymethacryloyloxyethyl carbonate, t-amylperoxymethacryloyloxyethyl carbonate, t-hexylperoxymethacryloyloxyethyl carbonate, 1,1,3,3-tetra Methyl butyl peroxymethacryloyloxyethyl carbonate
G, cumyl peroxymethacryloyloxyethyl carbonate, p-isopropylcumylperoxymethacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate-carbonate, t-amyl Peroxyacryloyloxyethoxyethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate, 1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate, Cumyl peroxyacryloyloxyethoxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate, t-butylperoxymethacryloyloxyethoxyethyl carbonate
Bonate, t-amyl peroxymethacryloyloxyethoxyethyl carbonate, t-hexylperoxymethacryloyloxyethoxyethyl carbonate, 1,1,
3,3-tetramethylbutyl peroxymethacryloyloxyethoxyethyl carbonate, cumyl peroxymethacryloyloxyethoxyethyl carbonate, p-isopropylcumylperoxymethacryloyloxyethoxyethyl carbonate, t-butyl peroxyacryloyloxyisopropyl carbonate, t-amylperoxyacryloyloxyisopropyl carbonate, t-
Hexyl peroxyacryloyloxy isopropyl car
Bonnet, 1,1,3,3-tetramethylbutyl peroxyacryloyloxyisopropyl carbonate, cumyl peroxyacryloyloxyisopropyl carbonate
P-isopropylcumylperoxyacryloyloxyisopropylcarbonate, t-butylperoxymethacryloyloxyisopropylcarbonate, t-amylperoxymethacryloyloxyisopropylcarbonate, t-hexylperoxy Methacryloyloxyisopropyl carbonate, 1,1,3,3-tetramethylbutylperoxymethacryloyloxyisopropyl carbonate, cumylperoxymethacryloyloxyisopropyl carbonate, p-isopropylcumyl Peroxymethacryloyloxyisopropyl carbonate and the like can be exemplified.

Further, the compounds represented by the general formula 2 include t-butylperoxyallylcarbonate, t-butylperoxyallylcarbonate and t-butylperoxyallylcarbonate.
Amyl peroxy allyl carbonate, t-hexyl peroxy allyl carbonate, 1,1,3,3-tetramethylbutyl peroxy allyl carbonate, p-menthane peroxy allyl carbonate, Cumyl peroxyallyl carbonate, t-butyl peroxymethallyl carbonate
Bonate, t-amyl peroxymethallyl carbonate
G, t-hexyl peroxymethallyl carbonate,
1,1,3,3-tetramethylbutyl peroxymethallyl carbonate, p-menthane peroxymethallyl carbonate, cumyl peroxymethallyl carbonate, t-
Butyl peroxyallyloxyethyl carbonate, t-
Amyl peroxyallyloxyethyl carbonate, t-
Hexyl peroxyallyloxyethyl carbonate, t
-Butyl peroxymetalaryloxyethyl carbonate,
t-amyl peroxymetalaryloxyethyl carbonate;
t-hexyl peroxymetalaryloxyethyl carbonate
G, t-butyl peroxyallyloxyisopropyl car
Carbonate, t-amylperoxyaryloxyisopropyl carbonate, t-hexylperoxyallyloxyisopropyl carbonate, t-butylperoxymetalaryloxyisopropyl carbonate, t-amylperoxymetalloxyisopropyl carbonate Examples thereof include carbonate and t-hexylperoxymetalaryloxyisopropyl carbonate.

Of these, t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-butylperoxyallylcarbonate, t-butylperoxy Methallyl carbonate.

The thermoplastic resin used in the present invention includes:
Polyamide resin, polyester resin, polyacea
Engineering plastics such as polyester resins, polycarbonate resins, polyphenylene ether resins, polyphenylene ether resins, and polyarylate resins; olefin resins such as polyethylene and polypropylene; polystyrene; Impact polystyrene,
General-purpose plastics such as styrene resin such as ABS, acrylic resin, and vinyl chloride resin, and thermoplastic elastomers such as styrene thermoplastic elastomer, olefin thermoplastic elastomer, and urethane thermoplastic elastomer can be given.

Among these resins, polycarbonate resins, polyphenylene ether resins, polyarylate resins, olefin resins, styrene resins, acrylic resins and vinyl chloride resins, and styrene resins are particularly preferred. Thermoplastic elastomers, olefin-based thermoplastic elastomers, and urethane-based thermoplastic elastomers have a high fluidity improving effect.

In the present invention, the graft copolymer is
The amount is preferably 0.1 to 60 parts by weight, more preferably 0.5 to 50 parts by weight, most preferably 1 to 40 parts by weight based on 100 parts by weight of the thermoplastic resin composition. When the amount of the graft copolymer is less than 0.1 part by weight, the fluidity is insufficiently improved, and when the amount exceeds 50 parts by weight, the appearance is deteriorated and the mechanical properties are deteriorated.

In the present invention, an inorganic filler can be compounded, and the compounding ratio thereof is the same as that of the thermoplastic resin, especially the resin component 1 containing the thermoplastic elastomer and the graft copolymer.
It is 150 parts by weight or less with respect to 00 parts by weight. If the amount of the inorganic filler is more than 150 parts by weight, the fluidity of the molded product is undesirably reduced.

The inorganic filler may be in the form of a powder, granules, a plate, a scale, a needle, a sphere, a hollow, a fiber, or the like. Specifically, calcium sulfate, calcium silicate, clay, diatomaceous earth, talc, alumina, silica sand, glass powder, iron oxide, metal powder, graphite, silicon carbide, silicon nitride, silica, boron nitride, aluminum nitride, carbon Powdery and granular fillers such as black; metal foils such as mica, glass plate, sericite, pyrophyllite, and aluminum flakes; and flat or scale-like fillers such as graphite; silas balloons, metal balloons, and glass balloons And hollow fibers such as glass fibers, carbon fibers, graphite fibers, whiskers, metal fibers, silicon carbide fibers, mineral fibers such as asbestos and wostonite.

The surface of the above-mentioned inorganic filler may be stearic acid, oleic acid, palmitic acid or a metal salt thereof,
It is preferable to apply a surface treatment using paraffin wax, polyethylene wax or a modified product thereof, organic silane, organic borane, organic titanate, or the like.

The thermoplastic resin composition of the present invention has a temperature of 1
Melting at 20-350 ° C, preferably 150-330 ° C
Produced by mixing. The above temperature is 120 ° C
If it is less than 1, melting is incomplete or the melt viscosity is high, mixing is insufficient, and phase separation or delamination appears in the molded product, which is not preferable. When the temperature exceeds 350 ° C.,
Decomposition or gelation of the mixed resin occurs, which is not preferable.

As a method of melting and mixing, Banbury
A method using a commonly used kneader such as a mixer, a pressure kneader, a kneading extruder, a twin-screw extruder, or a roll can be employed. Since the resin composition of the present invention has excellent fluidity, it can be molded by any one of injection molding, extrusion molding, vacuum molding, and blow molding. Among them, the injection molding method is more preferable from the viewpoint of fluidity and appearance of a molded product, the extrusion molding method is more preferable from the viewpoint of moldability and sheet appearance of a molded sheet, and the vacuum molding method is more preferable from the viewpoint of deep drawing formability.

In general, among thermoplastic resins, especially thermoplastic elastomers have poor flow properties, heat resistance and mechanical properties. On the other hand, the above-mentioned vinyl polymer is excellent in these properties as compared with the thermoplastic elastomer, but has a poor compatibility and therefore has little effect when added as it is. Accordingly, in the present invention, a graft copolymer forming a multiphase structure comprising a thermoplastic elastomer or a polyolefin-based (co) polymer portion having good compatibility with the thermoplastic elastomer and a vinyl-based polymer portion capable of exhibiting the above-mentioned properties is provided. Obtaining a polymer,
This graft copolymer was added to a thermoplastic resin, especially a thermoplastic elastomer. Therefore, the graft copolymer has good compatibility with the thermoplastic elastomer, is uniformly dispersed in the thermoplastic elastomer, and exists in a stable state. As a result, the flow characteristics of the thermoplastic resin composition are improved, the appearance of the surface of the molded product is excellent, and the mechanical properties such as tensile strength are not reduced.

In the present invention, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide, organic flame retardants such as halogen-based and phosphorus-based, and organic fillers such as wood powder can be used without departing from the gist of the present invention. Additives such as agents, antioxidants, UV inhibitors, lubricants, dispersants, coupling agents, foaming agents, crosslinking agents, coloring agents, and other thermoplastic resins and thermoplastic elastomers may be added.

[0057]

The present invention will be described below in more detail with reference to Reference Examples, Examples and Comparative Examples. (Reference Example 1, Production of Graft Copolymer (IIA)) _A stainless steel autoclave having a volume of 5 l was charged with 2500 g of pure water.
And polyvinyl alcohol as a suspending agent.
5 g were dissolved. Among them, hydrogenated styrene, which is a styrene-based thermoplastic elastomer as an olefin polymer,
700 g of butadiene-styrene triblock polymer “Septon 2063” (trade name, manufactured by Kuraray Co., Ltd.) was added, and the mixture was stirred and dispersed. Separately, 1.5 g of benzoyl peroxide "Nipper-B" (trade name, manufactured by NOF Corporation) as a radical polymerization initiator, and t-butylperoxymethacryloyloxyethyl carbonate as a radical polymerizable organic peroxide. 6 g and 1.5 g of n-dodecylmercaptan "1-dodecanethiol" (trade name, manufactured by NOF Corporation) as a molecular weight modifier were dissolved in 300 g of stearyl methacrylate as a vinyl monomer. -Introduced and stirred into a tocle.

Then, the autoclave was heated to 60 to 65 ° C. and stirred for 2 hours to obtain a vinyl monomer containing a radical polymerization initiator and a radically polymerizable organic peroxide.
Impregnated in hydrogenated styrene-butadiene-styrene triblock polymer. Next, raise the temperature to 80-85 ° C,
The temperature was maintained for 7 hours to complete the polymerization, followed by washing with water and drying to obtain a grafting precursor (IIa). The number average polymerization degree of the stearyl methacrylate polymer in the grafting precursor (IIa) was measured by high-temperature GPC (150-Cvplus Waters ™), and was 120.

Next, the grafting precursor (IIa)
Was extruded at 180 ° C. with a Labo Plastomill single-screw extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.), and a grafting reaction was performed to obtain a graft copolymer (II _A ).

[0060] Observation by the graft copolymer (II _A) a scanning electron microscope "JEOL JSM T300" (manufactured by JEOL Ltd.), particle size from 0.2 to 0.
It was a multiphase structure in which 4 μm spherical resin was uniformly dispersed.

At this time, the grafting efficiency of the stearyl methacrylate polymer was 55.1% by weight.

Reference Example 2, Graft Copolymer (II _B )
In Reference Example 1, "Septon 2063" was replaced by "TPE3885" which is an olefinic thermoplastic elastomer.
(Trade name, manufactured by Sumitomo Chemical Co., Ltd.), stearyl methacrylate as a 2-ethylhexyl methacrylate monomer, and 1.5 g of benzoyl peroxide as di-3,5,
The procedure of Reference Example 1 was repeated, except that 5 g of 5-trimethylhexanoyl peroxide "Paroyl 355" (trade name, manufactured by NOF Corporation) was used.
b) and a graft copolymer (II _B ) were obtained. At this time, the number average degree of polymerization of the 2-ethylhexyl methacrylate polymer in the graft copolymer (II _B ) was 180, and the graft efficiency was 62.5%. The resin dispersed in the graft copolymer (II _B ) has an average particle size of 0.1.
2 to 0.4 μm.

Reference Example 3, Graft Copolymer (II _C )
In Reference Example 1, "Septon 2063" was replaced with a urethane-based thermoplastic elastomer "Chramylon U8".
165 ”(trade name, manufactured by Kuraray Co., Ltd.), stearyl methacrylate to lauryl methacrylate, and 1.5 g of benzoyl peroxide to 3 g of“ paroyl 355 ”.
The graft copolymer (II _C ) was obtained by repeating Reference Example 1 except that the above was changed. At this time, the graft copolymer (II
The number average polymerization degree of the lauryl methacrylate copolymer in _C ) was 160, and the grafting efficiency was 53.9%. The average particle size of the resin dispersed in the graft copolymer (II _C ) was 0.3 to 0.5 μm.

Reference Example 4, Graft Copolymer (II _D )
Preparation of Reference Example 1 A graft copolymer (II _D ) was obtained by repeating Reference Example 1 except that stearyl methacrylate was changed to methyl methacrylate. At this time, the number average polymerization degree of the methyl methacrylate copolymer in the graft copolymer (II _D ) was 180, and the graft efficiency was 5
9.7%. The average particle diameter of the resin dispersed in the graft copolymer (II _D ) is 0.2 to 0.4 μm.
Met.

(Reference Example 5, Graft Copolymer (II _E )
In Reference Example 1, "Septon 2063" was replaced with ethylene-ethyl acrylate copolymer "Lexlon A4200"
Reference Example 1 was repeated except that (trade name, manufactured by Nippon Polyolefin Co., Ltd.) was used.
_IE ) was obtained. At this time, the number average polymerization degree of the stearyl methacrylate polymer in the graft copolymer (II _E ) was 1
20, the grafting efficiency was 55.2%. The resin dispersed in the graft copolymer (II _E ) had an average particle size of 0.2 to 0.4 μm.

(Reference Example 6, Graft Copolymer (II _F )
Production of Reference Example 5 The procedure of Reference Example 5 was repeated except that 300 g of stearyl methacrylate was changed to 60 g of stearyl methacrylate and 240 g of lauryl methacrylate, and 1.5 g of benzoyl peroxide was changed to 3 g of "paroyl 355". Combined (II _F )
I got At this time, the number average polymerization degree of stearyl methacrylate and lauryl methacrylate copolymer in the graft copolymer (II _F ) was 140, and the graft efficiency was 57.1%.
Met. The resin dispersed in the graft copolymer (II _F ) had an average particle size of 0.2 to 0.4 μm.

(Reference Example 7, Graft Copolymer (II _G )
In Reference Example 1, except that “Septon 2063” was changed to polypropylene “Sumitomo Noblen S131” (trade name, manufactured by Sumitomo Chemical Co., Ltd.) and stearyl methacrylate was changed to 2-ethylhexyl methacrylate.
Reference Example 1 was repeated to obtain a graft copolymer (II _G ). At this time, the number average polymerization degree of the 2-ethylhexyl methacrylate polymer in the graft copolymer (II _G ) was 18
0, the grafting efficiency was 52.8%. The resin dispersed in the graft copolymer (II _G ) had an average particle size of 0.3 to 0.5 μm.

(Reference Example 8, Graft Copolymer (II _H )
In manufacturing) Reference Example 1, "Septon 2063" polyethylene "Sumikathene G401" was changed to (trade name, manufactured by Sumitomo Chemical Co., Ltd.), the graft copolymer by repeating Example 1 _(II H) I got At this time, the number average polymerization degree of the stearyl methacrylate polymer in the graft copolymer (II _H ) was 170, and the graft efficiency was 62.
1%. The average particle size of the resin dispersed in the graft copolymer (II _H) is 0.3~0.5μm
Met.

(Reference Example 9, Graft Copolymer (II _I )
Production of 60 g of the grafting precursor (IIa) obtained in Reference Example 2, 28 g of “Septon 2063”, and polylauryl methacrylate (described in the ALDRICH catalog, Mw = 4)
7000) was extruded at 180 ° C. with a Labo Plastomill single screw extruder to obtain a graft copolymer (II _I ). At this time, the graft efficiency of the stearyl methacrylate polymer in the graft copolymer was 26.8%. Further, the graft copolymer (II)
The average particle size of the resin dispersed in _I ) is from 0.6 to 0.5.
It was 8 μm.

(Reference Example 10, Production of Blend (II _J )) 500 g of “Septon 2063” and 500 g of polylauryl methacrylate were extruded at 180 ° C. with a Labo Plastomill single screw extruder (manufactured by Toyo Seiki Seisaku-sho, Ltd.).
A blend (II _J ) was obtained. At this time, the blend (I
The grafting efficiency of the polylauryl methacrylate polymer in I _J ) was 0.1% or less. The resin dispersed in the blend (II _J ) has an average particle size of 15 μm.
m.

Examples 1 to 6 and Comparative Examples 1 and 2 Graft copolymers II _A , II _D and I obtained in Reference Examples
_{I E, II F, II G} , II H, II I, a II _J 30
After dry blending 70% by weight of “Septon 2063” by weight, the mixture was supplied to a coaxial twin-screw extruder having a screw diameter of 30 mm set at a cylinder temperature of 180 ° C., and granulated after extrusion. The granulated resin is dried at 60 ° C. for 24 hours,
The following tests were performed. Table 1 shows the results. (1) Tensile test: No. 2 dumbbell used (2) MFR: 190 ° C 2.16 kgf or 190 ° C 5 kgf (3) Spiral flow: Injection molding machine (manufactured by Tabata Machine Industry Co., Ltd. TS-
35-FV25 type), a mold having a semicircular Φ4.8 mm spiral groove was mounted, the injection speed was 95%, and the injection pressure was 800.
Injection molding is performed under the conditions of kgf / cm ² and mold temperature of 40 ° C.
The length of the formed spiral was measured and used as an index of fluidity. (4) Appearance of Molded Article The appearance of the molded article was visually judged for the presence or absence of delamination, and ranked as follows. State of delamination ：: No delamination at all △: Slight delamination X: Delamination

[0072]

[Table 1]

Examples 7 to 12 and Comparative Example 3 Graft copolymers II _B , II _E and I obtained in Reference Examples
_{I F, II G, II H} , II I, a II _J 30 wt%,
The same test as in the above example was conducted except that 70% by weight of "TPE3885" was dry blended. Table 2 shows the results.

[0074]

[Table 2]

Examples 13 to 18 and Comparative Example 4 Graft copolymers II _C , II _E and I obtained in Reference Examples
_{I F, II G, II H} , II I, a II _J 30 wt%,
The same test as in the above example was conducted except that 70% by weight of "Chramiron U8165" was dry blended. Table 3 shows the results.

[0076]

[Table 3]

[0077] Except for changing the blending amount of the graft copolymer II _E obtained in Examples 19 to 22 and Comparative Example 6 Reference Example "TPE3885", was subjected to the same test as in the Example. Table 4 shows the results.

[0078]

[Table 4]

Comparative Example 7 30% by weight of process oil and "Septon 2063" 7
The same test as in the above example was performed except that 0% by weight was dry blended. Table 5 shows the results.

[0080] The graft copolymer II _A obtained in Example 23 Reference Example 10% by weight, polyphenylene - ether (IA) "NORYL 534J-80
1 "(trade name, manufactured by Japan-A-Plastic Co., Ltd.)
After 90% by weight of dry blending (indicated in the table as PPE), the mixture was fed to a coaxial twin-screw extruder with a screw diameter of 30 mm set at a cylinder temperature of 200 to 250 ° C., and granulated after extrusion. The granulated resin was dried at 60 ° C. for 24 hours and subjected to the following test. Table 5 shows the results. (1) Bending test: JIS K6758 Bending test piece 10 mm × 130 mm × 4 mm (2) Spiral flow: Injection molding machine (TS-35-FV25, manufactured by Tabata Machine Industry Co., Ltd.) at the molding temperature shown in Table 6.
A mold having a semicircular Φ4.8 mm spiral groove is mounted on the mold, and injection molding is performed under the conditions of an injection speed of 95%, an injection pressure of 800 kgf / cm ² , and a mold temperature of 40 ° C. The length was measured and used as an index of fluidity. (3) Appearance of Molded Article The appearance of the molded article was visually judged for the presence or absence of delamination, and ranked as follows. State of delamination ：: No delamination at all △: Slight delamination X: Delamination

Example 24 The PPE of Example 23 was replaced with polypropylene “Nisseki Polypro J
150G "(trade name, manufactured by Nippon Petrochemical Co., Ltd.), and the same test as in Example 23 was performed. Table 5 shows the results.

[0082] Example 25 Graft copolymer II _C 10 wt% obtained in Reference Example, polyphenylene - ether (IA) "NORYL 534J-80
1 "(trade name, manufactured by Japan-A-Plastic Co., Ltd.)
The same test as in Example 23 was performed, except that 90% by weight (shown as PPE in the table) was dry-blended. Table 5 shows the results.

[0083] The graft copolymer II _E obtained in Example 26 Reference Example 10% by weight,
ABS resin (IC) "Stylac ABS 283"
The same test as in Example 23 was carried out except that 90% by weight (trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.) (shown in the table as ABS) was dry-blended. Table 6 shows the results.

Comparative Examples 8 to 11 The engineering plastics of Examples 23 to 26 were tested in the same manner as in Example 23. Table 5 shows the results.

[0085]

[Table 5]

From these results, it can be seen that the specific graft copolymer has a great effect on improving the fluidity of the thermoplastic resin, especially the thermoplastic elastomer, and the resin composition has a mechanical property higher than that of the comparative example. It can be seen that the resin composition has improved fluidity while being maintained.

[0087]

The graft copolymer of the present invention has a great effect on improving the fluidity of a thermoplastic resin, especially a thermoplastic elastomer. The thermoplastic resin composition containing this graft copolymer has a high mechanical property. While improving only the fluidity and maintaining the appearance of the molded product surface. Therefore, it can be widely used for automobile parts, electric / electronic parts, industrial parts and the like.

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Claims (2)

[Claims] 1. A thermoplastic elastomer, non-polar α-
One or more of a polymer or / and a copolymer formed from an olefin monomer and a copolymer formed from a non-polar α-olefin monomer and a polar vinyl monomer as a constituent part The segment (A) and the segment (B) having a polymer or copolymer formed from a monomer mixture containing an alkyl ester of an unsaturated carboxylic acid having 8 to 24 carbon atoms, A graft copolymer, wherein one of the two segments forms a dispersed phase as fine particles of 0.001 to 10 μm on the other. 2. A thermoplastic resin composition comprising the graft copolymer according to claim 1.