JP4463435B2 - Filler dispersibility improving material, filler-containing resin composition and production method thereof - Google Patents

Description

【０１２６】
【実施例３】
市販のエチレンプロピレンゴム（Ｂ２）（商品名：三井ＥＰＴ３０７０）９５重量部に、亜鉛華 ５重量部、ステアリン酸 １重量部、タルク（平均粒径１５μｍ）８０重量部、酸化チタンを２０重量部、流動パラフィン２０重量部、老化防止剤N-イソプロピル-N'-フェニル-p-フェニレンジアミンを１重量部、製造例３で得られたジブロック共重合体（ＥＰＲ−Ｏ−ＰＥＭＡ）５重量部を１．７リットルのバンバリーミキサーを用い１４０〜１５０℃で５分間混合した。得られた未加硫配合ゴムのムーニー粘度（ＭＬ1+4（１００℃））は４４であった。さらに得られたゴム組成物に、加硫促進剤テトラメチルチウラムモノスルフィドを０．５重量部、加硫促進剤N-オキシジエチレン-2-ベンゾチアゾールスルフェンアミドを１．２重量部、および硫黄１．５重量部を加え、６インチミキシングロール（前ロール、後ロールともに６０℃）で５分間混合し、厚さ３ｍｍのシートを得た。
【０１２７】
このようにして得られたシートからプレス成形機を用い、１６０℃で１０分間の、圧縮成形を行い、厚さ２ｍｍの加硫ゴムシートを得た。得られたシートについて、ＪＩＳ Ｋ ６３０１に基づき、測定温度２３℃、引張速度５００ｍｍ／分の引張試験を行い、破断伸びおよび破断強度を測定した。結果を表２に示す。
【０１２８】
【比較例３】
エチレンプロピレンゴム（Ｂ２）１００重量部、亜鉛華 ５重量部、ステアリン酸 １重量部、タルク ８０重量部、酸化チタンを２０重量部、流動パラフィン２０重量部、老化防止剤N-イソプロピル-N'-フェニル-p-フェニレンジアミンを１重量部用いて未加硫配合ゴムを製造した以外は、実施例３と同様にして、加硫ゴムを製造し、破断伸びおよび破断強度を測定した。結果を表２に示す。実施例３に比べ、ムーニー粘度が高く、破断強度が低い。
【０１２９】
【表２】

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a filler dispersibility improving material, a filler-containing resin composition and a method for producing the same, and more specifically, a filler dispersibility improving material capable of greatly improving the mechanical properties of polyolefin, and a filler-containing resin composition having excellent mechanical properties. Thing and its manufacturing method.
[0002]
BACKGROUND OF THE INVENTION
Polyolefins such as polypropylene and polyethylene are molded by various methods and used for various purposes. However, these materials may not have sufficient heat resistance, rigidity, and strength depending on applications, and in that case, they are reinforced with a filler such as talc or glass fiber. However, since polyolefin has low polarity and most fillers have polarity, the reinforcing effect of the filler is sufficient due to insufficient dispersion and poor adhesion at the interface between the filler and polyolefin. Often not. For this reason, various silane coupling agents and titanate coupling agents may be added during the melt compounding, or the surface of the filler may be treated with a higher fatty acid, but the effect is not sufficient. .
[0003]
Attempts have also been made to obtain a composite material in which an organic polymer material is inserted between silicate layers constituting a layered silicate. For example, there is a clay mineral / polyamide resin composition characterized in that a layered silicate is treated with an amino acid or a nylon salt and further impregnated with a monomer for polymerization (Japanese Patent Publication No. 58-35211, Japanese Patent Publication No. 58-35542). Issue gazette). Japanese Laid-Open Patent Publication No. 62-74957 discloses a composite material in which a part of a polyamide polymer chain is ionically bonded to a silicate layer, and the thickness of the silicate layer constituting the layered silicate is 7 to 12 mm. A composite material in which a polyamide-containing resin is mixed into a silicate layer having an interlayer distance of 30 mm or more and a part of the polyamide polymer chain is ionically bonded to the silicate layer has also been reported.
[0004]
On the other hand, in polyolefin, a method of using a layered silicate that has been finely dispersed by melt-kneading a layered silicate treated with the above alkylamine-based swelling agent, a modified polyolefin and a polyolefin as a filler has been studied. However, this method did not have a sufficient reinforcing effect.
[0005]
OBJECT OF THE INVENTION
The present invention was made in order to solve the problems in the prior art as described above, and has a filler dispersibility improving material excellent in reinforcing effect and dispersibility improving effect, filler reinforcing property and dispersibility. It aims at providing the outstanding filler containing resin composition and its manufacturing method.
[0006]
Summary of the Invention
  The filler dispersibility improving material according to the present invention is characterized by comprising an olefin-based block copolymer (A) represented by the following general formula (I);
      PO-f-R (I)
(In the formula, PO represents a polyolefin segment composed of a repeating unit derived from an olefin having 2 to 20 carbon atoms, and having a weight average molecular weight of 2,000 or more, and f represents an ether bond.TheR is obtained by a chain polymerization reaction and has a weight average molecular weight of 500 or more.Methacrylate polymerIndicates a segment. ).
[0007]
The filler-containing resin composition according to the present invention is characterized by comprising the olefin block copolymer (A) and a filler.
The filler is preferably a layered silicate in which ions between layers are exchanged with organic ammonium ions.
The method for producing a filler-containing resin composition according to the present invention includes the step of polymerizing or copolymerizing an olefin having 2 to 20 carbon atoms, and then in the presence of the polyolefin obtained by the polymerization and a filler. The filler-containing resin composition is obtained by polymerization or copolymerization.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the filler dispersibility improving material, filler-containing resin composition and production method thereof according to the present invention will be specifically described.
The filler dispersibility improving material according to the present invention comprises the following olefin block copolymer (A).
[0009]
Olefin block copolymer (A)
The olefin block copolymer (A) is represented by the following general formula (I).
PO-f-R (I)
In the formula, PO is a polyolefin segment composed of repeating units derived from an olefin having 2 to 20 carbon atoms, and specifically, an olefin homopolymer or copolymer selected from olefins having 2 to 20 carbon atoms. It is a polymer. When this polyolefin segment has stereoregularity, it may be either isotactic polyolefin or syndiotactic polyolefin.
[0010]
Examples of the olefin having 2 to 20 carbon atoms include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, and nonconjugated dienes.
Specific examples of the linear or branched α-olefin include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -Methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene , 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc., 2 to 20, preferably 2 to 10 carbon atoms Can be mentioned.
[0011]
Examples of the cyclic olefin include those having 3 to 20 carbon atoms, preferably 5 to 15 such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p- Mono or polyalkyl styrenes such as ethyl styrene are mentioned.
[0012]
Examples of conjugated dienes include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,3-hexadiene. , 1,3-octadiene and the like having 4 to 20, preferably 4 to 10 carbon atoms.
Non-conjugated dienes include, for example, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2 -Methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1 , 4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene -2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2 -5 carbon atoms such as norbornadiene 0, preferably include the 5 to 10.
[0013]
The polyolefin segment has a weight average molecular weight of usually 2,000 or more, preferably 2,000 to 1,000,000, more preferably 2,000 to 500,000, particularly preferably 5,000 to 100,000. It is desirable to be in
Examples of the polyolefin segment include ethylene homopolymers, ethylene polymers such as ethylene / α-olefin copolymers; propylene polymers such as propylene homopolymers and propylene / α-olefin copolymers; butene homopolymers, Preferred are butene polymers such as butene / ethylene copolymer; 4-methyl-1-pentene polymers such as 4-methyl-1-pentene homopolymer.
[0014]
In the general formula (I), f is an ether bond, an ester bond or an amide bond, and among these, an ether bond is preferable. The part f chemically bonds the polyolefin segment and the following functional segment.
Note that f may include a part of the structure formed by the following chain polymerization reaction, for example, radical polymerization reaction, ring-opening polymerization reaction, or ionic polymerization reaction.
[0015]
In the general formula (I), R is a functional segment obtained by radical polymerization reaction, ring-opening polymerization reaction or ionic polymerization reaction, and represents a repeating unit containing an unsaturated hydrocarbon and / or a repeating unit containing a hetero atom. The functional segment is preferably contained, and more preferably obtained by radical polymerization reaction or ring-opening polymerization reaction. The PO and R are preferably segments made of different polymers.
[0016]
The repeating unit forming the functional segment is composed of radically polymerizable monomers such as methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate, vinyl acrylate (VA), butyl acrylate (BA), styrene, acrylonitrile, vinyl acetate and the like. Derived repeating units: lactones, lactams, 2-oxazolines, cycloethers such as β-propiolactone, β-butyrolactone, δ-valerolactone, glycolide, lactide, ε-caprolactone, α-pyrrolidone, γ And ring-opening polymerizable monomers such as -butyrolactam, ε-caprolactam, ethylene oxide, propylene oxide, epichlorohydrin, oxetane, tetrahydrofuran, and octamethylcyclotetrasiloxane.
[0017]
Examples of the ion polymerizable monomer include anionic polymerizable monomers such as (meth) acrylic acid ester, acrylonitrile, and acrylamide.
This functional segment has a weight average molecular weight (Mw) of usually 500 or more, preferably 500 to 1,000,000, more preferably 500 to 500,000, particularly preferably 1,000 to 500,000. It is desirable.
[0018]
Specific examples of the functional segment include a styrene homopolymer, a styrene polymer such as a styrene / maleic anhydride copolymer, a vinyl acetate polymer; an acrylate polymer; a methyl methacrylate homopolymer, Methacrylic acid ester polymer such as ethyl methacrylate homopolymer; vinylformamide polymer; acrylamide polymer, cyclic ester polymer; cyclic amide polymer; cyclic ether polymer; oxazoline polymer; Examples include a segment made of a fluorine-based polymer.
[0019]
The functional segment is preferably 0.01 to 99.99% by weight, preferably 1 to 99% by weight, more preferably 1 to 95% by weight, particularly preferably relative to the olefinic block copolymer (A). It is preferably included in an amount of 5 to 90% by weight.
The melt flow rate (MFR; ASTM D 1238, 230 ° C., load 2.16 kg) of the olefin block copolymer (A) used in the present invention is usually 0.01 to 2000 g / 10 min, preferably 0.05. It is desirable to be -1000 g / 10 minutes, more preferably 0.1-1000 g / 10 minutes.
[0020]
In the olefin block copolymer (A), PO is a random copolymer of polypropylene, polyethylene, ethylene and an α-olefin having 3 or more carbon atoms, or a random copolymer of propylene and an α-olefin having 4 or more carbon atoms. It is preferably a copolymer segment, and in particular, a comonomer content selected from ethylene and an α-olefin having 4 or more carbon atoms is selected from polypropylene and a comonomer content selected from α-olefins having 3 or more carbon atoms. Polyethylene having an ethylene content of less than 10 mol%, an ethylene content of 10 to 90 mol%, a random copolymer having an α-olefin content of 3 or more carbon atoms of 90 to 10 mol%, a propylene content of 10 to 90 mol%, and carbon atoms Preferably, it is a segment of a random copolymer having an α-olefin content of several 4 or more and 90 to 10 mol%. Properly, f is preferably an ether bond or an ester bond, R is, the solubility parameter δ (cal / cm)^0.5Is preferably a segment having 9 or more, more preferably 10 or more segments. Examples of the segment having a solubility parameter of 9 or more include polyethyl methacrylate, polymethyl acrylate, and polyε-caprolactam.
[0021]
The solubility parameter can be easily obtained from known methods and databases (for example, Polymer Handbook, Fourth Edition, VII, pp. 675) as long as the primary structure of the polymer chain is known.
In the olefin block copolymer (A), PO is an ethylene / α-olefin copolymer or polypropylene, f is an ether bond, and R is a poly from the viewpoint of filler dispersibility and filler affinity. Ethyl methacrylate, styrene / maleic anhydride copolymer or nylon-6 is preferred.
[0022]
As an example of a preferable olefin block copolymer (A), more specifically, PO is an ethylene / propylene copolymer (propylene content: 10 to 90 mol%, Mw: 2,000 to 500,000). A block copolymer in which f is an ether bond and R is polyethyl methacrylate (Mw: 500 to 500,000),
A block copolymer in which PO is polypropylene (Mw: 2,000 to 500,000), f is an ether bond, and R is a styrene / maleic anhydride copolymer (Mw: 500 to 500,000),
Examples thereof include a block copolymer in which PO is polypropylene (Mw: 2,000 to 500,000), f is an ether bond, and R is nylon-6 (Mw: 500 to 500,000).
[0023]
Process for producing olefin block copolymer (A)
Such an olefin type block copolymer (A) can be manufactured as follows.
The olefin block copolymer (A) used in the present invention, for example, first produces a polyolefin having a terminal group 13 element bonded thereto, and then in the presence of the polyolefin, a chain polymerization reaction such as a radical polymerization reaction, It can manufacture by forming active species, such as a ring polymerization reaction and an ionic polymerization reaction, and performing these reactions.
[0024]
A polyolefin having a group 13 element bonded to the terminal can be produced by coordination polymerization with a transition metal. For example, an olefin having 2 to 20 carbon atoms as described above in the presence of a conventionally known olefin polymerization catalyst. Is produced by homopolymerization or copolymerization. The polyolefin produced here becomes a polyolefin segment of the olefin-based block copolymer (A) (hereinafter sometimes referred to as “PO part”).
[0025]
Conventionally known olefin polymerization catalysts include TiCl._ThreeCatalyst, MgCl₂Supported TiCl_FourAnd a metallocene catalyst, and a metallocene catalyst is preferably used.
Examples of the metallocene catalyst preferably used include conventionally known metallocene catalysts. Examples of metallocene catalysts include metallocene compounds of transition metals such as titanium, vanadium, chromium, zirconium and hafnium. The metallocene compound can be used in a liquid or solid form under the use conditions. Moreover, these do not need to be a single compound, may be supported on other compounds, may be a homogeneous mixture with other compounds, and may be complex compounds or compound compounds with other compounds. There may be.
[0026]
For the production of polyolefin, it is preferable to use a metallocene compound having a chiral structure having C2 symmetry or C1 symmetry among conventionally known metallocene catalysts.
Examples of chiral metallocene compounds having C2 symmetry include rac-ethylene-bis (indenyl) zirconium dichloride, rac-ethylene-bis (tetrahydroindenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,3,5- Trimethylcyclopentadienyl) zirconium dichloride, rac-dimethylsilylene-bis [1- (4-phenylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis [1- (2-methyl-4-phenylindenyl)] Zirconium dichloride, rac-dimethylsilylene-bis {1- [2-methyl-4- (1-naphthyl) indenyl]} zirconium dichloride, rac-dimethylsilylene-bis {1- [2-methyl-4- (2-naphthyl) ) Indenyl]} zirconium dichloride, rac-dimethylsilylene-bis {1- [2-methyl-4- (1-anthracenyl) indenyl]} zirconium dichloride Lido, rac-dimethylsilylene-bis {1- [2-methyl-4- (9-anthryl) indenyl]} zirconium dichloride, rac-dimethylsilylene-bis {1- [2-methyl-4- (9-phenanthryl) Indenyl]} zirconium dichloride, rac-dimethylsilylene-bis {1- [2-methyl-4- (o-chlorophenyl) indenyl]} zirconium dichloride, rac-dimethylsilylene-bis {1- [2-methyl-4- ( Pentafluorophenyl) indenyl]} zirconium dichloride, rac-dimethylsilylene-bis [1- (2-ethyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis {1- [2-ethyl-4- (1-naphthyl) indenyl]} zirconium dichloride, rac-dimethylsilylene-bis {1- [2-ethyl-4- (9-phenanthryl) indenyl]} zirconium dichloride, rac-dimethylsilylene-bis [1- (2-n-propyl-4-phenylindenyl)] zirconium dichloride, rac-dimethylsilylene-bis {1- [2-n-propyl-4- (1-naphthyl) indenyl]} zirconium dichloride, rac-dimethylsilylene Preferred examples include -bis {1- [2-n-propyl-4- (9-phenanthryl) indenyl]} zirconium dichloride and the like.
[0027]
Metallocene compounds having a chiral structure having C1 symmetry include ethylene [2-methyl-4- (9-phenanthryl) -1-indenyl] (9-fluorenyl) zirconium dichloride, ethylene [2-methyl-4- (9- Phenanthryl) -1-indenyl] (2,7-dimethyl-9-fluorenyl) zirconium dichloride, dimethylsilylene (9-fluorenyl) (3-t-butylcyclopentadienyl) zirconium dichloride, diphenylsilylene (9-fluorenyl) ( Preferred examples include 3-t-butylcyclopentadienyl) zirconium dichloride and the like.
[0028]
Examples of the metallocene compound that is preferably used among conventionally known metallocene compounds include metallocene compounds having only one substituted cyclopentadienyl group.
For example, (tertiary butyramide) (tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (tertiary butylamide) (tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediyl titanium dichloride, (methylamide) (tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediylzirconium dichloride, (methylamide) (tetramethyl-η^Five-Cyclopentadienyl) -1,2-ethanediyltitanium dichloride, (ethylamide) (tetramethyl-η^Five-Cyclopentadienyl) methylene titanium dichloride, (tertiary butylamide) dimethyl (tetramethyl-η^Five-Cyclopentadienyl) silane titanium dichloride, (tertiary butylamido) dimethyl (tetramethyl-η^Five-Cyclopentadienyl) silane zirconium dibenzyl, (benzylamido) dimethyl (tetramethyl-η^Five-Cyclopentadienyl) silane titanium dichloride, (phenylphosphide) dimethyl (tetramethyl-η^Five-Cyclopentadienyl) silane zirconium dibenzyl and the like.
[0029]
Further, among the conventionally known metallocene compounds, the metallocene compound preferably used has two substituted cyclopentadienyl groups, and these two cyclopentadienyl groups are (substituted) alkylene, (substituted) silylene, etc. Also included are metallocene compounds that are not bonded by the bonding group.
For example, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfo Nato), bis (ethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (Butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium dichloride, bis (methylbutyl Clopentadienyl) zirconium bis (methanesulfonate), bis (trimethylcyclopentadienyl) zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis ( (Hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, and the like.
[0030]
The above metallocene compounds may be used alone or in combination of two or more._ThreeCatalyst, MgCl₂Supported TiCl_FourThe catalyst may be used in combination with other olefin polymerization catalysts such as a system catalyst and a post metallocene catalyst.
In the production of polyolefin, the metallocene compound is used in combination with the following organometallic catalyst component. TiCl_ThreeCatalyst, MgCl₂Supported TiCl_FourAlso when a system catalyst or a postmetallocene catalyst is used, it is used in combination with the following organometallic catalyst component.
[0031]
The post metallocene catalyst is a transition metal complex containing a nitrogen atom or an oxygen atom in the ligand, and a conventionally known one is preferably used as the transition metal complex. Examples of the post metallocene catalyst catalyst include transition metal complexes as described in the following documents.
1) M. Brookhart et al., J. Am. Chem. Soc. 1995, 117, 6414-6415
2) M. Brookhart et al., J. Am. Chem. Soc. 1996, 118, 267-268
3) D.H.McConville et al., Macromolecules 1996, 29, 5241-5243
4) R.F.Jordan et al., Organanometallics 1997, 16, 3282-3302
5) R.H.Grubbs et al., Organanometallics 1998,17,3149-3151
6) S. Collins et al., Organometallics 1999, 18, 2731-2733
7) M.S.Eisen et al., Organanometallics 1998, 17, 3155-3157
8) M.S.Eisen et al., J.Am.Chem.Soc. 1998,120,8640-8636
9) R.F.Jordan et al., J.Am.Chem.Soc. 1997,119,8125-8126
10) K. Hakala et al., Macromol. Rapid Commun. 18, 634-638 (1997)
The organometallic catalyst component preferably includes an element selected from Group 13 of the periodic table. Among them, an organoaluminum compound, an organic boron compound, a complex alkyl compound of Group 1 element of the periodic table and aluminum or boron, and the like are preferable. It is done.
[0032]
As an organoaluminum compound, the compound shown with the following general formula can be illustrated, for example.
R^a _nAlX_3-n
(Wherein R^aRepresents a hydrocarbon group having 1 to 12 carbon atoms, X represents halogen or hydrogen, and n is 0 to 3. )
R^aIs a hydrocarbon group having 1 to 12 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group. Specifically, methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, Such as cyclopentyl, cyclohexyl, phenyl, tolyl.
[0033]
Specifically, as such an organoaluminum compound,
Trialkylaluminums such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri-2-ethylhexylaluminum;
Trialkenyl aluminum such as triisoprenyl aluminum;
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesquichloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, etc. Alkyl aluminum sesquihalides;
Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, ethylaluminum dibromide;
Examples include alkylaluminum hydrides such as diethylaluminum hydride, diisobutylaluminum hydride, and ethylaluminum dihydride.
[0034]
As the organoaluminum compound, a compound represented by the following general formula can also be used.
R^a _nAlY_3-n
In the above formula, R^aIs the same as above,
Y is -OR^bGroup, -OSiR^c _ThreeGroup, -OAlR^d ₂Group, -NR^e ₂Group, -SiR^f _ThreeGroup or -N (R^g) AlR^h ₂A group, n is 1-2, R^b, R^c, R^dAnd R^hAre methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl, and the like, and R^eIs a hydrogen atom, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., and R^fAnd R^gAre methyl, ethyl and the like.
[0035]
Specific examples of such an organoaluminum compound include the following compounds.
(I) R^a _nAl (OR^b)_3-n  A compound represented by, for example,
Dimethylaluminum methoxide, diethylaluminum ethoxide, diisobutylaluminum methoxide, etc.
(Ii) R^an Al (OSiR^c)_3-n  A compound represented by, for example,
Et₂Al (OSiMe_Three), (Iso-Bu)₂Al (OSiMe_Three), (Iso-Bu)₂Al (OSiEt_Three)Such,
(Iii) R^a _nAl (OAR)^d ₂)_3-n  A compound represented by, for example,
Et₂AlOAlEt₂, (Iso-Bu)₂AlOAl (iso-Bu)₂ Such,
(Iv) R^a _nAl (NR^e ₂)_3-n  A compound represented by, for example,
Me₂AlNEt₂, Et₂AlNHMe, Me₂AlNHEt, Et₂AlN (Me_ThreeSi)₂, (Iso-Bu)₂AlN (Me_ThreeSi)₂Such,
(V) R^a _nAl (SiR^f _Three)_3-n  A compound represented by, for example,
(Iso-Bu)₂AlSiMe_ThreeSuch,
(Vi) R^a _nAl [N (R^g) -AlR^h ₂]_3-n  A compound represented by, for example,
Et₂AlN (Me) -AlEt₂(Iso-Bu)₂, AlN (Et) Al (iso-Bu)₂Such.
[0036]
In addition, similar compounds, for example, an organoaluminum compound in which two or more aluminums are bonded via an oxygen atom or a nitrogen atom can be given.
Specifically, (C₂H_Five)₂AlOAl (C₂H_Five)₂, (C_FourH₉)₂AlOAl (C_FourH₉)₂, (C₂H_Five)₂AlN (C₂H_Five) Al (C₂H_Five)₂ Such.
Furthermore, aluminoxanes such as methylaluminoxane, ethylaluminoxane, propylaluminoxane, and butylaluminoxane can be exemplified.
[0037]
Moreover, the organoaluminum compound represented by the following general formula can also be used.
R^aAlXY
(Wherein R^a, X and Y are the same as above)
Organic boron compounds include triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris ( p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, texylborane, dicyclohexylborane, dicyamilborane, diisopinocanphenylborane, 9-borabicyclo [3.3.1] nonane, dimethyl Examples thereof include borane, dichloroborane, catecholborane, B-bromo-9-borabicyclo [3.3.1] nonane, borane-triethylamine complex, and borane-methyl sulfide complex.
[0038]
Further, an ionic boron compound may be used as the organic boron compound. Such compounds include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron, trimethylammonium tetra (o-tolyl) boron, tri (n-butyl) Ammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, N, N-dimethylanilinium tetra ( Phenyl) boron, dicyclohexylammonium tetra (phenyl) boron, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, bis [ And tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and the like.
[0039]
Examples of complex alkylated products of Group 1 elements of the periodic table and aluminum include compounds represented by the following general formula.
M¹AlR^j _Four
(Where M¹Represents Li, Na or K, R^jRepresents a hydrocarbon group having 1 to 15 carbon atoms. )
Specifically, LiAl (C₂H_Five)_Four, LiAl (C₇H₁₅)_FourEtc.
[0040]
The organoboron compound and the complex alkylated product of Group 1 element of the periodic table and boron are compounds of the above-described organoaluminum compound and the complex alkylated product of Group 1 element of the periodic table and aluminum substituted with boron. Can be mentioned.
The said organometallic catalyst component can be used individually by 1 type or in combination of 2 or more types.
[0041]
The organometallic catalyst component is preferably used in combination with a compound having a hydrogen-13 group element bond and a trialkylaluminum or aluminoxane or an ionic boron compound. A compound having a hydrogen-boron bond is preferred. These compounds may be used for polymerization after mixing, or may be added to a polymerization system after having initiated polymerization using only trialkylaluminum, aluminoxane or ionic boron compound, and then having a hydrogen-13 group element bond. preferable.
[0042]
Examples of the compound having a hydrogen-13 group element bond include diethylaluminum hydride, diisobutylaluminum hydride, ethylaluminum dihydride, etc. among organoaluminum compounds; 9-borabicyclo [3.3.1] nonane among organoboron compounds, Examples thereof include dimethylborane, dichloroborane, and catecholborane.
[0043]
The olefin polymerization catalyst as described above may be preliminarily polymerized. There is no particular limitation on the method for carrying out the prepolymerization. For example, the prepolymerization can be carried out in the presence of an inert solvent, and the prepolymerization can be carried out under relatively mild conditions by adding an olefin and each catalyst component to the inert solvent. preferable. At this time, it may be carried out under the condition that the produced prepolymer is dissolved in the polymerization medium, or may be carried out under the condition where it is not dissolved, but it is preferably carried out under the condition where it is not dissolved.
[0044]
Examples of the olefin used for the prepolymerization include α-olefins having 2 or more carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-1-butene. 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1 -Hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. . Two or more of these may be used in combination. The α-olefin used in the prepolymerization may be the same as or different from the α-olefin used in the olefin polymerization described later, but the same olefin as used in the olefin polymerization is preferable.
[0045]
Specific examples of the inert solvent include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane. Aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene. These may be used in combination.
[0046]
Of these inert solvents, it is particularly preferable to use an aliphatic hydrocarbon. The prepolymerization can be performed in a state where the α-olefin is in a liquid state, or can be performed under a gas phase condition. The prepolymerization can be performed in any of a batch type, a semi-continuous type, and a continuous type. Further, in the prepolymerization, it is preferable to use a catalyst having a concentration higher than the catalyst concentration in the system in the main polymerization.
[0047]
The polyolefin to be the PO part of the olefin block copolymer (A) is homopolymerized or copolymerized with an olefin having 2 to 20 carbon atoms as described above in the presence of the above olefin polymerization catalyst ( Hereinafter, it may be simply referred to as “olefin polymerization”.
The olefin polymerization can be carried out in any of liquid phase polymerization methods such as solution polymerization and suspension polymerization, or gas phase polymerization methods. As the reaction solvent for the suspension polymerization, the above-mentioned inert solvent can be used, or a liquid olefin can be used at the reaction temperature. The reaction temperature is usually in the range of −50 ° C. to 200 ° C., preferably 0 ° C. to 150 ° C. The polymerization pressure is usually 0.1 to 100 atm, preferably 1 to 50 atm. Olefin polymerization can be carried out in any of batch, semi-continuous, and continuous methods, and when it is carried out in two or more stages, the reaction conditions may be the same or different.
[0048]
In the olefin polymerization, a polyolefin having a weight average molecular weight of usually 2,000 or more, preferably 2,000 to 1,000,000 is produced. At this time, it is preferable that molecular hydrogen which is a general molecular weight regulator is not present in the polymerization system, and the molecular weight is adjusted by any of the above-mentioned organometallic catalyst component concentration, polymerization temperature, and olefin concentration (polymerization pressure). It is preferable to carry out by controlling one or more kinds. Specifically, as a method for preparing the molecular weight, for example, in suspension polymerization in which molecular hydrogen is not substantially present, increasing the concentration of the organometallic catalyst component can reduce the molecular weight of the resulting polyolefin, In suspension polymerization in which molecular hydrogen is not substantially present, the molecular weight of the resulting polyolefin can be lowered by increasing the polymerization temperature.
[0049]
One end of the polyolefin obtained as described above is an end bonded with a group 13 element or an unsaturated bond end. Whether one end of the polyolefin is a terminal to which a group 13 element is bonded or an unsaturated bond terminal depends on the polymerization conditions such as the type and / or amount of the organometallic catalyst component used and the polymerization temperature.
When one end of the polyolefin is an unsaturated bond end, a compound containing a group 13 element is reacted to convert the end to a group 13 element bonded. In addition, even when the obtained polyolefin is a mixture of one having a group 13 element bonded to one end and one having an unsaturated bond end on one end, the one end is unsaturated bond, if necessary. You may convert the terminal of polyolefin which is a terminal into the terminal which group 13 element combined.
[0050]
The compound containing a group 13 element used in the reaction is selected from the compounds exemplified as the organic compound catalyst component described above, and the compounds exemplified as the organoaluminum compound or the organoboron compound are preferably used. Among these, a trialkylaluminum, a dialkylaluminum hydride or a boron compound having one or more hydrogen-boron bonds is more preferable, and a boron compound having one or more hydrogen-boron bonds is particularly preferable. Most preferred compounds include 9-borabicyclo [3.3.1] nonane, which may be a monomer or a dimer.
[0051]
The reaction of a polyolefin having one end of an unsaturated bond and a compound containing a group 13 element is performed, for example, as follows.
(1) 0.1 to 50 g of polypropylene having a vinylidene group at the end and 0.01 to 5 mol / liter-octane solution of diisobutylaluminum hydride in an amount of 5 to 1000 ml are mixed and refluxed for 0.5 to 6 hours. .
(2) 0.1 to 50 g of polypropylene having a terminal vinylidene group, 5 to 1000 ml of anhydrous tetrahydrofuran, and 0.05 to 10 mol of 0.1 to 50 ml of 9-borabicyclo [3.3.1] nonane The liter-tetrahydrofuran solution is mixed and stirred at 20-65 ° C. for 0.5-24 hours.
[0052]
The polyolefin used as the PO part of an olefin type block copolymer (A) is manufactured as mentioned above. A group 13 element is bonded to one end of the obtained polyolefin. The group 13 element is preferably boron.
Next, chain polymerization active species such as radical polymerization reaction, ring-opening polymerization reaction, and ionic polymerization reaction are formed in the presence of the polyolefin having a group 13 element bonded to one end, and these reactions are performed to carry out the olefin block copolymer. A polymer (A) is manufactured. By this reaction, the f part is formed between the group 13 element bonded to the terminal and the polyolefin segment, and a polymer produced by a chain polymerization reaction such as radical polymerization reaction, ring-opening polymerization reaction, ionic polymerization reaction, It becomes a functional segment (hereinafter sometimes referred to as “R portion”). Part f may include a part of a structure formed by a chain polymerization reaction such as a radical polymerization reaction, a ring-opening polymerization reaction, or an ionic polymerization reaction.
[0053]
This polymerization reaction is performed, for example, as follows.
(1) When the group 13 element bonded to one end of the polyolefin is boron, a radical is generated by oxidizing a carbon-boron bond with molecular oxygen in the presence of a radical polymerizable monomer. Do.
Specifically, a polyolefin having boron bonded to one end is oxidized with molecular oxygen in the presence of a radical polymerizable monomer. This converts the terminal boron into peroxyborane (—O—O—B). When the peroxyborane is stirred in the presence of a radical polymerizable monomer, the O—O bond is cleaved to generate a radical, and the generated alkoxy radical (—O^*) Serves as an initiator, and radical polymerization of the radical polymerizable monomer proceeds.
[0054]
Examples of the radical polymerizable monomer include methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate, vinyl acrylate (VA), butyl acrylate (BA), styrene, acrylonitrile, vinyl acetate and the like. These radically polymerizable monomers may be used alone or in combination of two or more.
[0055]
Termination of radical polymerization can be performed by precipitating the polymer in methanol. As described above, an olefin block copolymer (A) in which the f part is an ether bond or an ester bond and the R part is a radical polymer can be produced.
(2) When the group 13 element bonded to one end of the polyolefin is aluminum, active species are generated by oxidizing the carbon-aluminum bond with molecular oxygen to perform a ring-opening polymerization reaction.
[0056]
Specifically, the carbon-aluminum bond is oxidized with molecular oxygen, thereby converting the aluminum at the end of the PO moiety into aluminum oxide (—O—Al). The ring-opening polymerizable monomer is subjected to ring-opening polymerization using the obtained aluminum oxide as an active species.
Examples of the ring-opening polymerizable monomer include lactones, lactams, 2-oxazolines, cycloethers, and the like. Specifically, β-propiolactone, β-butyrolactone, δ-valerolactone, glycolide, lactide, Examples include ε-caprolactone, α-pyrrolidone, γ-butyrolactam, ε-caprolactam, ethylene oxide, propylene oxide, epichlorohydrin, oxetane, tetrahydrofuran, and octamethylcyclotetrasiloxane. These ring-opening polymerizable monomers may be used alone or in combination of two or more.
[0057]
The ring-opening polymerization reaction is usually performed at a temperature of 0 to 100 ° C. for 30 minutes to 12 hours, preferably 1 hour to 6 hours. The ring-opening polymerization reaction can be stopped by precipitating the polymer in methanol. As described above, an olefin block copolymer (A) in which the f part is an ether bond or an ester bond and the R part is a ring-opening polymer can be produced.
(3) A group 13 element bonded to one end of the polyolefin is converted into a hydroxyl group, an amino group, an aldehyde group, or a halogen, and then a ring-opening polymerization active species is generated to perform a ring-opening polymerization reaction.
[0058]
For example, a ring-opening polymerization active species is produced by adding a sodium hydroxide solution and a hydrogen peroxide solution to a polyolefin bonded with boron at one end and reacting at 40 ° C. to 50 ° C. for 3 to 5 hours to form boron into a hydroxyl group. This can be carried out by reacting butyllithium with this and then reacting with diethylaluminum chloride to convert the hydroxyl group into aluminum oxide.
[0059]
The ring-opening polymerizable monomer is subjected to a ring-opening polymerization reaction using the aluminum oxide obtained by such a method as an active species. The ring-opening polymerization reaction is performed in the same manner as in the above method (2). Further, instead of aluminum oxide, another metal alkoxide, metal halide, or metal amine may be bonded to one end of the polyolefin as an active species for the ring-opening polymerization reaction. Active species other than aluminum oxide are generated using a hydroxyl group, amino group, aldehyde group or halogen bonded to one end of the polyolefin. Among these, it is preferable to use aluminum oxide as an active species. As described above, an olefin block copolymer (A) in which the f part is an ether bond, an ester bond or an amide bond and the R part is a ring-opening polymer can be produced.
[0060]
As an example of an ionic polymerization reaction, for example, when an anionic polymerization reaction is performed, an anionic polymerization can be performed after converting a polyolefin having a hydroxyl group at the terminal to a polyolefin having a lithium, potassium, sodium, phosphorus-containing group, or the like at the terminal. It can be obtained by polymerizing various monomers. As an example, a method for producing a block copolymer having a (meth) acrylic acid ester as an example of a segment in which the R portion is an anionic polymer using a polyolefin having lithium at the terminal will be described.
[0061]
Preparation of polyolefin with terminal lithium
A polyolefin having lithium at the terminal can be obtained by reacting the polyolefin having a hydroxyl group at the terminal with an organic lithium compound. The reaction between the polyolefin having a hydroxyl group at the terminal and the organolithium compound is usually carried out in a solvent.
[0062]
Examples of the organic lithium compound include alkyl lithium such as butyl lithium, propyl lithium, ethyl lithium, and methyl lithium; alkoxy lithium such as butoxy lithium, propoxy lithium, ethoxy lithium, and methoxy lithium. In the present invention, alkyl lithium is more preferably used.
[0063]
Examples of the solvent used for the reaction include the same hydrocarbons as exemplified as the inert hydrocarbon medium.
When the polyolefin having a terminal hydroxyl group is reacted with the organolithium compound, the organolithium compound is used in an amount of 0.1 to 100 mol, preferably 0.2 to 10 mol, per 1 mol of the hydroxyl group of the polyolefin end. . The reaction temperature is usually −100 to 100 ° C., preferably 0 to 80 ° C., and the reaction time is usually 0.1 to 48 hours, preferably 0.5 to 12 hours.
[0064]
In this way, a polyolefin having lithium at the terminal represented by the following general formula (II) is produced.
PO-O-Li (II)
In the formula, PO represents a polyolefin segment having a weight average molecular weight of 1,000 to 10,000,000, preferably 3,000 to 1,000,000, more preferably 5,000 to 500,000. The terminal Li polyolefin preferably has Mw / Mn of 2 or more, preferably 3 to 15, more preferably 4 to 14.
[0065]
Production of block copolymers
Next, for example, (meth) acrylic acid ester is anionically polymerized in the presence of the terminal Li polyolefin to obtain a polyolefin block copolymer comprising a polyolefin segment and a (meth) acrylic acid ester segment.
The polymerization is carried out by mixing the solvent, the terminal Li polyolefin and the (meth) acrylic acid ester, or by mixing the terminal Li polyolefin and a liquid (meth) acrylic acid ester. An anionic polymerization active species can be formed by mixing the terminal Li polyolefin, the solvent, and the (meth) acrylic acid ester.
[0066]
Examples of the solvent include aliphatic hydrocarbons such as hexane and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene and toluene; diethyl ether, dioxane, tetrahydrofuran (THF), monoglyme, and diglyme. An ether solvent such as is used. These solvents can be used singly or in combination of two or more. Of these, aromatic hydrocarbons and ether solvents are preferably used.
[0067]
Examples of (meth) acrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, vinyl acrylate, 2-methacrylic acid 2- Examples include methoxyethyl and 2- (N, N-diethylamino) ethyl methacrylate. These (meth) acrylic acid esters can be used singly or in combination of two or more. As a combination of (meth) acrylic acid esters, two or more selected from acrylic esters, two or more selected from methacrylic esters, one or more selected from acrylic esters and one or more selected from methacrylic esters. And combinations thereof.
[0068]
In addition, compounds useful for the formation of anionic polymerization active species such as triphenylphosphine, α, α′-dipyridyl, hexamethylphosphoramide (HMPA), titanium tetrachloride, alkyllithium, and alkoxylithium may be added during polymerization. Good.
The polymerization is usually performed at a polymerization temperature of −100 ° C. to 100 ° C., preferably −80 ° C. to 80 ° C., more preferably −70 ° C. to 70 ° C. for 1 minute to 500 hours, preferably 10 minutes to 300 hours, more preferably. Is carried out over 15 minutes to 150 hours. In this polymerization, the terminal Li polyolefin is 0.001 to 100 mol / liter, preferably 0.005 to 50 mol / liter, more preferably 0.01 to 10 mol / liter, and further preferably 0.1 to 5 mol. Used at a concentration of mol / liter. The (meth) acrylic acid ester is usually used at a concentration of 0.001 to 500 mol / liter, preferably 0.005 to 300 mol / liter, more preferably 0.01 to 150 mol / liter.
[0069]
It is preferable to produce a poly (meth) acrylic acid ester segment having stereoregularity by polymerization as described above. That is, a stereoregular poly (substituted acrylate) having a triad syndiotacticity (rr) of 70% or more or a triad isotacticity (mm) of 70% or more is preferable.
Rr and mm are obtained by dissolving the sample in nitrobenzene-d5.¹H-NMR is measured and determined by the ratio of the peak area of rr or the peak area of mm to the sum of the peak areas of rr, mr, and mm detected in the vicinity of 0.85, 1.05, and 1.25 ppm, respectively.
[0070]
As described above, a polymer containing a block copolymer in which a polyolefin segment (PO) and a poly (meth) acrylic ester segment are chemically bonded can be produced. Whether or not the polymer includes a chemically bonded polymer with an acrylate segment can be determined by, for example, the molecular weight of the obtained polymer, solubility in an organic solvent, or spectroscopic analysis. That is, the molecular weight of the polymer obtained by the method of the present invention shows a high value with respect to the molecular weight of PO of the terminal Li polyolefin, corresponding to the polyolefin segment of the olefin block copolymer polymer obtained by the method of the present invention. The dissolution behavior in the organic solvent of the mixture of the polymer and the polymer corresponding to the segment of the polymer produced by anionic polymerization of the polymer indicates that the olefin block copolymer obtained by the method of the present invention is dissolved in the organic solvent. The terminal structure of the olefinic block copolymer obtained by the method of the present invention is different from that of the behavior.¹³The target block copolymer can be produced by detecting peaks derived from chemical bonds between the polyolefin segment and the poly (meth) acrylate segment of the polymer produced by anionic polymerization as analyzed by C-NMR. Can be judged.
[0071]
In the chain polymerization reaction such as the above radical polymerization reaction, ring-opening polymerization reaction, and ionic polymerization reaction, a polymer having a weight average molecular weight of usually 500 or more, preferably 500 to 1,000,000 is produced.
Such an olefin type block copolymer (A) is excellent in the dispersibility of a filler and affinity with a filler.
[0072]
Filler dispersibility improving material
The olefin block copolymer (A) as described above can be used as a filler dispersibility improving material.
The filler dispersibility improving material according to the present invention is used, for example, when mixing a thermoplastic resin and a filler. Examples of the thermoplastic resin include thermoplastic resins as described later, and polyolefin is preferable.
[0073]
Although the usage-amount of a filler dispersibility improving material is not specifically limited, For example with respect to 100 weight part of thermoplastic resins, it is the quantity of 0.01-100 weight part, Preferably it is 0.1-20 weight part.
The filler dispersibility improving material according to the present invention has high affinity with the filler, and can improve the dispersibility of the filler. When such filler dispersibility improving material is used, mechanical properties such as rigidity, hardness, heat resistance, impact resistance, and elongation of the thermoplastic resin composition containing the filler can be improved.
[0074]
Filler-containing resin composition
The filler-containing resin composition according to the present invention comprises the olefin block copolymer (A) and the following filler (filler).
Examples of the filler used in the present invention include inorganic fillers and organic fillers.
[0075]
As inorganic fillers, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, calcium titanate, barium sulfate, calcium sulfite Talc, clay, mica, asbestos, glass fiber, glass flake, glass bead, calcium silicate, montmorillonite, bentonite, boron fiber, carbon fiber, carbon black, carbon nanofiber, aluminum powder, molybdenum sulfide and the like. Furthermore, what combined the organic substance chemically with the inorganic filler which was illustrated above is also mentioned.
[0076]
Examples of the organic filler include fibers such as wholly aromatic polyamide fibers, aliphatic polyamide fibers, polyester fibers, and cellulose fibers, and fine dispersions such as liquid crystal polyester and polyamide.
Among these fillers, a layered compound is preferable, and a layered silicate having swelling property or cleavage property in a dispersion medium such as water or alcohol is particularly preferably used. Such layered silicates are generally of a type having a two-layer structure having an octahedral layer with aluminum or magnesium as the central metal on the upper part of the silica tetrahedral layer, and a silica tetrahedral layer such as aluminum or magnesium. Is a type having a three-layer structure in which an octahedral layer having a central metal is narrowed from both sides. Examples of the former two-layer structure type include kaolinite group and antigolite group, and examples of the latter three-layer structure type include smectite group, vermiculite group, and mica group depending on the number of interlayer cations.
[0077]
More specifically, these layered silicates include kaolinite, dickite, nacrite, halloysite, antigolite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectorite, tetrasi Examples include lyric mica, sodium teniolite, muscovite, fluoride mica, margarite, talc, vermiculite, phlogopite, xanthophyllite, chlorite.
[0078]
Moreover, in this invention, what processed the layered silicate with the organic substance (henceforth an organic modified silicate) can also be used as a layered silicate.
Among the above-mentioned layered silicates, smectite group, vermiculite group and mica group are preferable among the above layered silicates, and smectite group is particularly preferable. Examples of the smectite group include montmorillonite, beidellite, nontronite, saponite, soconite, stevensite, and hectorite.
[0079]
The organically modified silicate can be prepared, for example, by immersing a layered silicate in a dispersion medium to swell or cleave it, and then organizing ions between layers of the layered silicate.
Examples of the dispersion medium for swelling or cleaving the layered silicate include alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol, and diethylene glycol, water, dimethylformamide, dimethyl sulfoxide, acetone, and the like. Water is preferred.
[0080]
The layered silicate swollen or cleaved in this way organicizes ions between layers. When the ions between the layers are cations such as sodium ions, it is preferable to exchange them with organic ammonium ions. Examples of the compound used for the exchange reaction include 12-aminododecanoic acid and dimethyldioctadecylammonium chloride.
In the filler-containing resin composition according to the present invention, the olefin block copolymer (A) is usually 10 to 90 parts by weight, preferably 20 to 80 parts by weight, and the filler is usually 90 to 10 parts by weight, preferably 80. ~ 20 parts by weight.
[0081]
The filler-containing resin composition according to the present invention may contain two or more olefin-based block copolymers and may contain two or more fillers.
In addition, the filler-containing resin composition according to the present invention may contain conventionally known additives used for the following thermoplastic resins, nucleating agents, and other synthetic resins in an arbitrary ratio.
Thermoplastic resin
Examples of the thermoplastic resin include polyolefin, polyamide, polyester, polyacetal, polystyrene, acrylonitrile / butadiene / styrene copolymer (ABS), polycarbonate, polyphenylene oxide, and polyacrylate.
[0082]
Specific examples of polyolefins include ethylene polymers such as ethylene homopolymers, ethylene / α-olefin copolymers, ethylene / polar group-containing vinyl copolymers; propylene homopolymers, propylene / α-olefin copolymers. Propylene-based polymers such as; butene-based polymers such as butene homopolymer; 4-methyl-1-pentene-based polymers such as 4-methyl-1-pentene homopolymer; 3-methyl-1-butene homopolymer Examples include 3-methyl-1-butene polymers such as hexene; hexene polymers such as hexene homopolymer. Among these, an ethylene polymer, a propylene polymer, and a 4-methyl-1-pentene polymer are preferable, and in the case of an ethylene polymer, an ethylene / polar group-containing vinyl copolymer is preferable.
[0083]
Specific examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate, and polybutylene terephthalate; polylactic acid, polyglycolic acid, poly-β-hydroxybutyric acid, poly-ε-caprolactone, and polybutylene succinate. And aliphatic polyesters such as polyethylene succinate.
[0084]
Specific examples of polyamides include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12, and nylon-46; aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines, and the like. It is done. Among these, nylon-6 is particularly preferable.
Specific examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde and the like. Among these, polyformaldehyde is particularly preferable.
[0085]
Polystyrene may be a homopolymer of styrene, or a binary copolymer of styrene and acrylonitrile, methyl methacrylate, or α-methylstyrene.
ABS includes a structural unit derived from acrylonitrile in an amount of 20 to 35 mol%, a structural unit derived from butadiene in an amount of 20 to 30 mol%, and a structural unit derived from styrene. ABS contained in an amount of 40 to 60 mol% is preferably used.
[0086]
Polycarbonates include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyphenyl) Examples thereof include polymers obtained from butane and the like. Of these, polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is particularly preferred.
[0087]
As the polyphenylene oxide, poly (2,6-dimethyl-1,4-phenylene oxide) is preferably used.
As the polyacrylate, polymethyl methacrylate or polybutyl acrylate is preferably used.
The above thermoplastic resins may be used alone or in combination of two or more.
[0088]
The blending amount is not particularly limited, but the olefin block copolymer (A) is usually 0.01 to 150 parts by weight and the filler is 0.01 to 300 parts by weight, preferably 100 parts by weight of the thermoplastic resin. 0.1-20 parts by weight of olefin block copolymer (A), 0.1-40 parts by weight of filler, more preferably 0.5-10 parts by weight of olefin block copolymer (A), filler Is preferably used in an amount of 0.5 to 20 parts by weight.
[0089]
Moreover, when mix | blending the said filler containing resin composition with a thermoplastic resin, 0.01-450 weight part of the said filler containing resin composition is preferable with respect to 100 weight part of thermoplastic resins, Preferably it is 0.1-60 weight part More preferably, it is used in an amount of 1 to 30 parts by weight.
Method for producing filler-containing resin composition
The filler-containing resin composition according to the present invention can be prepared by mixing the olefin block copolymer (A) and a filler.
[0090]
As a mixing method, any mixing method can be employed, for example, a method of removing the solvent after dispersing the olefin block copolymer (A) and the filler in the solvent, a roll, an extruder, and a Brabender. A method of melt-mixing the olefin block copolymer (A) and the filler using a device such as the above, and mixing the olefin block copolymer (A) and the filler in a powder state using a Henschel mixer, a ribbon blender, or the like. The method etc. are mentioned.
[0091]
Moreover, as a manufacturing method of a filler containing resin composition, after superposing | polymerizing or copolymerizing a C2-C20 olefin, in the presence of the polyolefin obtained by the said polymerization and a filler, a radically polymerizable monomer, There is a method of polymerizing or copolymerizing a ring-opening polymerizable monomer or an ion polymerizable monomer. Specifically, in the method for producing the olefin block copolymer (A) as described above, chain polymerization such as radical polymerization, ring-opening polymerization, or ionic polymerization is performed in the presence of a filler.
[0092]
The filler used in such a method is preferably a swellable or cleaved layered compound, more preferably an organically modified silicate, and an organically modified silicate in which ions between layers are exchanged with organic ammonium ions. Particularly preferred. The organically modified silicate used here may be further impregnated with a radically polymerizable monomer or a ring-opening polymerizable monomer, or may be impregnated with a polymerization solvent such as toluene, xylene, hexane, or decane.
[0093]
In the filler-containing resin composition obtained by such a method, the filler is very well dispersed in the olefin block copolymer (A), and the olefin block copolymer (A), the filler, Excellent adhesion at the interface and excellent physical properties such as elastic modulus and heat resistance.
Application
The filler dispersibility improving material of the present invention can be used for thermoplastic resins and thermosetting resins using fillers, and is preferably used for polyolefins.
[0094]
Moreover, the thermoplastic resin and thermosetting resin containing the filler dispersibility improving material of the present invention, and the filler-containing resin composition can be molded by any known method.
For example, it can be manufactured by calendar molding, extrusion molding, injection molding, blow molding, press molding, stamping molding, or the like.
[0095]
In extrusion molding, a sheet or film (unstretched), a pipe, a tube, an electric wire and the like can be formed.
The stretched film can be obtained by stretching an extruded sheet or extruded film (unstretched) as described above, for example, by a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method, or a uniaxial stretching method. Moreover, an inflation film can also be manufactured from the thermoplastic resin or filler-containing resin composition containing the filler dispersibility improving material according to the present invention.
[0096]
Filaments can be made, for example, by extruding the molten composition through a spinneret.
The injection-molded body can be produced by adopting known conditions using a conventionally known injection molding apparatus and injection-molding the composition into various shapes.
The blow molded product can be manufactured using a known blow molding apparatus under known conditions.
[0097]
An example of the press-molded body is a mold stamping molded body.
The molded body obtained by such a method is used in a wide range of applications from household goods to industrial goods. Examples of the molded body obtained by such a method include electrical parts, electronic parts, automotive parts, mechanical mechanism parts, food containers, films, sheets, fibers, and the like. More specifically, for example, printers, personal computers, and the like. Office / OA equipment such as word processors, keyboards, PDAs (small information terminals), telephones, facsimiles, copiers, ECRs (electronic cash registers), calculators, electronic notebooks, electronic dictionaries, cards, holders, stationery, etc. Appliances such as TV, VTR, video camera, radio cassette, tape recorder, mini-disc, CD player, speaker, LCD, etc. Connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor sealing materials, Lines, cables, transformers, deflecting yokes, distribution boards, and the like electric and electronic parts and communication devices such as watches.
[0098]
In addition, seats (filling, dressing, etc.), belts, ceilings, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, foil covers, mattress covers, airbags, insulation, hanging hands, hanging hands Bands, wire clothing materials, electrical insulation materials, paints, coating materials, upholstery materials, flooring materials, corner walls, deck panels, covers, plywood, ceiling plates, partition plates, side walls, carpets, wallpaper, wall coverings, exteriors Materials, interior materials, roofing materials, sound insulation plates, heat insulation plates, window materials, etc., automobiles, vehicles, ships, aircraft and building materials; clothing, curtains, sheets, plywood, synthetic fiber boards, carpets, doormats, sheets, buckets, Life / sporting goods such as hoses, containers, glasses, bags, cases, goggles, skis, rackets, tents, musical instruments and the like.
[0099]
Furthermore, bottles for shampoos and detergents, seasoning bottles for edible oil, soy sauce, bottles for beverages such as mineral water and juice, containers for heat-resistant foods such as lunch boxes and bowls for steaming bowls, dishes such as dishes and chopsticks Other various food containers, packaging films, packaging bags and the like.
[0100]
【The invention's effect】
The filler dispersibility improving material of the present invention has higher affinity with the filler than conventionally known polyolefins, and can improve the dispersibility of the filler.
The filler-containing resin composition according to the present invention is excellent in mechanical properties such as rigidity, hardness, heat resistance, impact resistance, and elongation. Further, this filler-containing resin composition has particularly high dispersibility in polyolefin. When this filler-containing resin composition is blended with a resin such as polyolefin, the mechanical properties of the polyolefin can be improved with a small addition. For example, when used for polypropylene alloys for injection molding, ethylene / propylene rubber, polyethylene for electric wires, etc., moldability is improved, and mechanical properties such as rigidity, hardness, heat resistance, impact resistance and elongation are improved.
[0101]
With the method for producing a filler-containing resin composition according to the present invention, a filler is finely dispersed in a resin, and a composition having excellent affinity between the filler and the resin can be obtained. The composition thus obtained can improve the mechanical properties by adding a small amount to, for example, a polyolefin resin.
[0102]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
[0103]
[Production Example 1]
[Preparation of catalyst solution]
Methylaluminoxane and ethylenebis (indenyl) zirconium dichloride are mixed in toluene at a ratio where the zirconium concentration is 0.00011 mmol / liter and the molar ratio of aluminum to zirconium (Al / Zr) is 350 (appropriate amount if necessary) Of toluene was added), and the mixture was stirred for 15 minutes to perform a pre-activation treatment to prepare a catalyst solution (1).
[0104]
[polymerization]
500 ml of purified toluene was charged into a glass reactor having an internal volume of 500 ml sufficiently purged with nitrogen, propylene was circulated at a rate of 100 liters per hour, and stirred at 75 ° C. with stirring at 600 rpm using a magnetic stir bar. Hold for a minute. Next, 24.3 mg of triisobutylaluminum in terms of aluminum atom was charged into the reactor. Furthermore, 0.46 mg of the catalyst solution (1) was charged in terms of zirconium atoms. After polymerization for 60 minutes at 80 ° C. and normal pressure, a small amount of isopropanol was added to terminate the polymerization. After completion of the polymerization, the reaction solution was poured into 2 liters of dilute hydrochloric acid in methanol to precipitate the polymer. The precipitated polymer was washed twice with methanol, and the obtained polymer was dried at 80 ° C. under reduced pressure overnight.
[0105]
The obtained polypropylene (PP) was 87.0 g, and the catalytic activity was 17.4 kg / mmol-Zr · hr. The Mw of this polypropylene was 5,500. As a result of IR analysis, it was confirmed that an unsaturated bond was present at the polymer terminal.
[Hydroboration]
In a dry box filled with argon, 5.0 g of polypropylene having an unsaturated bond at the end suspended in 100 ml of degassed dry tetrahydrofuran (THF) was placed in a glass flask equipped with a magnetic stirrer, and 9-BBN. 14.5 ml of a THF solution (0.5 M) was added. The slurry was stirred at 55 ° C. for 5 hours in a dry box, filtered, washed with degassed and dried isopropyl alcohol (IPA), and dried under reduced pressure to obtain polypropylene having a terminal boron (PP-B). .
[0106]
[EMA polymerization]
The sealed flask was charged with 5.0 g of the PP-B, suspended by adding 79.3 g of dry EMA (ethyl methacrylate) and 80 ml of THF, and then the reaction was started by blowing 9.4 ml of dry oxygen. Subsequently, after stirring at room temperature for 2 hours, 100 ml of methanol was added to stop the reaction. The precipitated polymer was extracted with a soxhlet extractor in a mixed solvent of acetone and heptane over 24 hours in a nitrogen atmosphere, and as an insoluble component, polypropylene-O-polyethyl methacrylate diblock copolymer (PP-O- PEMA).
[0107]
The weight average molecular weight (Mw) of the PEMA part calculated from the following formula of this diblock copolymer:₂) Was 2,000.
Mw₂= Mw₁・ (W₂-W₁) / W₁
In the above formula
Mw₁: Mw of PP part
Mw₂: Mw of PEMA polymerization part
W₁: Weight of PP-B used for EMA polymerization
W₂: Yield of diblock copolymer
Respectively.
[0108]
[Production Example 2]
[Preparation of catalyst solution]
Methylaluminoxane and dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride in toluene have a zirconium concentration of 0.00011 mmol / liter and a molar ratio of aluminum to zirconium (Al / Zr) of 350. The catalyst solution (2) was prepared by mixing at a ratio (adding an appropriate amount of toluene as necessary) and stirring for 15 minutes for preactivation.
[0109]
[polymerization]
400 ml of purified toluene was charged into a glass reactor with an internal volume of 500 ml sufficiently purged with nitrogen, propylene was allowed to flow at a rate of 100 liters per hour, and stirred at 45 ° C. at 600 rpm with a magnetic stirrer. Hold for 10 minutes. Next, 1.8 mg of the catalyst solution (2) was charged into the reactor in terms of zirconium atoms. After polymerization at 50 ° C. and normal pressure for 60 minutes, a small amount of isopropanol was added to terminate the polymerization. After completion of the polymerization, the reaction solution was poured into 2 liters of dilute hydrochloric acid in methanol to precipitate the polymer. After further washing twice with methanol, the obtained polymer was dried at 80 ° C. under reduced pressure overnight. The obtained polypropylene was 39.4 g, and the catalytic activity was 2.0 kg / mmol-Zr · hr. The Mw of this polypropylene was 13,000. Moreover, melting | fusing point Tm measured by DSC was 141.6 degreeC. As a result of IR analysis, it was confirmed that an unsaturated bond was present at the polymer terminal.
[0110]
[Hydroboration]
In a dry box filled with argon, 10 g of polypropylene having an unsaturated bond at the terminal suspended in 100 ml of degassed dry THF was placed in a glass flask equipped with a magnetic stir bar, and a THF solution of 9-BBN (0 .5M) 6.2 ml was added. The slurry was stirred in a dry box at 55 ° C. for 5 hours, then filtered, washed with degassed dry IPA, and dried under reduced pressure to obtain polypropylene having a terminal boron (PP-B).
[0111]
[Styrene / maleic anhydride copolymer]
20 g of the PP-B was put into a sealed flask, 4 g of dry styrene (St) and 4 g of maleic anhydride (MAH) were added and suspended, and then 15.9 ml of dry oxygen was blown to initiate the reaction. After stirring at 45 ° C. for 2 hours, 100 ml of methanol was added to stop the reaction. The precipitated polymer was extracted and collected with a mixed solvent of acetone and heptane over 24 hours in a nitrogen atmosphere using a Soxhlet extractor, and a polypropylene-O-styrene / maleic anhydride copolymer diblock copolymer ( PP-OP (St · MAH)) was obtained.
[0112]
The weight average molecular weight (Mw) of the P (St · MAH) part calculated by the following formula of this diblock copolymer:₂) Was 2,000.
Mw₂= Mw₁・ (W₂-W₁) / W₁
In the above formula
Mw₁: Mw of PP part
Mw₂: Mw of P (St · MAH) part
W₁: Weight of PP-B used for St / MAH copolymerization
W₂: Yield of diblock copolymer
Respectively.
[0113]
[Production Example 3]
[Pre-activation treatment of catalyst components]
Ratio in which methylaluminoxane and meso-dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride have a zirconium concentration of 0.00011 mmol / liter and a molar ratio of aluminum to zirconium (Al / Zr) of 350. In toluene (appropriate amount of toluene was added if necessary) and stirred for 15 minutes to perform pre-activation treatment to obtain catalyst solution (3).
[0114]
[polymerization]
Into a glass reactor with an internal volume of 500 ml sufficiently purged with nitrogen, 250 ml of purified toluene was charged, ethylene was passed at a rate of 90 liters per hour, and propylene was passed at a rate of 110 liters per hour, and stirred at 600 revolutions per minute at 45 ° C. Hold for 10 minutes. Next, 0.045 mg (0.0005 mmol) of the catalyst solution (3) in terms of zirconium atom was charged into the reactor. After polymerization at 60 ° C. and normal pressure for 20 minutes, a small amount of isopropanol was added to terminate the polymerization. After completion of the polymerization, the reaction solution was poured into 2 liters of dilute hydrochloric acid in methanol to precipitate the polymer. After further washing with methanol twice, the obtained polymer was dried at 130 ° C. under reduced pressure overnight. The obtained ethylene / propylene random copolymer (EPR) was 2.7 g, and the catalytic activity was 16.2 kg / mmol-Zr · h. The ethylene content determined from IR analysis was 70.7%, and an unsaturated bond was present at the polymer terminal. Mw was 5,600.
[0115]
[Hydroboration]
In a dry box filled with argon, 5.0 g of EPR having an unsaturated bond at the end suspended in 100 ml of degassed and dried tetrahydrofuran (THF) was placed in a glass flask equipped with a magnetic stir bar. -14.2 ml of a THF solution (0.5 M) of borabicyclo [3.3.1] nonane (9-BBN) was added. The slurry was stirred at 55 ° C. for 5 hours in a dry box, filtered, washed with degassed and dried isopropyl alcohol, and dried under reduced pressure to obtain EPR (EPR-B) having boron at the terminal.
[0116]
[EMA polymerization]
The above EPR-B (5.0 g) was placed in a sealed flask, and 77.9 g of dried ethyl methacrylate (EMA) and 80 ml of THF were added and suspended. Then, 9.2 ml of dry oxygen was blown to initiate the reaction. Subsequently, after stirring at room temperature for 2 hours, 100 ml of methanol was added to stop the reaction. The precipitated polymer was extracted with a soxhlet extractor in a mixed solvent of acetone and heptane over 24 hours in a nitrogen atmosphere, and EPR-O-polyethyl methacrylate diblock copolymer (EPR-O-PEMA) was used as an insoluble component. Got.
[0117]
The weight average molecular weight (Mw) of the PEMA part calculated from the following formula of this diblock copolymer:₂) Was 2,000.
Mw₂= Mw₁・ (W₂-W₁) / Mw₁
In the above formula
Mw₁: Mw of EPR part,
Mw₂: Mw of PEMA department
W₁: Weight of EPR-B used for EMA polymerization
W₂: Yield of diblock copolymer
Respectively.
[0118]
[Example 1]
Propylene / ethylene block copolymer (B1) (MFR measured at 230 ° C. = 27 g / 10 min, decane soluble part = 14.3%) 87 parts by weight, talc (C1) (average particle size 15 μm) 10 parts by weight And 3 parts by weight of the diblock copolymer (PP-O-PEMA) produced in Production Example 1, Irganox 1010 (trade name, manufactured by Ciba Specialty Chemicals), Irgafos 168 (trade name, manufactured by Ciba Specialty Chemicals) Then, 0.1 parts by weight of calcium stearate was added, and the resin was melted and mixed at a cylinder temperature of 200 ° C. in a nitrogen atmosphere in a 20 mmφ twin-screw extruder to produce pellets. About the obtained pellet, cylinder temperature 200 ° C., mold temperature 40 ° C., injection pressure 1000 kg / cm²Were subjected to injection molding to obtain test pieces for evaluating various physical properties. The obtained test piece was held at 23 ° C. for 168 hours, and then subjected to the following test. The results are shown in Table 1.
[0119]
Flexural modulus (FM)
The bending elastic modulus was measured in accordance with ASTM D638 using an injection-molded test piece having a length of 5 inches, a width of 1/2 inch, and a thickness of 1/8 inch.
Izod impact strength (IZ)
In accordance with ASTM D258, measurement was performed at 23 ° C. using a 1/4 inch thick test piece (rear notch).
[0120]
Thermal deformation temperature (HDT)
The thermal deformation temperature was measured according to ASTM D648 using an injection molded test piece having a length of 5 inches, a width of 1/4 inch, and a thickness of 1/2 inch.
[0121]
[Example 2]
After 40 g of Na-type montmorillonite was dispersed in 1000 ml of distilled water at 70 ° C., a solution prepared by previously mixing 20 g of 12-aminododecanoic acid and 2 ml of hydrochloric acid in 100 ml of distilled water was introduced for 2 hours. The mixture was stirred at 70 ° C. to exchange metal ions between layers of montmorillonite with organic cations. Next, the obtained precipitate was filtered, washed sufficiently with warm water and purified, and then freeze-dried and pulverized to obtain 27 g of organic montmorillonite (C2).
[0122]
92 parts by weight of propylene / ethylene block copolymer (B1), 5 parts by weight of the above-mentioned organic montmorillonite (C2) and the diblock copolymer (PP-OP (St · MAH)) 3 produced in Production Example 2 Irganox in the weight part^TM1010, Irgaphos^TM168 and 0.1 parts by weight of calcium stearate were added, respectively, and melt-mixed and injection-molded in the same manner as in Example 1 to obtain test pieces for evaluating various physical properties. The obtained test piece was held at 23 ° C. for 168 hours, and then tested in the same manner as in Example 1. The results are shown in Table 1.
[0123]
[Comparative Example 1]
90 parts by weight of propylene / ethylene block copolymer (B1), 10 parts by weight of talc (C1), and Irganox^TM1010, Irgaphos^TM168 and calcium stearate were used in the same manner as in Example 1 except that 0.1 part by weight of each was used, and melt-mixed and injection-molded to obtain various physical property evaluation test pieces. The obtained test piece was held at 23 ° C. for 168 hours, and then tested in the same manner as in Example 1. The results are shown in Table 1.
[0124]
[Comparative Example 2]
95 parts by weight of propylene / ethylene block copolymer (B1), 5 parts by weight of organic montmorillonite (C2), and Irganox^TM1010, Irgaphos^TM168 and calcium stearate were used in the same manner as in Example 1 except that 0.1 part by weight of each was used, and melt-mixed and injection-molded to obtain various physical property evaluation test pieces. The obtained test piece was held at 23 ° C. for 168 hours, and then tested in the same manner as in Example 1. The results are shown in Table 1.
[0125]
[Table 1]

[0126]
[Example 3]
95 parts by weight of commercially available ethylene propylene rubber (B2) (trade name: Mitsui EPT3070), 5 parts by weight of zinc white, 1 part by weight of stearic acid, 80 parts by weight of talc (average particle size 15 μm), 20 parts by weight of titanium oxide, 20 parts by weight of liquid paraffin, 1 part by weight of the anti-aging agent N-isopropyl-N′-phenyl-p-phenylenediamine, and 5 parts by weight of the diblock copolymer (EPR-O-PEMA) obtained in Production Example 3 It mixed for 5 minutes at 140-150 degreeC using the 1.7 liter Banbury mixer. The resulting unvulcanized compounded rubber had a Mooney viscosity (ML1 + 4 (100 ° C.)) of 44. Further, the obtained rubber composition was mixed with 0.5 parts by weight of the vulcanization accelerator tetramethylthiuram monosulfide, 1.2 parts by weight of the vulcanization accelerator N-oxydiethylene-2-benzothiazole sulfenamide, and sulfur. 1.5 parts by weight was added and mixed for 5 minutes with a 6 inch mixing roll (both front roll and rear roll at 60 ° C.) to obtain a sheet having a thickness of 3 mm.
[0127]
The sheet thus obtained was subjected to compression molding at 160 ° C. for 10 minutes using a press molding machine to obtain a vulcanized rubber sheet having a thickness of 2 mm. The obtained sheet was subjected to a tensile test at a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min based on JIS K 6301, and the elongation at break and the strength at break were measured. The results are shown in Table 2.
[0128]
[Comparative Example 3]
100 parts by weight of ethylene propylene rubber (B2), 5 parts by weight of zinc white, 1 part by weight of stearic acid, 80 parts by weight of talc, 20 parts by weight of titanium oxide, 20 parts by weight of liquid paraffin, anti-aging agent N-isopropyl-N'- A vulcanized rubber was produced in the same manner as in Example 3 except that 1 part by weight of phenyl-p-phenylenediamine was used to produce an unvulcanized compounded rubber, and elongation at break and strength at break were measured. The results are shown in Table 2. Compared to Example 3, Mooney viscosity is high and breaking strength is low.
[0129]
[Table 2]

Claims (4)

A filler dispersibility improving material comprising an olefin block copolymer (A) represented by the following general formula (I);
PO-f-R (I)
(In the formula, PO represents a polyolefin segment composed of a repeating unit derived from an olefin having 2 to 20 carbon atoms, and having a weight average molecular weight of 2,000 or more,
f represents an ether bond,
R represents a methacrylate polymer segment obtained by a chain polymerization reaction and having a weight average molecular weight of 500 or more. ).   A filler-containing resin composition comprising the olefin block copolymer (A) according to claim 1 and a filler.   The filler-containing resin composition according to claim 2, wherein the filler is a layered silicate in which ions between layers are exchanged with organic ammonium ions.   The polymerized or copolymerized olefin having 2 to 20 carbon atoms, and then polymerized or copolymerized with a chain polymerizable monomer in the presence of the polyolefin and filler obtained by the polymerization. A method for producing a filler-containing resin composition comprising obtaining a filler-containing resin composition.