JP2001288272A - Resin dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin dispersion that is excellent in dispersion stability to an organic medium and exhibits good adhesion in adhesive bonding of a polyolefin to a metal or a polar resin. SOLUTION: The resin dispersion is prepared by dispersing in an organic medium an olefin block copolymer (A) represented by formula I : PO-f-R, wherein PO is a polyolefin segment which comprises a repeating unit derived from a 2-20C olefin and has a weight average molecular weight of not less than 2,000l; f is an ether linkage, an ester linkage or an amide linkage; and R is a functional segment which is produced by a chain polymerization reaction and comprises a repeating unit having a weight average molecular weight of not less than 500.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin dispersion exhibiting good adhesion when, for example, a polyolefin is bonded to a metal or a polar resin.

[0002]

BACKGROUND OF THE INVENTION Olefin-based polymers such as ethylene (co) polymer and propylene (co) polymer have poor affinity for other resins and metals and are difficult to adhere to other members. It is. For this reason, various adhesives have been studied for bonding an olefin polymer to another resin or metal.

For example, JP-A-63-12651 proposes a resin dispersion of a modified polyolefin as an adhesive between polypropylene and a metal such as aluminum. However, these modified polyolefins have insufficient dispersibility in an organic medium, and may cause a problem that the dispersion aggregates in a gel state during long-term storage.

The present inventors have conducted intensive studies in view of such prior art, and as a result, it has been found that a polyolefin segment and a functional segment obtained by a radical polymerization reaction or a ring-opening polymerization reaction are bonded by an ether bond or the like. The olefin-based block copolymer or the olefin-based polymer composition containing the copolymer has good dispersibility and dispersion stability in an organic medium, and a resin dispersion having high adhesion to a polyolefin can be obtained. This led to the completion of the present invention.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin dispersion having excellent dispersibility and dispersion stability in an organic medium, and exhibiting good adhesiveness when bonding a polyolefin to a metal or a polar resin. And

[0006]

SUMMARY OF THE INVENTION The resin dispersion according to the present invention comprises an olefin block copolymer (A) represented by the following general formula (I):
Is dispersed in an organic medium; PO-fR (I) wherein PO is a repeating unit derived from an olefin having 2 to 20 carbon atoms, and has a weight average molecular weight. Is 2,
A polyolefin segment greater than or equal to 000, f
Represents an ether bond, an ester bond or an amide bond, R represents a chain polymerization reaction, and has a weight average molecular weight of 5
3 shows a functional segment containing a repeating unit that is greater than or equal to 00. ).

A resin dispersion according to another aspect of the present invention is an olefin polymer composition containing the olefin block copolymer (A) and a thermoplastic resin (B) other than the olefin block copolymer (A). It is characterized in that the substance (C) is dispersed in an organic medium.

[0008]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the resin dispersion according to the present invention will be specifically described. The resin dispersion according to the present invention,
An olefin block copolymer (A) represented by the following general formula (I) is dispersed in an organic medium. Olefin-based block copolymer (A) PO-fR (I) In the formula, PO is a polyolefin segment composed of a repeating unit derived from an olefin having 2 to 20 carbon atoms. An olefin homopolymer or copolymer selected from olefins having 2 to 20 atoms. When this polyolefin segment has stereoregularity, it may be either an isotactic polyolefin or a syndiotactic polyolefin.

Examples of the olefin having 2 to 20 carbon atoms include linear or branched α-olefins, cyclic olefins, aromatic vinyl compounds, conjugated dienes, and non-conjugated 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,
2 to 2 carbon atoms such as 1-octadecene and 1-eicosene
0, preferably 2 to 10.

Examples of the cyclic olefin include those having 3 to 20, preferably 5 to 15 carbon atoms, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, and vinylcyclohexane. As the aromatic vinyl compound, for example, styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-methylstyrene Mono- or polyalkylstyrenes such as ethylstyrene are mentioned.

Examples of the conjugated diene include 1,3-butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,
3-dimethylbutadiene, 4-methyl-1,3-pentadiene,
Examples thereof include those having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, such as 1,3-pentadiene, 1,3-hexadiene, and 1,3-octadiene. 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, methylenenorbornene, 5-vinylnorbornene, 5-
Ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2- C5-20, preferably 5-1 carbon atoms such as ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,2-norbornadiene.
0.

The polyolefin segment has a weight average molecular weight of usually 2,000 or more, preferably 2,000 to 2,000.
1,000,000, more preferably 10,000-80
0000, particularly preferably 50,000 to 500,00.
It is desirable to be in the range of 0. As the polyolefin segment, ethylene homopolymer, ethylene polymer such as ethylene / α-olefin copolymer; propylene homopolymer, propylene polymer such as propylene / α-olefin copolymer; butene homopolymer, Preferred are a butene-based polymer such as a butene-ethylene copolymer; and a 4-methyl-1-pentene-based polymer such as a 4-methyl-1-pentene homopolymer.

In the general formula (I), f is an ether bond, an ester bond or an amide bond, and among them, an ether bond is preferable. Such a part f may include a part of a structure obtained by the following chain polymerization reaction, for example, a ring opening polymerization reaction, a radical polymerization reaction, or an ionic polymerization reaction. This part f chemically bonds the above-mentioned polyolefin segment and the following functional segment.

In the above general formula (I), R is a functional segment obtained by a radical polymerization reaction, a ring-opening polymerization reaction or an ionic polymerization reaction, and contains a repeating unit containing an unsaturated hydrocarbon and / or a hetero atom. It is preferably a functional segment containing a repeating unit, and more preferably obtained by a radical polymerization reaction or a ring-opening polymerization reaction.
Further, it is preferable that PO and R are segments composed of different polymers.

The repeating unit forming the functional segment is a radical polymer such as methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl methacrylate, vinyl acrylate (VA), butyl acrylate (BA), styrene, acrylonitrile, vinyl acetate and the like. Repeating units derived from a reactive monomer; lactones, lactams, 2-oxazolines, cycloethers such as β-propiolactone, β-butyrolactone,
δ-valerolactone, glycolide, lactide, ε-caprolactone, α-pyrrolidone, γ-butyrolactam, ε-
Ring-opening polymerizable monomers such as caprolactam, ethylene oxide, propylene oxide, epichlorohydrin, oxetane, tetrahydrofuran, and octamethylcyclotetrasiloxane.

Further, as the ionic polymerizable monomer,
Anionic polymerizable monomers such as (meth) acrylates, acrylonitrile, acrylamide and the like can be mentioned. This functional segment has a weight average molecular weight (M
w) is usually 500 or more, preferably 5000 to 1,000.
000, more preferably 2,000 to 800,00
0, particularly preferably in the range of 10,000 to 500,000.

Specific examples of the functional segment include styrene homopolymers, styrene-based polymers such as styrene / maleic anhydride copolymers, and vinyl acetate-based polymers;
Acrylic ester polymer; methacrylic ester polymer such as methyl methacrylate homopolymer; vinyl formamide polymer; acrylamide polymer, cyclic ester polymer; cyclic amide polymer; cyclic ether polymer An oxazoline-based polymer; a segment comprising a fluorine-containing polymer and the like.

The functional segment is preferably 0.01 to 9 based on the olefin block copolymer (A).
9.99% by weight, preferably 1 to 99% by weight, more preferably 1 to 95% by weight, particularly preferably 1 to 90% by weight
Is preferably contained in an amount of 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 200 g / 10 min, preferably 0.05. -100 g / 10 min, more preferably 0.05-80 g / 10 min.

The olefin block copolymer (A) is
In terms of good dispersibility in a solvent and excellent heat sealability with a polyolefin, the PO portion is an ethylene homopolymer,
Random copolymer of ethylene and α-olefin having 3 to 20 carbon atoms (content of α-olefin having 3 to 20 carbon atoms is less than 10 mol%), propylene homopolymer, propylene / ethylene random copolymer (ethylene Content of less than 10 mol%), random copolymer of propylene and α-olefin having 4 to 20 carbon atoms (content of less than 10 mol% of α-olefin having 4 to 20 carbon atoms), ethylene and 3 to 20 carbon atoms Random copolymer with an α-olefin of 20 (ethylene content: 10 to 90 mol%, C3 to C20)
Α-olefin content of 90 to 10 mol%), a random copolymer of propylene and an α-olefin having 4 or more carbon atoms (propylene content of 10 to 90 mol%, carbon atom of 4
Α-olefin content of 90 to 10 mol%) and R is a homopolymer of (meth) acrylic acid such as polymethyl methacrylate or a derivative thereof or (meth)
A copolymer of two or more monomers selected from acrylic acid and derivatives thereof, or a polyalkylene glycol having 2 to 4 carbon atoms such as polyethylene glycol and polypropylene glycol, polyvinyl alcohol, poly (2-hydroxyalkyl methacrylate), and the like. Preferably, it is a polyhydroxyalkyl (meth) acrylate.

The olefin block copolymer (A) is
In that stable dispersibility and good heat sealability are obtained,
PO is an ethylene homopolymer, ethylene and carbon atoms of 3 to
A random copolymer with an α-olefin of 20 (α-olefin content of less than 10 mol% of 3 to 20 carbon atoms), a propylene homopolymer, a propylene / ethylene random copolymer (ethylene content of less than 10 mol%), A random copolymer of propylene and an α-olefin having 4 to 20 carbon atoms (content of an α-olefin having 4 to 20 carbon atoms of less than 10 mol%), and a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms Random copolymer (ethylene content 10 to 90
Mole%, α-olefin content of 3 to 20 carbon atoms 90
-10 mol%), propylene and α- having 4 or more carbon atoms.
Random copolymer with olefin (propylene content 10
Wherein R is a homopolymer of (meth) acrylic acid such as polymethyl methacrylate or a derivative thereof, or (meth) acrylic acid. And a copolymer of two or more types of monomers selected from derivatives thereof and a polycyclic ester such as polycaprolactone.

More specifically, as preferred examples of the olefin block copolymer (A), PO is polypropylene (Mw: 2,000 to 1,000,000), f is an ether bond, and R is poly ( 2-hydroxyethyl methacrylate) (Mw: 500 to 1,000,000) is a block copolymer in which PO is polypropylene (Mw: 2,000 to
1,000,000), f is an ether bond, R is a polyethylene glycol (Mw: 500 to 1,000,000) block copolymer, and PO is an ethylene / butene copolymer (butene content: 0.1 to 30 mol). %, Mw: 2,000
-1 million), f is an ether bond, R is a polycaprolactone (Mw: 500-1,000,000) block copolymer, and PO is an ethylene-octene copolymer (octene content: 0.1-30) Mol%, Mw: 2,000
0 to 1,000,000), f is an ether bond, R is a polycaprolactone (Mw: 500 to 1,000,000) block copolymer, and PO is an ethylene / octene copolymer (octene content: 0.1 to 1,000,000). 30 mol%, Mw: 2,000
0 to 1,000,000), f is an ether bond, and R is polymethyl methacrylate (Mw: 5 to 1,000,000)
Is a block copolymer, PO is an ethylene / octene copolymer (octene content: 0.1 to 30 mol%, Mw:
2,000 to 1,000,000), f is an ether bond, and R is polycaprolactone (Mw: 500 to 100).
Block copolymer, PO is an ethylene / octene copolymer (octene content: 0.1 to 30 mol%, M
w: 2,000 to 1,000,000), f is an ether bond, and R is a St / MAH copolymer (Mw: 500 to 1).
000,000).

When the olefin block copolymer (A) as described above is used for the dispersion, the dispersibility in the organic medium is higher than when a conventionally known modified polyolefin obtained by modifying a polyolefin with a polar monomer is used. Excellent in adhesion to paint when used as a primer for polypropylene coating. Method for producing olefin-based block copolymer (A) Such an olefin-based block copolymer (A) can be produced as follows.

The olefin block copolymer (A) used in the present invention is prepared, for example, by first producing a polyolefin having a group 13 element bonded to its terminal, and then conducting a chain polymerization reaction, for example, a radical polymerization in the presence of the polyolefin. It can be produced by forming active species such as a reaction, a ring-opening polymerization reaction and an ionic polymerization reaction and performing these reactions.

In order to produce a polyolefin having a terminal group 13 element bonded thereto, first, the above-mentioned olefin having 2 to 20 carbon atoms is homopolymerized or copolymerized in the presence of a conventionally known catalyst for olefin polymerization. Let it. The polyolefin produced here is a polyolefin segment of the olefin-based block copolymer (A) (hereinafter referred to as “PO part”).
There is that. ).

Examples of conventionally known olefin polymerization catalysts include TiCl ₃ -based catalysts, MgCl ₂ -supported TiCl ₄ -based catalysts, metallocene-based catalysts, and post-metallocene-based catalysts. Metallocene-based catalysts are preferably used.
Examples of preferably used metallocene catalysts include conventionally known metallocene catalysts. Examples of metallocene catalysts include transition metal metallocene compounds such as titanium, vanadium, chromium, zirconium, and hafnium. The metallocene compound may be used in a liquid state or a solid state under the use conditions. Also,
These need not be a single compound, but may be supported on another compound, may be a homogeneous mixture with another compound, and may be a complex compound or a complex compound with another compound. Is also good.

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 the metallocene compound having a chiral structure having C2 symmetry include rac-ethylene-bis (indenyl) zirconium dichloride, rac-ethylene-bis (tetrahydroindenyl) zirconium dichloride, and 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-dimethyl Silylene-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, 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, ra
c-dimethylsilylene-bis {1- [2-n-propyl-4- (1-naphthyl) indenyl]} zirconium dichloride, rac-
Dimethylsilylene-bis {1- [2-n-propyl-4- (9-phenanthryl) indenyl]} zirconium dichloride is a preferred example.

Examples of the metallocene compound having a C1 symmetry and having a chiral structure include ethylene [2-methyl-4- (9-phenanthryl) -1-indenyl] (9-fluorenyl) zirconium dichloride and 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) (3-t
-Butylcyclopentadienyl) zirconium dichloride and the like can be mentioned as preferred examples.

Further, among conventionally known metallocene compounds,
Preferably used metallocene compounds include substituted
Metallocene with only one cyclopentadienyl group
Compounds are also included. For example, (tertiary butylamide) (teto
Lamethyl-η^Five-Cyclopentadienyl) -1,2-ethanedii
Ruzirconium dichloride, (tertiary butyl amide)
Tramethyl-η ^Five-Cyclopentadienyl) -1,2-ethanedi
Il titanium dichloride, (methylamide) (tetramethyl-
η^Five-Cyclopentadienyl) -1,2-ethanediylzirconi
Umm dichloride, (methylamide) (tetramethyl-η^Five-S
Clopentadienyl) -1,2-ethanediyl titanium dichloride
De, (ethylamide) (tetramethyl-η^Five-Cyclopentadi
Enyl) methylene titanium dichloride, (tertiary butyl
Mido) dimethyl (tetramethyl-η^Five-Cyclopentadie
Nil) silane titanium dichloride, (tertiary butylamido)
Do) dimethyl (tetramethyl-η^Five-Cyclopentadieni
Le) silane zirconium dibenzyl, (benzylamido)
Do) dimethyl (tetramethyl-η^Five-Cyclopentadieni
Le) silane titanium dichloride, (phenyl phosphide)
Dimethyl (tetramethyl-η^Five-Cyclopentadienyl)
Silane zirconium dibenzyl and the like.

Further, among the conventionally known metallocene compounds, the metallocene compound preferably used has two substituted cyclopentadienyl groups, and the two cyclopentadienyl are (substituted) alkylene, (substituted) ) Metallocene compounds that are not bonded by a bonding group such as silylene are also included. For example, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxycyclolide, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate) 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 Cyclopentadienyl)
Zirconium bis (methanesulfonato), bis (trimethylcyclopentadienyl) zirconium dichloride,
Bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, and the like.

The above metallocene compounds may be used alone.
Two or more kinds may be used in combination._Threesystem
Catalyst, MgCl_TwoSupported TiCl_FourBased catalyst, post metallo
Combination with other olefin polymerization catalysts such as styrene catalysts
They may be used together. In the production of polyolefin,
Metallocene compounds are combined with the following organometallic catalyst components
Used. Also, TiCl_ThreeSystem catalyst, MgCl_TwoResponsible
Holding type TiCl _Four-Based catalyst or post-metallocene-based catalyst
Also used in combination with the following organometallic catalyst components
used.

The post-metallocene catalyst is a transition metal complex containing a nitrogen atom or an oxygen atom in a ligand, and a conventionally known transition metal complex is preferably used. Examples of post-metallocene catalysts include transition metal complexes as described in the following references. 1) M. Brookhart et al., J. Am. Chem. Soc. 1995, 117, 6414-
6415 2) M. Brookhart et al., J. Am. Chem. Soc. 1996, 118, 267-2
68 3) DHMcConville et al., Macromolecules 1996, 29, 52
41-5243 4) RFJordan et al., Organometallics 1997,16,3282-
3302 5) RHGrubbs et al., Organometallics 1998, 17, 3149-
3151 6) S. Collins et al., Organometallics 1999, 18, 2731-2
733 7) MSEisen et al., Organometallics 1998, 17, 3155-3
157 8) MSEisen et al., J. Am. Chem. Soc. 1998, 120, 8640-86
36 9) RFJordan et al., J. Am. Chem. Soc. 1997, 119, 8125-8
126 10) K. Hakala et al., Macromol. Rapid Commun. 18, 634-6
38 (1997) The organometallic catalyst component preferably contains an element selected from Group 13 of the periodic table. Among them, an organoaluminum compound, an organic boron compound, a complex alkyl compound of aluminum or boron with a Group 1 element of the periodic table And the like.

As the organoaluminum compound, for example, compounds represented by the following general formula can be exemplified. R ^a _n AlX _3-n (wherein, R ^a represents a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen or hydrogen, n represents a 0 to 3.) R ^a is a carbon atom A hydrocarbon group of Formulas 1 to 12, such as an alkyl group, a cycloalkyl group or an aryl group,
Specific examples include methyl, ethyl, n-propyl, isopropyl, isobutyl, pentyl, hexyl, octyl, cyclopentyl, cyclohexyl, phenyl, tolyl and the like.

Specific examples of such an organoaluminum compound include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, tri2-aluminum, and the like.
Trialkylaluminums such as ethylhexylaluminum; trialkenylaluminums such as triisoprenylaluminum; dimethylaluminum chloride;
Diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride,
Dialkyl aluminum halides such as dimethyl aluminum bromide, methyl aluminum sesquichloride,
Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; alkyl aluminum dihalides such as methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride, ethyl aluminum dibromide; diethyl Alkyl aluminum hydrides such as aluminum hydride, diisobutyl aluminum hydride and ethyl aluminum dihydride are exemplified.

As the organoaluminum compound, the following
A compound represented by the general formula can also be used. R^a _nAlY_3-n In the above formula, R^aIs the same as above, and Y is -O
R^bGroup, -OSiR^c _ThreeGroup, -OAlR^d _TwoGroup, -NR
^e _TwoGroup, -SiR^f _ThreeGroup or -N (R^g) AlR^h _TwoIn the base
And n is 1-2, R^b, R^c, R^dAnd R^hIs
Chill, ethyl, isopropyl, isobutyl, cyclohexyl
Sil, phenyl and the like;^eIs a hydrogen atom, methyl,
Ethyl, isopropyl, phenyl, trimethylsilyl
Which is R^fAnd R^gIs methyl, ethyl and the like.

Specific examples of such an organoaluminum compound include the following compounds. (I) ^a compound represented by R ^a _n Al (OR ^b ) _3-n , for example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, and (ii) R ^a n Al (OSiR ^c ) _3- n _n , for example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂
Al (OSiMe ₃ ), (iso-Bu) ₂ Al (OSiEt ₃ ), etc., and (iii) compounds represented by R ^a _n Al (OAlR ^d ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ , (iso-Bu) ) ₂ AlOAl
(Iso-Bu) _{2, ^{etc., (iv) R a n Al}} (NR e 2) a compound represented by _3-n, e.g., Me ₂ AlNEt _2, Et ₂ AlNHM
e, Me ₂ AlNHEt, Et ₂ AlN (Me ₃ Si) ₂ , (iso-B
u) ₂ AlN (Me ₃ Si) ₂ and (v) R ^a _n Al (Si
R ^f ₃ ) A compound represented by _3-n , for example, (iso-Bu) ₂ Al
Such as ^{_{SiMe 3, (vi) R a}} n Al [N (R ^g) -Al
R ^h ₂ ] _3-n , for example, Et ₂ AlN (M
e) -AlEt ₂ (iso-Bu) ₂ , AlN (Et) Al (iso-Bu)
₂ etc.

Compounds similar to this, such as oxygen
, Two or more aluminum atoms are bonded via a nitrogen atom
Organic aluminum compounds can be mentioned. concrete
Contains (C_TwoH_Five)_TwoAlOAl (C_TwoH_Five)_Two, (C_FourH₉)_TwoAl
OAl (C_FourH₉) _Two, (C_TwoH_Five)_TwoAlN (C_TwoH_Five) Al (C_Two
H_Five)_Two Such. Furthermore, methyl aluminoxane, ethyl alcohol
Minoxane, propylaluminoxane, butylalumino
Aluminoxanes such as xane can be mentioned.

Also, an organoaluminum compound represented by the following general formula can be used. R ^a AlXY (where R ^a , X and Y are the same as above) Examples of the organic boron compound 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, Disiamyl borane, diisopinocan phenyl borane, 9-borabicyclo
[3.3.1] Nonane, dimethylborane, dichloroborane, catecholborane, B-bromo-9-borabicyclo [3.3.1] nonane, borane-triethylamine complex, borane-methylsulfide complex and the like.

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) boron 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 [tri (n-butyl) ammonium] nonaborate, bis [Tri (n-butyl) ammonium] decaborate and the like can be mentioned.

Examples of the complex alkylated product of Group 1 element and aluminum of the periodic table include compounds represented by the following general formula. M ¹ AlR ^j ₄ (in the formula, M ¹ represents Li, Na or K, and R ^j represents a hydrocarbon group having 1 to 15 carbon atoms.) Specifically, LiAl (C ₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) ₄
And the like.

Examples of the organoboron compound and the complex alkylated product of boron with the Group 1 element of the periodic table include the above-mentioned organoaluminum compound and the complex alkylated product of aluminum with the Group 1 element of the periodic table in which aluminum is substituted with boron. Can be mentioned. The organometallic catalyst components can be used alone or in combination of two or more.

The organometallic catalyst component is preferably used in combination with a compound having a hydrogen-13 group element bond and a trialkylaluminum, an aluminoxane or an ionic boron compound. The compound is preferably a compound having a hydrogen-boron bond. These compounds may be used for polymerization after mixing, or after starting polymerization using only trialkylaluminum or aluminoxane or ionic boron compound, a compound having a hydrogen-13 group element bond may be added to the polymerization system. preferable.

Examples of the compound having a hydrogen group 13 element bond include diethylaluminum hydride, diisobutylaluminum hydride and ethylaluminum dihydride among the organic aluminum compounds; and 9-borabicyclo [3.
3.1] Nonane, dimethylborane, dichloroborane, catecholborane and the like.

The olefin polymerization catalyst as described above may be preliminarily polymerized. There is no particular limitation on the method of performing the prepolymerization, for example, can be performed in the presence of an inert solvent,
It is preferable to add the olefin and each catalyst component to the inert solvent and carry out prepolymerization under relatively mild conditions. At this time, the reaction may be performed under the condition that the produced prepolymer is dissolved in the polymerization medium, or may be performed under the condition that the prepolymer is not dissolved.
It is preferably performed under conditions that do not dissolve.

Examples of the olefin used for the prepolymerization include α-olefins having 2 or more carbon atoms. Specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 3-methyl-olefin. 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 and the like. These may be used in combination of two or more. The α-olefin used in the prepolymerization may be the same as or different from the α-olefin used in the olefin polymerization described below, but is preferably the same as the olefin used in the olefin polymerization.

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; and halogenated hydrocarbons such as ethylene chloride and chlorobenzene. These may be used in combination.

Among these inert solvents, it is particularly preferable to use an aliphatic hydrocarbon. The prepolymerization is α-
The reaction can be carried out in a state in which the olefin is in a liquid state, or under gas phase conditions. The prepolymerization can be performed in any of a batch system, a semi-continuous system, and a continuous system. Further, in the preliminary polymerization, it is preferable to use a catalyst having a higher concentration than the catalyst concentration in the system in the main polymerization.

The above olefin block copolymer (A)
The polyolefin to be the PO portion of the olefin is a homopolymerization or copolymerization of the olefin having 2 to 20 carbon atoms as described above in the presence of the olefin polymerization catalyst as described above (hereinafter, referred to as “Polyolefin”).
Sometimes simply referred to as “olefin polymerization”. ). The olefin polymerization can be carried out by any of a liquid phase polymerization method such as solution polymerization and suspension polymerization or a gas phase polymerization method. As the reaction solvent for suspension polymerization, the above-mentioned inert solvent can be used, or an olefin that is liquid at the reaction temperature can be used. The reaction temperature is
Usually, it is 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 it is 1 to 50 atm. The olefin polymerization can be performed in any of a batch system, a semi-continuous system, and a continuous system. When the olefin polymerization is performed in two or more stages, the reaction conditions may be the same or different.

In the olefin polymerization, the weight average molecular weight is usually at least 2,000, preferably from 2,000 to 1,000,000.
00 polyolefin is produced. In this case, it is preferable that molecular hydrogen, which is a general molecular weight regulator, is not present in the polymerization system. It is preferable to control by controlling one or more kinds. Specifically, as a method for adjusting the molecular weight, for example, in suspension polymerization in which molecular hydrogen is substantially absent, increasing the concentration of the organometallic catalyst component can reduce the molecular weight of the obtained polyolefin, In suspension polymerization in which molecular hydrogen is substantially absent, raising the polymerization temperature can lower the molecular weight of the resulting polyolefin.

One end of the polyolefin obtained as described above is a terminal to which a group 13 element is bonded or an unsaturated bond terminal. Whether one end of the polyolefin is a group 13 element-bonded terminal or an unsaturated bond terminal depends on polymerization conditions such as the type and / or amount of the organometallic catalyst component used and the polymerization temperature. When one terminal of the polyolefin is an unsaturated bond terminal, a compound containing a Group 13 element is reacted to convert the compound into a terminal to which a Group 13 element is bonded.
In addition, when the obtained polyolefin is a mixture of one having a group 13 element bonded to one end and one having an unsaturated bond terminal at one end, if necessary, one end may have an unsaturated bond. You may convert the terminal of the polyolefin which is a terminal into the terminal which group 13 element couple | bonded.

The compound containing a group 13 element used in the reaction is selected from the compounds exemplified as the organic compound catalyst component, and the compounds exemplified as the organic aluminum compound or the organic boron compound are preferably used.
Among them, 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.

The reaction between a polyolefin having an unsaturated bond terminal at one end and a compound containing a Group 13 element is carried out, for example, as follows. 0.1 to 5 polypropylene having a vinylidene group at the end
0 g and 0.1 g of diisobutylaluminum hydride.
01-5 mol / l-octane solution is 5-1000
Mix with milliliters and reflux for 0.5-6 hours. 0.1 to 5 polypropylene having a vinylidene group at the end
0 g, 5 to 1000 ml of anhydrous tetrahydrofuran, and 0.1 to 50 ml of a solution of 9-borabicyclo [3.3.1] nonane in 0.05 to 10 mol / l-tetrahydrofuran. 0.
Stir for 5-24 hours.

As described above, a polyolefin to be the PO part of the olefin block copolymer (A) is produced. A group 13 element is bonded to one end of the obtained polyolefin. Preferably, the Group 13 element is boron. Next, in the presence of a polyolefin having a Group 13 element bonded to one end, chain polymerization active species such as a radical polymerization reaction, a ring-opening polymerization reaction, and an ionic polymerization reaction are formed, and these reactions are performed to perform olefin block copolymerization. A polymer (A) is produced. By this reaction, the 1
An f-part is formed between the group III element and the polyolefin segment, and a polymer produced by a chain polymerization reaction such as a radical polymerization reaction, a ring-opening polymerization reaction, or an ionic polymerization reaction has a functional segment (hereinafter referred to as “R part”). "). The 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, and an ionic polymerization reaction.

This polymerization reaction is carried out, 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 to cause a radical polymerization reaction. Do. Specifically, a polyolefin having boron bonded to one end is oxidized with molecular oxygen in the presence of a radically polymerizable monomer. This allows the terminal boron to become peroxyborane (-
OOB). The peroxyborane is stirred in the presence of a radically polymerizable monomer to produce O-O
The bond is cleaved to generate a radical, and the generated alkoxy radical (-O ^* ) acts as an initiator to cause radical polymerization of the radical polymerizable monomer.

The radical polymerizable monomers include methyl methacrylate (MMA) and ethyl methacrylate (E
MA), butyl methacrylate, vinyl acrylate (VA), butyl acrylate (BA), styrene, acrylonitrile, vinyl acetate, and the like.
These radically polymerizable monomers can be used alone,
It may be used in combination of more than one kind.

The termination of the radical polymerization can be carried out by precipitating the polymer in methanol. As described above, the olefin block copolymer (A) in which the f portion is an ether bond or an ester bond and the R portion is a radical polymer can be produced. (2) When the group 13 element bonded to one end of the polyolefin is aluminum, a carbon-aluminum bond is oxidized with molecular oxygen to generate an active species to perform a ring-opening polymerization reaction.

Specifically, the carbon-aluminum bond is oxidized with molecular oxygen, whereby aluminum at the terminal of the PO portion is converted into aluminum oxide (-O-Al). The ring-opening polymerizable monomer is subjected to ring-opening polymerization using the thus obtained aluminum oxide as an active species. As ring-opening polymerizable monomers, lactones, lactams, 2-
Oxazolines, cycloethers and the like, specifically, β-propiolactone, β-butyrolactone, δ-valerolactone, glycolide, lactide, ε-caprolactone, α-pyrrolidone, γ-butyrolactam, ε-caprolactam, Examples include 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.

The ring-opening polymerization reaction is carried out usually at a temperature of 0 to 100 ° C. for 30 minutes to 12 hours, preferably for 1 hour to 6 hours. The ring-opening polymerization reaction can be stopped by precipitating the polymer in methanol. As described above, the olefin block copolymer (A) in which the f portion is an ether bond or an ester bond and the R portion is a ring-opening polymer can be produced. (3) After converting a Group 13 element bonded to one end of the polyolefin into a hydroxyl group, an amino group, an aldehyde group or a halogen, a ring-opening polymerization reaction is performed by generating a ring-opening polymerization active species.

The ring-opening polymerization active species is produced, for example, by adding a sodium hydroxide solution and a hydrogen peroxide solution to a polyolefin having one end bonded to boron at 40 ° C. to 50 ° C.
The reaction can be performed by converting boron into a hydroxyl group by reacting for up to 5 hours, reacting butyllithium with this, and then reacting with diethylaluminum chloride to convert the hydroxyl group into aluminum oxide.

The above 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 to be an active species for the ring-opening polymerization reaction. Active species other than aluminum oxide are generated using a hydroxyl group, an amino group, an aldehyde group or a halogen bonded to one end of the polyolefin. Among these, it is preferable to use aluminum oxide as the active species. As described above, the olefin block copolymer (A) in which the f portion is an ether bond, an ester bond, or an amide bond and the R portion is a ring-opening polymer can be produced.

As an example of the ionic polymerization reaction, for example, in the case of performing an anionic polymerization reaction, after converting the above-mentioned polyolefin having a hydroxyl group at the terminal into a polyolefin having a lithium, potassium, sodium, phosphorus-containing group or the like at the terminal, It can be obtained by polymerizing a monomer capable of anion polymerization. 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 a terminal lithium is described.

Of a polyolefin having a terminal lithium
The prepared polyolefin having a terminal lithium is obtained by reacting the polyolefin having a terminal hydroxyl group with an organic lithium compound. The reaction between the polyolefin having a hydroxyl group at the terminal and the organolithium compound is usually performed in a solvent.

Examples of the organic lithium compound include alkyl lithium such as butyl lithium, propyl lithium, ethyl lithium and methyl lithium; and alkoxy lithium such as butoxy lithium, propoxy lithium, ethoxy lithium and methoxy lithium. In the present invention, alkyl lithium is more preferably used.

Examples of the solvent used in the reaction include the same hydrocarbons as those exemplified as the inert hydrocarbon medium. When reacting a polyolefin having a hydroxyl group at an end with an organolithium compound, the organolithium compound is added in an amount of 0.1 to 1 mol of the hydroxyl group at the end of the polyolefin.
To 100 mol, preferably 0.2 to 10 mol. The reaction temperature is generally -100 to 100C, preferably 0 to 80C, and the reaction time is usually 0.1 to 48.
Hours, preferably 0.5 to 12 hours.

Thus, a polyolefin having a terminal lithium represented by the following general formula (II) is produced. PO—O—Li (II) wherein PO has a weight average molecular weight of 1,000 to 10,000.
0,000, preferably 3,000 to 1,000,000,
More preferably, the polyolefin segment has a molecular weight of 5,000 to 500,000. The terminal Li polyolefin has Mw / Mn of 2 or more, preferably 3 to 15,
More preferably, it is desirable to be in the range of 4 to 14.

Production of Block Copolymer Next, for example, (meth) acrylate is anionically polymerized in the presence of the above-mentioned terminal Li polyolefin to form a polyolefin block copolymer comprising a polyolefin segment and a (meth) acrylate segment. Obtain a polymer. The polymerization is carried out by mixing a solvent, a terminal Li polyolefin and a (meth) acrylate, or
It is performed by mixing i-polyolefin and liquid (meth) acrylate. The anionic polymerization active species can be formed by mixing the terminal Li polyolefin, the solvent, and the (meth) acrylate.

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), Ether solvents such as monoglyme and diglyme are used. These solvents are 1
Species can be used alone or in combination of two or more. Among them, aromatic hydrocarbons and ether solvents are preferably used.

Examples of the (meth) acrylate include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, vinyl acrylate, and methacrylic acid. 2-methoxyethyl acid, 2- (N, N-diethylamino) ethyl methacrylate and the like. These (meth) acrylic acid esters can be used alone or in combination of two or more. As the combination of the (meth) acrylic ester, 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 In combination with

In the polymerization, a compound useful for forming an anionic polymerization active species such as triphenylphosphine, α, α'-dipyridyl, hexamethylphosphoramide (HMPA), titanium tetrachloride, alkyllithium and alkoxylithium is added. May be. Polymerization is usually -100 ° C
At a polymerization temperature of 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 15 minutes to 150 hours. Will be implemented. In this polymerization, the terminal Li polyolefin is 0.001 to 10
0 mol / liter, preferably 0.005 to 50 mol /
Liter, more preferably 0.01 to 10 mol / l, even more preferably 0.1 to 5 mol / l. The (meth) acrylic acid ester is usually used in an amount of 0.001 to 500 mol / l, preferably 0.1 to 500 mol / l.
005-300 mol / l, more preferably 0.0
It is used at a concentration of 1-150 mol / l.

It is preferable to produce a poly (meth) acrylate segment having stereoregularity by the above polymerization. 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
For and mm, the sample was dissolved in nitrobenzene-d5, and ¹ H-NMR was measured.
Rr, mr, mm detected near 5, 1.25 ppm
Peak area of rr to the sum of peak areas of
It is determined from the ratio of the peak area of m.

As described above, a polymer containing a block copolymer in which a polyolefin segment (PO) and a poly (meth) acrylate segment are chemically bonded can be produced. Whether or not the polymer containing the (meth) acrylate segment is chemically bonded can be determined by, for example, the molecular weight of the obtained polymer, the 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, and corresponds to the polyolefin segment of the olefin-based block copolymer polymer obtained by the method of the present invention. The dissolution behavior in an organic solvent of a mixture of a polymer and a polymer corresponding to a segment of a polymer produced by anionic polymerization of the polymer indicates that the olefin-based block copolymer obtained by the method of the present invention is soluble in an organic solvent. Behave differently, or
The terminal structure of the olefin-based block copolymer obtained by the method of the present invention is analyzed by ¹³ C-NMR to determine the chemical bond between the polyolefin segment and the poly (meth) acrylate segment of the polymer produced by anionic polymerization. It can be determined that the target block copolymer has been produced by detecting the derived peak.

In the above chain polymerization such as radical polymerization reaction, ring opening polymerization reaction and ionic polymerization reaction, the weight average molecular weight is usually 500 or more, preferably 5000 to 1,000.
Produce 000 polymer. The solvent dispersion according to the present invention is obtained by dispersing the olefin-based block copolymer (A) as described above in a solvent. The olefin-based block copolymer (A) may contain a conventionally known additive used as a filler or other resin in an arbitrary ratio.

The olefin polymer composition (C) and the solvent dispersion according to the present invention comprise an olefin containing the olefin block copolymer (A) and a thermoplastic resin (B) other than the olefin block copolymer (A). The system polymer composition (C) may be dispersed in a solvent. Thermoplastic resin (B) As the thermoplastic resin (B), polyolefin, polyamide, polyester, polyacetal, polystyrene,
Acrylonitrile-butadiene-styrene copolymer (A
BS), polycarbonate, polyphenylene oxide, polyacrylate and the like.

Specific examples of polyolefins include ethylene polymers such as ethylene homopolymer, ethylene / α-olefin copolymer, and ethylene / polar group-containing vinyl copolymer; propylene homopolymer, propylene / α-olefin Propylene-based polymers such as copolymers; butene-based polymers such as butene homopolymer; 4-methyl-1-pentene-based polymers such as 4-methyl-1-pentene homopolymer; 3-methyl-
3-methyl-1-butene polymers such as 1-butene homopolymer; hexene polymers such as hexene homopolymer; Among them, ethylene-based polymers, propylene-based polymers, and 4-methyl-1-pentene-based polymerizations are preferable, and in the case of ethylene-based polymers, ethylene / polar group-containing vinyl copolymers are preferable.

Specific examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate;
Polycaprolactone, polyhydroxybutyrate and the like can be mentioned. Among them, polyethylene terephthalate is particularly preferred. Specifically, as a polyamide, nylon-
6, Nylon-66, Nylon-10, Nylon-1
2, aliphatic polyamides such as nylon-46; and aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines. Among them, nylon-6 is particularly preferred.

Specific examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, and polybutyraldehyde. Among them, polyformaldehyde is particularly preferred. The polystyrene may be a homopolymer of styrene or a binary copolymer of styrene with acrylonitrile, methyl methacrylate, and α-methylstyrene.

The ABS contains 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 is derived from styrene. Structural unit 40 ~
ABS containing 60 mol% is preferably used. Examples of polycarbonate include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane,
Examples include polymers obtained from 2-bis (4-hydroxyphenyl) butane and the like. Among them, polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane is particularly preferable.

As the polyphenylene oxide, it is preferable to use poly (2,6-dimethyl-1,4-phenylene oxide). As the polyacrylate, it is preferable to use polymethyl methacrylate and polybutyl acrylate. Thermoplastic resin (B) as described above
May be used alone or in combination of two or more.

The olefin polymer composition (C) used in the present invention contains the olefin block copolymer (A) in an amount of 1 to 99% by weight, preferably 50 to 99% by weight.
99 to 1% by weight, preferably 5% by weight of the thermoplastic resin (B)
Desirably, it is contained in an amount of 0 to 1% by weight. The olefin polymer composition (C) may further include an inorganic filler, an organic filler, a heat stabilizer, a weather stabilizer, a colorant, and the like. Further, the olefin polymer composition (C) may contain a thermosetting resin.

Inorganic fillers include inorganic fillers such as silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, titanic acid. Calcium, barium sulfate, calcium sulfite, talc,
Clay, mica, asbestos, glass fiber, glass flake, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder,
Molybdenum sulfide and the like can be mentioned.

Among them, a layered compound is preferable, and a clay mineral having swelling / cleaving properties with respect to a dispersion medium is particularly preferably used. Such clay minerals are generally of a type having a two-layer structure having an octahedral layer having aluminum or magnesium as a central metal on the top of a tetrahedral layer of silica, and a type having a tetrahedral layer of silica containing aluminum or magnesium. It is classified into a type having a three-layer structure in which an octahedral layer serving as a central metal is narrowed from both sides. The former two-layer structure type includes kaolinite group and antigolite group, and the latter three-layer structure type includes smectite group, vermiculite group and mica group depending on the number of interlayer cations. Can be.

More specifically, these clay minerals include kaolinite, dickite, nacrite, halloysite, antigorite, chrysotile, pyrophyllite, montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, hectite. Light, tetrasilicyl mica, sodium teniolite, muscovite, margarite, talc, vermiculite, phlogopite, zansophyllite, chlorite and the like can be mentioned.

A clay mineral treated with an organic substance (hereinafter sometimes referred to as an organically modified clay mineral) can also be used as an inorganic layered compound. See Clay Encyclopedia). Among the above clay minerals, smectites, vermiculites, and micas are preferable, and smectites are more preferable, from the viewpoint of swelling or cleavage. Examples of the smectite group include montmorillonite, beidellite, nontronite, saponite, sauconite, stevensite, and hectorite.

The dispersion medium for swelling or cleaving the inorganic layered compound is, for example, in the case of a natural swellable clay mineral, water, alcohols such as methanol, ethanol, propanol, isopropanol, ethylene glycol and diethylene glycol, dimethylformamide, dimethyl sulfoxide, Acetone is mentioned, and alcohols such as water and methanol are more preferable.

In the case of organically modified clay minerals, aromatic hydrocarbons such as benzene, toluene, and xylene; ethers such as ethyl ether and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; n-pentane; aliphatic hydrocarbons such as n-hexane and n-octane; halogenated hydrocarbons such as chlorobenzene, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and perchloroethylene;
Examples include ethyl acetate, methyl methacrylate (MMA), dioctyl phthalate (DOP), dimethylformamide, dimethyl sulfoxide, methyl cellosolve, and silicone oil.

The olefin polymer composition (C) can be prepared by subjecting each component to various known methods, for example, a Henschel mixer,
It can be manufactured by a method of mixing with a blender, a ribbon blender, a tumbler blender, or the like, or a method of melting and kneading with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like, followed by granulation or pulverization. it can.

Resin Dispersion The resin dispersion according to the present invention comprises the olefin block copolymer (A) or the olefin polymer composition (C).
Is a solid dispersed in an organic medium. Examples of the organic medium include aromatic hydrocarbons such as benzene, toluene, and xylene, which are lipophilic solvents to polyolefin; aliphatic hydrocarbons such as hexane, heptane, octane, and decane; alicycles such as cyclohexane, cyclohexene, and methylcyclohexane. Aliphatic hydrocarbons such as aliphatic hydrocarbons, ethanol and isopropanol; ketone solvents such as acetone, methyl isobutyl ketone and methyl ethyl ketone; and halogenated hydrocarbons such as trichloroethylene, dichloroethylene and chlorobenzene.

In addition, alcohols, ketones, ethers, esters, and the like which are poor solvents for polyolefins
Cellsolves and the like. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, propanediol, phenol,
Diethyl ether, dipropyl ether, dibutyl ether, anisole, dioxane, tetrahydrofuran,
Examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, pentanone, hexanone, isophorone, acetophenone, acetic anhydride, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, ethyl cellosolve, and methyl cellosolve.

These can be used singly or in combination of two or more. In particular, it is possible to use a mixture of a parent solvent and a poor solvent in combination with the low-temperature fluidity of the resin dispersion.
It is preferable from the viewpoint of dispersion stability. The ratio between the parent solvent and the poor solvent is not particularly limited. In the resin dispersion of the present invention, pigments, fillers, stabilizers and other compounding agents known per se can be arbitrarily compounded within a range not to impair the object of the present invention.

To produce the resin dispersion of the present invention, for example, the above-mentioned olefin block copolymer (A) or olefin polymer composition (C) is mixed with the above-mentioned organic medium and completely heated. To dissolve. The temperature at the time of dissolution is usually 100 ° C to 150 ° C. Next, the solution is cooled to precipitate the olefin block copolymer (A) or the olefin polymer composition (C). At this time, it is preferable to set the composition of the organic medium in advance so as to precipitate in the range of 60 to 100 ° C, and to adjust the average cooling rate to 1 to 20 ° C / hour, preferably 2 to 10 ° C / hour. Further, the olefin-based block copolymer (A) or the olefin-based polymer composition (C) is dissolved in an organic medium consisting of only the lipophilic solvent, and after the precipitation is completed, a poor solvent is added, and the precipitation is further performed. Good.

The dispersed particles contained in the resin dispersion according to the present invention thus obtained are generally spherical, but need not necessarily be spherical. The average particle size of the dispersed particles is not particularly limited, but is usually 1 to 20 μm, preferably 5 to 1 μm.
5 μm. The particle concentration (solids concentration) in the resin dispersion is not particularly limited, but is usually 5 to 40% by weight.

Use The resin dispersion of the present invention exhibits excellent adhesive performance as an adhesive or heat sealant between metals, between polyolefins, or between a metal and a polyolefin.
It is also effectively used as a TP packaging adhesive, a laminating adhesive, a coating material or a primer.

[0092]

The resin dispersion according to the present invention has excellent dispersion stability in an organic medium and exhibits good adhesion when bonding a polyolefin to a metal or a polar resin.

[0093]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. The dispersed particle size was measured using a Microtrack manufactured by Honeywell.

Dispersion stability The solvent dispersion obtained in the example was placed in a sealable glass bottle, allowed to stand at room temperature, and after one month, it was confirmed whether or not the solvent phase and the resin phase were separated. Method for measuring heat seal strength against Al Each dispersion was treated with an aluminum foil (50 μm) using a bar coater.
m), air-dried, and set at 200 ° C
The coating was heated in an oven for 10 seconds to obtain a coated foil having a uniform coating film. The coated foil and the LLDPE sheet (thickness: 300 μm, manufactured by Akos Industry Co., Ltd.) are subjected to a method in accordance with JIS Z1707 at a temperature of 100 to 200 ° C. for 1 second.
Thermal bonding with a pressure of 1 kg / cm ² , and an additional 15 m
The sample was cut into a width of m. This sample was subjected to a 180 ° peel test at a measurement temperature of 23 ° C to measure the adhesive strength (tensile speed: 300 mm / min).

[0095]

[Production Example 1] [Pre-activation of catalyst] (Nt-butylamide) (tetramethyl-η) was placed in a glass container sufficiently purged with nitrogen.
⁽⁵ -cyclopentadienyl) dimethylsilanetitanium dichloride was weighed so that the titanium atom was 0.023 mmol, and a toluene solution of triphenylmethylpentakispentafluorophenylborate was weighed so that the boron atom was 0.69 mmol. added. An appropriate amount of toluene was added thereto to make the total amount 50 ml, and a catalyst solution (1) having a titanium concentration of 0.00046 mmol / ml was prepared.

[Olefin polymerization] 750 ml of purified heptane and 35 ml of purified 1-octene were charged into a 2-liter internal stainless steel autoclave sufficiently purged with nitrogen, and the system was replaced with ethylene. Then, the temperature of the system was adjusted to 60 ° C., and 0.375 mmol of triisobutylaluminum and the catalyst solution (1) were added in an amount of 0.007 as a titanium atom.
075 mmol was added. Thereafter, ethylene was introduced, and polymerization was started at a total pressure of 0.9 MPa. After the start of the polymerization, only ethylene was supplied. When a sharp rise in temperature was observed during the polymerization, the operation of stopping the ethylene supply and waiting for the temperature to drop to 70 ° C. was performed twice. The polymerization was carried out at a total pressure in the range of 0.5 to 0.9 MPa and a temperature of 70 ° C.
The polymerization was carried out for 6 minutes at a temperature of from 85 ° C to 85 ° C. When a predetermined time had elapsed, isopropanol was added to stop the reaction. After depressurization, the polymer solution was taken out, transferred into 4 liters of methanol, and sufficiently stirred. The solid portion was collected by filtration, washed with methanol, and then filtered under nitrogen flow for 120 minutes.
It dried at 500 degreeC and 500 mmHg for 12 hours.

The ethylene / octene random copolymer thus obtained weighed 66.0 g and had an activity of 88.
It was 0 kg / mmol-Ti · hr. As a result of IR analysis of the ethylene / octene random copolymer (EOR), the octene content was 12.6 mol%, and an unsaturated bond was present at the polymer terminal. Mw is 13
It was 2,400.

[Conversion of polymer terminal] In a dry box filled with argon, 100 g of EOR having an unsaturated bond at the terminal suspended in 100 ml of degassed and dried tetrahydrofuran (THF) was placed on a glass equipped with a magnetic stir bar. In a flask, add 9-borabicyclo [3.3.1] nonane (9-B
2.4 ml of a BN) THF solution (0.5 M) were added.
This slurry was stirred in a dry box at 55 ° C. for 5 hours, then filtered, washed with degassed and dried isopropyl alcohol, and dried under reduced pressure to obtain a boron-terminated ethylene / octene random copolymer (EOR-B). I got

10 g of EOR-B was degassed and dried in THF.
Suspended in 50 ml, under a nitrogen atmosphere, 0.2 g of NaO
1.0 ml of H-containing aqueous solution and 0.3 ml of methanol
Was added. After cooling to 0 ° C., an aqueous H ₂ O ₂ (30%) solution was added.
After adding 8 ml dropwise and reacting at 40 ° C. for 6 hours, 100 ml of methanol was added to stop the reaction. The obtained polymer was separated by filtration, heated under reflux in 100 ml of methanol for 2 hours, and then filtered again. This was dried under reduced pressure at 50 ° C. for 8 hours. The reaction solution was introduced into 2 liters of a methanol solution to precipitate a polymer, thereby obtaining an EOR having an OH group at its terminal (EOR-OH).

[Polycaprolactone polymerization] EOR-OH
3.5 g were suspended in dry toluene with dry toluene. An excess of n-butyllithium was added thereto, and the mixture was stirred for 12 hours. Then, filtration and washing with toluene were repeated to obtain a corresponding lithium oxide. This solid was reslurried with toluene, and 3 equivalents of diethylaluminum chloride were added and reacted for 12 hours to obtain EOR-aluminum oxide (EOR-OAlEt ₂ ). After washing with toluene and hexane and filtering, this polymer was suspended in 80 ml of toluene, 2.4 g of purified caprolactone was added, and the mixture was reacted at room temperature for 2.1 hours. After the reaction was stopped by adding 100 ml of methanol, the polymer was precipitated in acidic methanol, and the soluble portion was extracted and removed with acetone using a Soxhlet extractor to obtain EO.
RO-polycaprolactone diblock copolymer (EO
(RO-PCL).

The weight average molecular weight of the PCL portion of the diblock copolymer calculated by the following equation was 5,000. Mw ₂ = Mw ₁ · (W ₂ −W ₁ ) / W _{1 In the} above formula, Mw ₁ : Mw of the EOR part Mw ₂ : Mw W _{1 of the} PCL part: EOR-OAlE used for caprolactone polymerization
Weight of t ₂ W ₂ : Yield of diblock copolymer is shown.

[0102]

[Production Example 2] [Pre-activation of catalyst] (Nt-butylamide) (tetramethyl-η) was placed in a glass container sufficiently purged with nitrogen.
⁽⁵ -cyclopentadienyl) dimethylsilanetitanium dichloride was weighed so that the titanium atom was 0.023 mmol, and a toluene solution of triphenylmethylpentakispentafluorophenylborate was weighed so that the boron atom was 0.69 mmol. added. An appropriate amount of toluene was added thereto to make the total amount 50 ml, and a catalyst solution (2) having a titanium concentration of 0.00046 mmol / ml was prepared.

[Olefin polymerization] 750 ml of purified heptane and 35 ml of purified 1-octene were charged into a 2-liter stainless steel autoclave sufficiently purged with nitrogen, and the system was replaced with ethylene. Then, the temperature of the system was adjusted to 60 ° C., and 0.375 mmol of triisobutylaluminum and the catalyst solution (2) were added in an amount of 0.007 in terms of titanium atoms.
075 mmol was added. Thereafter, ethylene was introduced, and polymerization was started at a total pressure of 0.9 MPa. After the start of the polymerization, only ethylene was supplied. When a sharp rise in temperature was observed during the polymerization, the operation of stopping the ethylene supply and waiting for the temperature to drop to 70 ° C. was performed twice. The polymerization was carried out at a total pressure in the range of 0.5 to 0.9 MPa and a temperature of 70 ° C.
The polymerization was carried out for 6 minutes at a temperature of from 85 to 85 ° C. When a predetermined time had elapsed, isopropanol was added to stop the reaction. After depressurization, the polymer solution was taken out, transferred into 4 L of methanol, and sufficiently stirred. The solid part is collected by filtration,
After washing with methanol, under a nitrogen flow, 120 ° C., 50
It was dried at 0 mmHg for 12 hours.

The ethylene / octene random copolymer obtained as described above weighed 66.0 g and had an activity of 88.
It was 0 kg / mmol-Ti · h. This ethylene
As a result of IR analysis of the octene random copolymer (EOR), the octene content was 12.6 mol%, and an unsaturated bond was present at the polymer terminal. Mw is 13
It was 2,400.

[Hydroboration] In a dry box filled with argon, 20 g of the EOR suspended in 100 ml of degassed and dried THF was placed in a glass flask equipped with a magnetic stirrer, and a 9-BBN THF solution ( 0.5M) 2.
4 ml were added. Put this slurry in a dry box
After stirring at 5 ° C. for 5 hours, the mixture was filtered, washed with degassed and dried IPA, and dried under reduced pressure to obtain an ethylene-octene random copolymer having a boron terminal (EOR-B).

[Styrene / Maleic Anhydride Copolymer] 20 g of the above EOR-B was placed in a sealed flask, 10 g of dry styrene (St) and 10 g of maleic anhydride (MAH) were added.
g, 80 ml of THF was added and suspended, and then 1.6.
The reaction was started by blowing ml of dry oxygen. Then 4
After stirring at 5 ° C. for 5 hours, the reaction was stopped by adding 100 ml of methanol. The precipitated polymer was extracted and separated with acetone and heptane over 24 hours using a Soxhlet extractor under a nitrogen atmosphere, and EOR-O was extracted as an insoluble component.
-A styrene / maleic anhydride copolymer diblock copolymer (EOR-OP (St / MAH)) was obtained.

The weight average molecular weight of the P (St / MAH) portion of the diblock copolymer calculated by the following equation was 5,000. Mw ₂ = Mw ₁ · (W ₂ −W ₁ ) / W _{1 In the} above formula, Mw ₁ : Mw of the EOR part, Mw ₂ : Mw W _{1 of the} P (St / MAH) part: for styrene / maleic anhydride copolymerization EO used
Weight of RB W ₂ : Yield of diblock copolymer is shown.

[0108]

Example 1 55 g of the diblock copolymer (EOR-O-PCL) obtained in Production Example 1 and 495 g of toluene were placed in a 1-liter glass autoclave equipped with a stirrer.
After heating to 130 ° C. to completely dissolve the resin, the temperature was raised to 85 ° C. for 1 hour and from 85 ° C. to 40 ° C. for 4.5 hours.
The temperature was lowered from 30 ° C. to 30 ° C. in 30 minutes to obtain a resin dispersion. About the obtained resin dispersion, the dispersion particle diameter, dispersion stability, and Al heat-sealing resistance were measured. Table 1 shows the results.

[0109]

Example 2 A resin dispersion was obtained in the same manner as in Example 1 except that the diblock copolymer (EOR-OP (St / MAH)) obtained in Production Example 2 was used. About the obtained resin dispersion, the dispersion particle diameter, dispersion stability, and Al heat-sealing resistance were measured. Table 1 shows the results.

[0110]

[Table 1]

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Taku Kanda 6-1-2 Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals Co., Ltd. (72) Ryo Mori Inventor 6-Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture -1-2 Inside Mitsui Chemicals Co., Ltd. (72) Junji Tanji Inventor 6-1-2 Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Mitsui Chemicals Co., Ltd. (72) Hideyuki Kaneko 580 Nagaura, Sodegaura City, Chiba Prefecture −32 Mitsui Chemicals Co., Ltd. (72) Inventor Shunichi Hama 3-8-1 -106, Makuhari Hongo, Hanamigawa-ku, Chiba City, Chiba Prefecture (72) Inventor Shinichi Furushiro 580-32, Nagaura, Sodegaura City, Chiba Prefecture Mitsui Chemicals (72) Inventor Norio Kashiwa 580-32 Nagaura, Sodegaura-shi, Chiba F-term (reference) 4F070 AB08 AB09 CB05 4J002 BB03X BB04X BB05X BB12X BB14X BB17X BC03X BG04X BG06X BN15X BP03 CF03 06X CF07X CF08X CG00X CH07X CL01X CL03X GJ01 HA08

Claims (2)

[Claims] 1. A resin dispersion comprising an olefin-based block copolymer (A) represented by the following general formula (I) dispersed in an organic medium: PO-fR (I) (Wherein PO is composed of a repeating unit derived from an olefin having 2 to 20 carbon atoms, and has a weight average molecular weight of 2,2.
Represents a polyolefin segment having a molecular weight of not less than 000, f represents an ether bond, an ester bond or an amide bond, R represents a chain polymerization reaction, and has a weight average molecular weight of 500
The functional segment described above is shown. ). 2. The olefin block copolymer (A) according to claim 1, and a thermoplastic resin (B) other than (A).
A resin dispersion comprising: an olefin polymer composition (C) containing