JP2002167413A - Polar group-containing branched olefin copolymer and thermoplastic resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polar group-containing branched olefin copolymer which is excellent in the adhesion with a metal or polar resin, compatibility and flexibility, or the like. SOLUTION: The copolymer comprises the structural units (1), (2) and, if necessary, (3) [wherein R1 is an aliphatic hydrocarbon group; R2 is a hydrocarbon group; R3 is a hetero atom or hetero atom-containing group; (r) and (m) are 0 or 1; Z is a polymer segment obtained by any of the anionic polymerization, ring opening polymerization and polycondensation; X is hydroxyl group or epoxy group; (p) and (n) are 1-3; (q) is 0-2; O-Z may be the same or different each other when (p) is 2 or 3; X may be the same or different each other when (n) is 2 or 3].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a branched olefin copolymer containing a polar group and a thermoplastic resin composition containing this copolymer. The present invention also relates to a polar group-containing branched olefin copolymer having excellent surface hydrophilicity and antistatic properties and a thermoplastic resin composition.

[0002]

BACKGROUND OF THE INVENTION Generally, polyolefins are excellent in moldability, heat resistance, mechanical properties, hygiene compatibility, water vapor permeability, etc. and have good appearance of molded products. Widely used for molded products, hollow molded products, injection molded products, etc. However, since polyolefins do not contain polar groups in their molecules, they have low compatibility and adhesion with polar resins such as nylon and EVOH, and can be used by blending with these materials or by laminating them. It was difficult. Further, there is also a problem that a molded article made of polyolefin is inferior in surface hydrophilicity, antistatic property and the like.

In order to solve such a problem, a method of grafting a polar group-containing monomer to a polyolefin by using radical polymerization to improve affinity with a polar substance has been widely used. In the method, intermolecular cross-linking between polyolefins and breaking of molecular chains occur in parallel with the graft reaction, so that viscosity matching between the graft polymer and the polar resin is difficult, and the compatibility is sometimes insufficient. In addition, the appearance of the molded product was sometimes deteriorated due to the gel component generated by intermolecular cross-linking, the eyes generated by cutting molecular chains (foreign matter adhering to the lip of the die), and the like.

In order to improve the surface hydrophilicity and the antistatic property, a method of adding a small amount of a low molecular weight surfactant to a polyolefin and molding the polyolefin has been carried out. Bleeds out to the surface, which sometimes causes a problem of whitening of the film surface after molding. In addition, since the surfactant bleeding out on the surface flows out with water droplets attached thereto, there is a case where a problem that the effect does not last for a long time occurs.

[0005] The inventors of the present invention have conducted studies in view of the above problems, and as a result, have found that a copolymer having a specific molecular structure and a composition containing the same have excellent compatibility with a polar resin and excellent adhesion. The inventors have found that they have excellent surface hydrophilicity and antistatic properties, and have completed the present invention.

[0006]

An object of the present invention is to provide a polar group-containing branched olefin copolymer and a thermoplastic resin composition having excellent compatibility with a polar resin, excellent adhesiveness, and excellent surface hydrophilicity and antistatic properties. It is intended to be.

[0007]

SUMMARY OF THE INVENTION The polar group-containing branched olefin copolymer of the present invention comprises a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2). And

[0008]

Embedded image

(Wherein, R ¹ represents a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms or a hydrogen atom, R ² represents a hydrocarbon group, R ³ represents a hetero atom or A group containing a hetero atom; r represents 0 or 1;
Represents a polymer segment obtained by any of anionic polymerization, ring-opening polymerization and polycondensation, X represents a hydroxyl group or an epoxy group, p represents an integer of 1 to 3, q represents 0, 1 or 2, and p + q ≦ 3, when p is 2 or 3,
-Z may be the same or different, -O-Z when r is 0 in this case may be bonded to the same or different atom of R ^2, -O-Z when r is 1, R
³ may be bonded to the same or different atom, q is or different and X is each time 2, X when r is 0 attached to the same or different atom of R ² in this case And when r is 1, X may be bonded to the same or different atom of R ³ , and when p ≧ 1 and q ≧ 1, when r is 0, X and —O—Z
May be bonded to the same or different atoms of R ² ,
When r is 1, X and —O—Z may be bonded to the same or different atoms of R ³ , m represents 0 or 1,
n represents an integer of 1 to 3, and when n is 2 or 3, Xs may be the same or different from each other;
There may be X when 0 is attached to the same or different atom of R ^2, X when m is 1 may be attached to the same or different atom of R ^3. ).

The polar group-containing branched olefin copolymer according to the present invention has the general formula (2) wherein r is 0,
It is preferable that Z is a polymer segment obtained by anionic polymerization, and it is also preferable that Z in the general formula (2) is a polymer segment obtained by ring-opening polymerization and polycondensation. Polar group-containing olefin branched copolymer according to the present invention preferably has a molecular weight distribution of 3 or less, ¹³
In the C-NMR spectrum, the intensity ratio of Tαβ to Tαα + Tαβ (Tαβ / (Tαα + Tαβ)) is 1.
It is also preferably 0 or less.

The thermoplastic resin composition according to the present invention is characterized by containing the above-mentioned branched olefin copolymer having a polar group.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the polar group-containing branched olefin copolymer and the thermoplastic resin composition containing the copolymer according to the present invention will be described in detail. Polar group-containing branched olefin copolymer The polar group-containing branched olefin copolymer according to the present invention,
A structural unit represented by the following general formula (1) (hereinafter, referred to as structural unit (1)) and a structural unit represented by the following general formula (2) (hereinafter, referred to as structural unit (2)) are required. And a structural unit represented by the following general formula (3) (hereinafter, referred to as a structural unit (3)).

[0013]

Embedded image

In the general formula (1), R ¹ has 1 to 1 carbon atoms.
8 represents one group selected from 8 linear or branched aliphatic hydrocarbon groups or a hydrogen atom. 1 to 1 carbon atoms
As the linear or branched aliphatic hydrocarbon group of 8,
For example, methyl, ethyl, n-propyl, isopropyl, 2-
Methylpropyl, n-butyl, isobutyl, sec-butyl,
tert-butyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, pentyl, neopentyl, n-hexyl, 1-ethyl-1-methylpropyl, 1,1-diethylpropyl, 2-ethylhexyl, octyl, decyl, Dodecyl and the like. Among them, those having 1 to 10 carbon atoms, particularly those having 1 to 6 carbon atoms are preferable.

In the general formulas (2) and (3), R ² is a saturated or unsaturated aliphatic hydrocarbon group, alicyclic hydrocarbon group,
Shows a hydrocarbon group such as an aromatic hydrocarbon group. Examples of the saturated or unsaturated aliphatic hydrocarbon group include those having 1 to 2 carbon atoms.
0 linear or branched hydrocarbon groups, specifically, methylene, ethylene, trimethylene, methylethylene, tetramethylene, methyltrimethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene. , Decamethylene, undecamethylene, dodecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene, heptadecamethylene,
Octadecamethylene, nonadecamethylene, icosamethylene and the like can be mentioned.

The alicyclic hydrocarbon group has one of its structures.
A group having 3 to 20 carbon atoms having an alicyclic structure in the part is preferable
Specifically, cyclopropylene, cyclopentylene,
Cyclohexylene, cyclooctylene, etc.
You. As an aromatic hydrocarbon group, part of its structure
A ring-containing group having 6 to 20 carbon atoms is preferable, and
Has -Ph-, -Ph-CH_Two-, -Ph- (CH_Two)
_Two-, -Ph- (CH_Two)_Three-, -Ph- (CH_Two)₆-, -P
h- (CH_Two)_Ten-, -Ph- (CH_Two)₁₁-, -Ph- (C
H_Two)₁₂-, -Ph- (CH_Two)₁₄-And the like.

In the general formula (2), the valence of R ² is divalent when r is 1 and R ³ is bonded to R ² ;
Is 0 and p (—O—Z) and q X are bonded to R ² , the valence is (p + q + 1). In the general formula (3), the valence of R ² is divalent when m is 1 and R ³ is bonded to R ² , m is 0 and n X
Is bonded to R ² , it has (n + 1) valence.

[0018] and R ² in the general formula (2), the R ² of the general formula (3), may be the same or different from each other, but are preferably the same. General formulas (2) and (3)
In the formula, R ³ represents a hetero atom or a group containing a hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like, and an oxygen atom and a nitrogen atom are preferable.

Examples of the group containing a hetero atom include groups containing an oxygen atom, a nitrogen atom or a sulfur atom. Specific examples of a hetero atom or a group containing a hetero atom include, for example, -O-, -C (= O)-, -C (= O) O-, -OC
(= O) O-, -C (= O) NH-, -S-, and the like, and an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group containing these groups.

Specific examples include structures as shown in the examples of polar group-containing monomers described below. General formula (2)
In R ³ is preferably a carbon atom to heteroatom or heteroatoms in R ³ is bonded is bonded to R ^2, as such ^{examples, -R 2 -O-R-O} -Z,
^{-R 2 -C (= O) -R} -O-Z, -R 2 -C (= O) O-R
—O—Z, —R ² —OC (＝ O) O—R—O—Z, —R ² —
C (= O) NH-R -O-Z, -R 2 -S-R-O-Z
(However, R represents methylene, phenylene, or cyclohexylene.). Note that the above example shows a case where p is 1 and q is 0 in the general formula (2),
The same applies to other cases.

[0021] R ³ in the general formula (3), it is preferable that the carbon atom to heteroatom or heteroatoms in R ³ is bonded is bonded to R ^2, as such example -
R ² —O—R—X, —R ² —C (＝ O) —R—X, —R ² —
C (= O) O-R -X, -R 2 -OC (= O) O-R-X,
—R ² —C (＝ O) NH—R—X, —R ² —S—R—X (where R represents methylene, phenylene, cyclohexylene) and the like. Note that the above example is obtained by using the general formula (3)
Shows a case where n is 1, but the same applies to other cases.

When R ³ in formulas (2) and (3) contains a carbon atom, the number of carbon atoms forming R ³ is preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 10. 5 And R ³ in the general formula (2), and the R ³ in the general formula (3), may be the same or different from each other, but are preferably the same.

In the general formula (2), r represents 0 or 1.
When r is 0, -O-Z is bonded to any carbon atom forming the R ^2, when r is 1, -O-Z is bonded to any carbon atom forming the R ^3. In the general formula (3),
m represents 0 or 1. When m is 0, X is bonded to any carbon atom forming R ^2, and when m is 1, X is bonded to any carbon atom forming R ³ .

In the general formula (2), Z represents a polymer segment obtained by any of anionic polymerization, ring-opening polymerization and polycondensation. Examples of such polymer segments include segments obtained by anionic polymerization of methyl methacrylate, ethyl methacrylate, butyl acrylate, acrylonitrile, acrylamide alone or two or more types; lactone, lactide, siloxane, lactam, cyclic ether , Segments obtained by ring-opening polymerization of oxazoline, ethylene oxide, propylene oxide, etc .; obtained by polycondensation of monomers such as polycarboxylic acids and polyhydric alcohols, polycarboxylic acids and polyvalent amines, and hydroxycarboxylic acids. Segment and the like.

More specifically, examples of the polar monomer used for forming the polymer segment include (meth) acrylates such as methyl acrylate, methyl methacrylate, ethyl acrylate, propyl methacrylate, butyl acrylate, -Ethylhexyl methacrylate, lauryl acrylate, stearyl methacrylate, 1,1,1,3,3,3-hexafluoroisopropyl acrylate, 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 2,2,2- Trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 1H, 1H,
Monohydric alcohols such as 2H, 2H-heptadecafluorodecyl acrylate, allyl acrylate, allyl methacrylate, cyclohexyl methacrylate, isophonyl acrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofurfuryl acrylate, benzyl acrylate or β-phenylethyl methacrylate And monoesters of acrylic acid or methacrylic acid; 2-methoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-phenoxyethyl acrylate, 2-dicyclopentenyloxyethyl acrylate,
1-methoxy-2-propyl methacrylate, 3-methoxypropyl acrylate, 4-ethoxybutyl methacrylate, 6-methoxyhexamethyl acrylate, methoxydiethylene glycol acrylate, phenoxydipropylene glycol methacrylate, ethoxytripropylene glycol methacrylate, ethoxy polyethylene glycol acrylate or methoxy Monoesters of acrylic acid or methacrylic acid with a dihydric alcohol having one terminal protected by an ether bond such as polypropylene glycol methacrylate; ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol Diacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, diethylene glycol diacrylate, dipropylene glycol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate , Polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, glycerin triacrylate, glycerin trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, trimethylolpropane triacrylate, poly (ethylene oxide) triol triacrylate, poly (propylene oxide) Triol triacrylate, poly (propylene oxide)
Polyhydric esters in which acrylic acid or methacrylic acid is esterified with all hydroxy groups of polyhydric alcohols having a valency of at least valence such as trioltrimethacrylate; 2-benzoyloxyethyl acrylate, 2-benzoyloxyethyl methacrylate, 2 -Acetyloxyacrylate, 5-tetrahydrofurfuryloxycarbonylpentyl acrylate, 5-tetrahydrofurfuryloxycarbonylpentyl methacrylate, 2,2,6,6-tetramethyl-4-oxy-5-oxa-heptane-1,7 -Esters of an alcohol containing an ester bond such as diyl-diacrylate and acrylic acid or methacrylic acid; 2-tert-butyl-1,3-dioxycyclopentan-2'-yl methacrylate or 2-tert- Butyl-5-ethyl-
Esters of alcohols having a cyclic acetal bond such as 5-vinylcarbonyloxymethyl-1,3-dioxycyclohexane-2 '(2) -yl acrylate with acrylic acid or methacrylic acid; N-oxysuccinimide acrylate, N Esters of oxysuccinimide such as -oxysuccinimide methacrylate with acrylic acid or methacrylic acid; alcohols having a secondary amino group such as 2-dimethylaminoethyl acrylate or 2-ethylpropylaminoethyl methacrylate; acrylic acid or methacrylic acid Esters with an acid; esters of an alcohol having a cyano group such as 2-cyanoethyl acrylate and 2-cyanopropyl methacrylate with acrylic acid or methacrylic acid.

Examples of (meth) acrylonitriles include acrylonitrile, methacrylonitrile and the like. Acrylamides are acrylamide, N-monosubstituted or N, N-disubstituted acrylamides, for example, acrylamide; N-methylacrylamide, N-ethylacrylamide, N-propylacrylamide, N-butylacrylamide, N-octylacrylamide N-monosubstituted acrylamides such as N, N-phenylacrylamide, N-glycidylacrylamide, N, N'-ethylenebisacrylamide; N, N-dimethylacrylamide, N-ethyl-N-methylacrylamide, N, N-diethyl Acrylamide, N, N-
Di-n-propylacrylamide, N, N-dioctylacrylamide, N, N-diphenylacrylamide, N-ethyl-N
-Glycidylacrylamide, N, N-diglycidylacrylamide, N-methyl-N- (4-glycidyloxybutyl)
Acrylamide, N-methyl-N- (5-glycidyloxypentyl) acrylamide, N-methyl-N- (6-glycidyloxyhexyl) acrylamide, N-acryloylpyrrolidine, N-acryloyl-L-proline methyl ester, N
N, N-disubstituted monoacrylamides such as -acryloylpiperidine, N-acryloylmorpholine, 1-acryloylimidazole; N, N'-diethyl-N, N'-ethylenebisacrylamide, N, N'-dimethyl-N And N, N'-disubstituted bisacrylamides such as N, N'-hexamethylenebisacrylamide and di (N, N'-ethylene) bisacrylamide.

Examples of the vinylpyridines include vinyl- or isopropenyl-substituted pyridines such as 2-vinylpyridine, 2-isopropenylpyridine and 4-vinylpyridine. Examples of N-substituted maleimides include N-
Examples include N-aliphatic substituted maleimides such as methylmaleimide and N-ethylmaleimide; N-aromatic substituted maleimides such as N-phenylmaleimide and N- (4-methylphenyl) maleimide.

Examples of the vinyl ketones include methyl vinyl ketone, isopropenyl methyl ketone, ethyl vinyl ketone, ethyl isopropenyl ketone, butyl vinyl ketone, phenyl vinyl ketone and the like. Examples of the styrene derivatives include p-methoxycarbonylstyrene, p-tert-butoxycarbonylstyrene, p-cyanostyrene and the like.

Examples of the polar monomer include alkylene oxide compounds. Specifically, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide,
Epoxy compounds such as 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, and phenyl glycidyl ether are exemplified. Of these, ethylene oxide, propylene oxide, 1,2-butylene oxide and styrene oxide are preferred, propylene oxide and ethylene oxide are more preferred, and propylene oxide is even more preferred.

Among these, a polymer segment obtained by anionic polymerization of (meth) acrylic esters and a polymer segment obtained by ring-opening polymerization of ethylene oxide and propylene oxide are preferable. Although the molecular weight of the polymer segment is not particularly limited, for example, 200 to 1,000,000, preferably 500
The range is from 100,000 to 100,000.

When Z is a polyethylene oxide or a polypropylene oxide, the polar group-containing branched olefin copolymer has a coating property, a surface hydrophilicity (anti-fog property), an antistatic property, and a polar resin (urethane resin, epoxy resin). Etc.), excellent in adhesiveness / compatibility, moisture absorption, water absorption (when Z is contained at a high ratio), water dispersibility, oil resistance (when Z is contained at a high ratio), and biocompatibility.

When Z is PMMA, the polar group-containing branched olefin copolymer has surface hardness, adhesiveness to metal, pigment dispersibility, filler dispersibility, oil resistance (when Z is contained at a high ratio), polar Resin (acrylic resin, nylon, EVO
H) with excellent adhesiveness and compatibility. When Z is polyacrylonitrile or polyacrylamide, the polar group-containing branched olefin copolymer has a surface hardness, a surface hydrophilicity (anti-fog property), an antistatic property, a coating property, an adhesion to metal, a polar resin ( Polyacrylonitrile, polyacrylamide,
Excellent in adhesiveness / compatibility with polyamide, polyester, etc.), water dispersibility, biocompatibility, stimulus responsiveness, moisture absorption, and water absorption.

When Z is polyethyl methacrylate or polybutyl acrylate, the polar group-containing branched olefin copolymer has an adhesive property to a metal and an adhesive property to a polar resin (acrylic resin, nylon, EVOH, etc.). Excellent resistance and oil resistance. When Z is a polyamide (including a lactam ring-opening polymer), the polar group-containing branched olefin copolymer is excellent in adhesiveness / compatibility with a polar resin (such as polyamide), gas barrier properties, and oil resistance.

When Z is a polyester (including a lactone ring-opening polymer), the polar group-containing branched olefin copolymer is excellent in adhesiveness / compatibility with polar resins (such as polyester) and gas barrier properties. In the general formula (2), p is 1 to
Represents an integer of 3, and when p is 2 or 3, -OZ may be the same or different. When p is 2 or 3 and r is 0, -OZ may be bonded to the same atom or a different atom of R ² , and when p is 2 or 3 and r is 1 -O-Z may be bonded to the same atom or different atoms R ^3.

In the general formulas (2) and (3), X is a hydroxyl group or an epoxy group. X in the general formula (2) and X in the general formula (3) may be the same or different from each other, but are preferably the same. In the general formula (2), q
Represents 0, 1 or 2, and when q is 2, Xs may be the same or different. When q is 2 and r is 0, X may be bonded to the same atom or a different atom of R ² , and when q is 2 and r is 1, X is R
^It may be bonded to the same ³ atoms or different atoms.

In the case where p ≧ 1 and q ≧ 1,
When r is 0, X and -OZ are R ^TwoThe same or different
And when r is 1, X and-
O-Z is R^ThreeBond to the same or different atom of
Often, p + q ≦ 3. In the general formula (3), n is 1
X is the same as each other when n is 2 or 3.
It may be one or different. And n is 2 or 3
And when m is 0, X is R^TwoThe same atom of or different
May be bonded to an atom, and n is 2 or 3,
When m is 1, X is R^ThreeSame or different atom of
They may be combined.

In the branched olefin copolymer containing a polar group according to the present invention, the structural unit (1), the structural unit (2) and, if necessary, the structural unit (3) are usually randomly bonded. (Composition of Copolymer) The branched olefin copolymer containing a polar group according to the present invention comprises a structural unit (1) and a structural unit (2).
And the molar ratio to the total of the structural units (3) ((1):
((2) + (3)) is usually 99.99: 0.01 to
0.01: 99.99, preferably 99.95: 0.0
5-10: 90, more preferably 99.9: 0.1-
30:70. The molar ratio of the structural unit (2) to the structural unit (3) ((2) :( 3)) is usually 100:
0 to 0.01: 99.99, preferably 100: 0 to 1
0:99, more preferably 100: 0 to 10:90.

The polar group-containing branched olefin copolymer according to the present invention may contain two or more types of the structural unit (1) or two or more types of the structural unit (2).
Two or more structural units (3) may be included. In the present invention, as a preferred combination of the structural unit (1), the structural unit (2) and the structural unit (3), a structural unit selected from the examples of the structural unit (1) shown in Table 1 below and a structural unit (2) And a combination of a structural unit selected from the examples of the structural unit (3) and the examples of the -R ^2- (R ³ ) _r -O- part and the examples of the structural unit (3). -Z1-a, 1-
AZ2-a, 1-AZ3-a, 1-AZ4-a,
1-AZ-5-a, 1-AZ6-a, 1-AZ7-
a, 1-B-Z1-b, 1-B-Z2-b, 1-B-Z
3-b, 1-B-Z4-b, 1-B-Z5-b, 1-B
-Z6-b, 1-B-Z7-b, 1-C-Z1-c, 1
-C-Z2-c, 1-C-Z3-c, 1-C-Z4-
c, 1-C-Z5-c, 1-C-Z6-c, 1-C-Z
7-c, 2-AZ1-a, 2-AZ2-a, 2-A
-Z3-a, 2-AZ4-a, 2-AZ5-a, 2
-A-Z6-a, 2-A-Z7-a, 2-B-Z1-
b, 2-B-Z2-b, 2-B-Z3-b, 2-B-Z
4-b, 2-B-Z5-b, 2-B-Z6-b, 2-B
-Z7-b, 2-C-Z1-c, 2-C-Z2-c,
-C-Z3-c, 2-C-Z4-c, 2-C-Z5-
c, 2-C-Z6-c, 2-C-Z7-c, 3-AZ
1-a, 3-AZ2-a, 3-AZ3-a, 3-A
-Z4-a, 3-A-Z5-a, 3-A-Z6-a, 3
-A-Z7-a, 3-B-Z1-b, 3-B-Z2-
b, 3-B-Z3-b, 3-B-Z4-b, 3-B-Z
5-b, 3-B-Z6-b, 3-B-Z7-b, 3-C
-Z1-c, 3-C-Z2-c, 3-C-Z3-c,
-C-Z4-c, 3-C-Z5-c, 3-C-Z6-
c, 3-C-Z7-c, 4-AZ1-a, 4-AZ
2-a, 4-A-Z3-a, 4-A-Z4-a, 4-A
-Z5-a, 4-A-Z6-a, 4-A-Z7-a,
-B-Z1-b, 4-B-Z2-b, 4-B-Z3-
b, 4-B-Z4-b, 4-B-Z5-b, 4-B-Z
6-b, 4-B-Z7-b, 4-C-Z1-c, 4-C
-Z2-c, 4-C-Z3-c, 4-C-Z4-c,
-C-Z5-c, 4-C-Z6-c, 4-C-Z7-
c, 5-AZ1-a, 5-AZ2-a, 5-AZ
3-a, 5-A-Z4-a, 5-A-Z5-a, 5-A
-Z6-a, 5-A-Z7-a, 5-B-Z1-b, 5
-B-Z2-b, 5-B-Z3-b, 5-B-Z4-
b, 5-B-Z5-b, 5-B-Z6-b, 5-B-Z
7-b, 5-C-Z1-c, 5-C-Z2-c, 5-C
-Z3-c, 5-C-Z4-c, 5-C-Z5-c, 5
-C-Z6-c, 5-C-Z7-c, 6-A-Z1-
a, 6-A-Z2-a, 6-A-Z3-a, 6-AZ
4-a, 6-A-Z5-a, 6-A-Z6-a, 6-A
-Z7-a, 6-B-Z1-b, 6-B-Z2-b, 6
-B-Z3-b, 6-B-Z4-b, 6-B-Z5-
b, 6-B-Z6-b, 6-B-Z7-b, 6-CZ
1-c, 6-C-Z2-c, 6-C-Z3-c, 6-C
-Z4-c, 6-C-Z5-c, 6-C-Z6-c, 6
-C-Z7-c, 7-A-Z1-a, 7-A-Z2-
a, 7-A-Z3-a, 7-A-Z4-a, 7-AZ
5-a, 7-A-Z6-a, 7-A-Z7-a, 7-B
-Z1-b, 7-B-Z2-b, 7-B-Z3-b, 7
-B-Z4-b, 7-B-Z5-b, 7-B-Z6-
b, 7-B-Z7-b, 7-C-Z1-c, 7-CZ
2-c, 7-C-Z3-c, 7-C-Z4-c, 7-C
-Z5-c, 7-C-Z6-c, 7-C-Z7-c, 8
-AZ1-a, 8-AZ2-a, 8-AZ3-
a, 8-A-Z4-a, 8-A-Z5-a, 8-AZ
6-a, 8-A-Z7-a, 8-B-Z1-b, 8-B
-Z2-b, 8-B-Z3-b, 8-B-Z4-b, 8
-B-Z5-b, 8-B-Z6-b, 8-B-Z7-
b, 8-C-Z1-c, 8-C-Z2-c, 8-C-Z
3-c, 8-C-Z4-c, 8-C-Z5-c, 8-C
-Z6-c, 8-C-Z7-c, 9-A-Z1-a, 9
-A-Z2-a, 9-A-Z3-a, 9-A-Z4-
a, 9-A-Z5-a, 9-A-Z6-a, 9-AZ
7-a, 9-B-Z1-b, 9-B-Z2-b, 9-B
-Z3-b, 9-B-Z4-b, 9-B-Z5-b, 9
-B-Z6-b, 9-B-Z7-b, 9-C-Z1-
c, 9-C-Z2-c, 9-C-Z3-c, 9-C-Z
4-c, 9-C-Z5-c, 9-C-Z6-c, 9-C
-Z7-c. In the examples of the combination, numerals indicate examples of the structural unit (1), A, B, and C indicate examples of —R ² — (R ³ ) _r —O— of the structural unit (2), Z1 to Z7 represent examples of the Z portion of the structural unit (2), and a, b and c represent -R ^{2 of the} structural unit (3).
- illustrates an exemplary (R ³⁾ _m -X _n unit.

[0039]

[Table 1]

(Other Copolymerization Components) The branched olefin copolymer containing a polar group according to the present invention contains the structural unit (1) and the structural unit (2) as long as the object of the present invention is not impaired.
And a structural unit other than the structural unit (3). Here, examples of the structural unit that may be included include a cyclic olefin excluding a polar group-containing monomer represented by the following formula (4), a non-conjugated polyene, a hydroxyl group-containing ethylenically unsaturated compound, and an amino group-containing ethylene. And structural units derived from an unsaturated unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an aromatic vinyl compound, an unsaturated carboxylic acid and its derivatives, a vinyl ester compound, and vinyl chloride.

When these structural units are contained, the amount of these structural units is 2 mol% or less, preferably 1.5 mol%, based on all the monomers constituting the polar group-containing branched olefin copolymer. Or less, more preferably 1.0 mol% or less. (Physical Properties of the Copolymer) The weight average molecular weight (Mw) of the polar group-containing branched olefin copolymer according to the present invention is usually 50.
The molecular weight distribution (Mw / Mn) is usually 3 or less, preferably 2.8 or less, more preferably 2.5 or less. It is.

When the molecular weight distribution (Mw / Mn) is 3 or less, the polar group-containing branched olefin copolymer is excellent in the orientation of the polar group at the interface with the polar substance, and has good adhesion to the polar substance and a good phase. Excellent solubility. Where Mw and M
w / Mn was determined by GPC (gel permeation chromatography) using an orthodichlorobenzene solvent,
Determined by data obtained at 0 ° C.

Further, the branched olefin copolymer containing a polar group is represented by Tαα + Tαβ in the ¹³ C-NMR spectrum.
Ratio of Tαβ to (Tαβ / (Tαα + Tα
β)) is 1.0 or less, preferably 0.8 or less, more preferably 0.5 or less. Intensity ratio (Tαβ / (Tαα
+ Tαβ)) is 1.0 or less, the polar group-containing branched olefin copolymer is excellent in the orientation of the polar group to the interface with the polar substance.

Here, T in the ¹³ C-NMR spectrum
αα and Tαβ are peak intensities of CH ₂ in a structural unit derived from an α-olefin having 4 or more carbon atoms, and represent two types of CH ₂ having different positions with respect to a tertiary carbon as shown below. are doing.

[0045]

Embedded image

The Tαβ / (Tαα + Tαβ) intensity ratio can be determined as follows. The ¹³ C-NMR spectrum of the polar group-containing branched olefin copolymer is measured using, for example, a JEOL-GX270 NMR measuring device manufactured by JEOL Ltd. The measurement was carried out using a mixed solution of hexachlorobutadiene / d6-benzene = 2/1 (volume ratio) adjusted to a sample concentration of 5% by weight, and 67.
8 MHz, 25 ° C., d6-benzene (128 ppm) standard. The measured ¹³ C-NMR spectrum was analyzed by Lindemann Adams (Analysis Chemistry 43, p1245 (19
71)), JCRandall (ReviewMacromolecular Chemistry
Physics, C29, 201 (1989)).
The (Tαα + Tαβ) intensity ratio is determined.

(Production Method) The polar group-containing branched olefin copolymer according to the present invention comprises, for example, (a) an α-olefin having 2 to 20 carbon atoms and a polar group represented by the following general formula (4): After producing a polar group-containing olefin copolymer by copolymerizing with the containing monomer, anion polymerization from the X part of the copolymerized polar group-containing monomer,
A method of forming a Z portion opening polymerization or ^{_{polycondensation, CH 2 = CH-R 2}} - (R 3) m - (X) n ... (4) ( ^{wherein, R 2, R 3, X} , m And n have the same meanings as R ² , R ³ , X, m and n in the general formula (3), respectively.) (B) α-olefin having 2 to 20 carbon atoms and the general formula (4) After producing a polar group-containing olefin copolymer by copolymerizing with a polar group-containing monomer represented by, and X part of the copolymerized polar group-containing monomer, by anionic polymerization, ring-opening polymerization or polycondensation (C) a method of copolymerizing an α-olefin having 2 to 20 carbon atoms with a macromonomer represented by the following general formula (5);

[0048]

Embedded image

(Wherein, R ² , R ³ , Z, X, p, q, and r are, respectively, R ² , R ³ , Z,
It is synonymous with X, p, q and r. ). First, the method (a) will be specifically described. In the method (a), α having 2 to 20 carbon atoms is used.
-After the olefin and the polar group-containing monomer represented by the general formula (4) are copolymerized to produce a polar group-containing olefin copolymer, the olefin is contained in the X part of the copolymerized polar group-containing monomer. A polymer segment (Z) is formed from the polar group to be formed by anionic polymerization, ring-opening polymerization or polycondensation.

The structural unit derived from the polar group-containing monomer represented by the general formula (4) in the polar group-containing olefin copolymer, and the polar unit contained in any of the X parts in the structural unit When a polymer segment is formed from a group, the structural unit is a structural unit (2), which is a structural unit derived from the polar group-containing monomer represented by the general formula (4), and When a polymer segment was not formed from the polar group contained in any of the X parts,
It becomes the structural unit (3).

Examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene and 4-hexene.
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 and the like. Among them, it is preferable to use at least two kinds selected from ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.

The polar group-containing monomer represented by the general formula (4) includes 4-penten-1-ol and 5-hexen-1-ol.
All, 6-hepten-1-ol, 7-octen-1-ol,
Ω-alkenyl alkols such as 8-nonen-1-ol, 9-decene-1-ol, 10-undecen-1-ol and 11-dodesen-1-ol; 5-hexen-2-ol, 6- Heptene-2-
All, 7-octen-2-ol, 8-nonen-2-ol, 9-
Decene-2-ol, 10-undecene-2-ol, 6-hepten-3-ol, 7-octen-3-ol, 8-nonen-3-ol, 9-decene-3-ol, 10-undecene- 3-all, 11-
Dodecene-3-ol, 7-octen-4-ol, 8-nonene-4
-All, 9-decene-4-ol, 10-undecene-4-ol, 8-nonen-5-ol, 9-decene-5-ol, 10-undecene-5-ol, etc. Alcohols in the form of 2-ethyl-5-hexen-1-ol, 3-methyl
-6-hepten-1-ol, 3-methyl-7-octen-1-ol, 4-methyl-8-nonen-1-ol, 3-ethyl-9-decene-
1-ol, 2-methyl-10-undecen-2-ol, 2,2-dimethyl-7-octen-1-ol, 3-ethyl-2-methyl-8-nonen-1-ol, 2,2, Alcohols in which the hydrocarbon moiety is branched, such as 3-trimethyl-9-decene-1-ol and 2,3,3,4-tetramethyl-10-undecene-2-ol; 9-decene-1, Diols such as 2-diol, 10-undecene-1,2-diol, 11-dodecene-1,2-diol, 11-dodecene-1,2-diol, 10-undecene-1,2,3-triol, etc. Wherein X is a hydroxyl group in the above general formula (4), such as triols, 5-hexene epoxide, 6-heptene epoxide, 7-octene epoxide, 8-nonene epoxide, 9-decene epoxide, and 10-undecene epoxide , 1
Ω-alkenyl epoxides such as 1-dodecene epoxide; 2-methyl-5-hexene epoxide, 2-methyl-6-heptene epoxide, 2-methyl-7-octene epoxide, 2-
In the above general formula (4), such as ω-alkenyl epoxides in which the hydrocarbon moiety is branched, such as methyl-8-nonene epoxide, 2-methyl-9-decene epoxide and 2-methyl-10-undecene epoxide Compounds in which X is an epoxy group are exemplified.

The polar group-containing monomer also includes a compound represented by the following formula.

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

In addition to the above, n-nonyl-1-ol, 1,2-epoxy-nonyl, n-undecyl-1-ol, 4-
Hexeniloxyphenol and the like. The α-olefin having 2 to 20 carbon atoms and the general formula (4)
The copolymerization with the polar group-containing monomer represented by the following formula (A) is, for example, a compound of a transition metal selected from Groups 3 to 10 of the periodic table (Group 3 includes lanthanoids and actinoids); (B-1) an organic aluminum oxy compound, (B-2) a compound which reacts with the compound (A) to form an ion pair, and (B-3) at least one compound selected from organic aluminum compounds. In the presence of an olefin polymerization catalyst.

As the transition metal compound (A), a known organic metal complex can be used in addition to the Ziegler-Natta catalyst and the metallocene catalyst. Preferred compounds as the transition metal compound (A) are as follows. For example, the following are mentioned.

[0059]

Embedded image

(In the formula, M ¹ represents a transition metal atom belonging to Groups 3 to 10 of the periodic table, and R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ may be the same or different from each other; A nitrogen-containing group, a phosphorus-containing group, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom, Of the groups represented by ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ , some of the groups adjacent to each other may be linked to form a ring together with the carbon atom to which those groups are bonded, and X ¹ and X ^Two
May be the same or different, and have 1 carbon atom
Represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom, and Y ¹ represents 1 to 20 carbon atoms. A divalent hydrocarbon group having 1 to 2 carbon atoms
0 divalent halogenated hydrocarbon group, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group,-
O -, - CO -, - S -, - SO -, - SO 2 -, - Ge -, - Sn
^{-, - NR 21 -, -} P (R 21) -, - P (O) (R 21) -, - BR 21 -
Or —AlR ²¹ — (wherein R ²¹ may be the same or different, and is a hydrocarbon group having 1 to 20 carbon atoms;
A halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a halogen atom). )

[0061]

Embedded image

(Wherein, M ¹ represents a transition metal atom selected from Groups 3 to 10 of the periodic table, Cp represents a cyclopentadienyl group π-bonded to M ¹ or a derivative thereof;
¹ represents an oxygen atom, a sulfur atom, a boron atom or a ligand containing an element of the 14th group of the periodic table, and Y ¹ represents a ligand containing an atom selected from a nitrogen atom, a phosphorus atom, an oxygen atom and a sulfur atom. X ¹ may be the same or different, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group containing 20 or less carbon atoms and optionally having one or more double bonds, 20 The following silyl groups containing a silicon atom or germanyl groups containing a germanium atom are shown. )

[0063]

Embedded image

(Wherein M ¹ represents a transition metal atom selected from Groups 3 to 10 of the periodic table, and R ¹¹ to R ¹⁴ , R ¹⁷ to R ²⁰ and R ⁴¹ may be the same or different from each other; A hydrocarbon group having 1 to 40 carbon atoms,
40 represents a halogenated hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom, and R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁷ , R ¹⁸ , R ¹⁹ ,
Of the groups represented by R ²⁰ and R ⁴¹ , some of the groups adjacent to each other may be linked to form a ring together with the carbon atom to which those groups are bonded, and X ¹ and X ² may be the same as each other. Which may be different, represents a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a hydrogen atom or a halogen atom, Y ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, or a divalent Tin-containing group, -O-, -CO-, -S-, -S
_{O -, - SO 2 -,} - Ge -, - Sn -, - NR 21 -, - P (R 21)
-, - P (O) ( R 21) -, - BR 21 - or -AlR ²¹ - (provided that, R ²¹ may be the same or different from each other, a hydrocarbon group having 1 to 20 carbon atoms, carbon atoms A halogenated hydrocarbon group of Formulas 1 to 20, a hydrogen atom or a halogen atom.). )

[0065]

Embedded image

(Where M¹Is selected from groups 3 to 10 of the periodic table
Represents a transition metal atom¹¹, R^{1 Two}, R⁴¹And R
⁴²May be the same or different, and have 1 carbon atom
-40 hydrocarbon groups, halogenation of 1-40 carbon atoms
Hydrocarbon group, oxygen-containing group, sulfur-containing group, silicon-containing
R, a halogen atom or a hydrogen atom;¹¹, R¹²,
R ⁴¹, R⁴²Of the groups represented by
Ring together with the carbon atom to which the
May be formed, and X¹And X^TwoAre the same as each other
Hydrocarbons which may be different and have 1 to 20 carbon atoms
Group, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen
Containing group, sulfur containing group, silicon containing group, hydrogen atom or
Y represents a halogen atom;¹Is divalent having 1 to 20 carbon atoms
Hydrocarbon group (provided that R¹¹, R¹², R⁴¹And R⁴²Nosu
Y is when all are hydrogen atoms¹Is not ethylene
No. ), Divalent halogenated hydrocarbons having 1 to 20 carbon atoms
Silicon group, divalent silicon-containing group, divalent germanium-containing
Group, divalent tin-containing group, -O-, -CO-, -S-, -SO-,
-SO_Two-, -Ge-, -Sn-, -NR^{twenty one}-, -P (R^{twenty one})-, -P
(O) (R^{Two 1})-, -BR^{twenty one}-Or-AlR^{twenty one}-(However, R
^{twenty one}May be the same or different, and have 1 carbon atom
To 20 hydrocarbon groups, halogenation of 1 to 20 carbon atoms
It is a hydrocarbon group, a hydrogen atom or a halogen atom. )
Show. )

[0067]

Embedded image

(In the formula, M ¹ represents a transition metal atom selected from Groups 3 to 10 of the periodic table, R ⁴¹ and R ⁴² may be the same or different from each other, and may be a carbon atom having 1 to 40 carbon atoms. group, a halogenated hydrocarbon group having 1 to 40 carbon atoms, an oxygen-containing group, a sulfur-containing group, a silicon-containing group, a halogen atom or a hydrogen atom, among the groups represented by R ^41, R ^42, adjacent to each other May be linked to form a ring with the carbon atoms to which those groups are attached,
X ¹ and X ² may be the same or different from each other, and include a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, a sulfur-containing group, and a silicon-containing group. represents a hydrogen atom or a halogen atom, Y ¹
Is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin-containing group, -O -, - CO -, - S -, - SO -, - SO 2 -, - Ge -, -
^{Sn -, - NR 21 -,} - P (R 21) -, - P (O) (R 21) -, - BR
²¹ - or -AlR ²¹ - (provided that, R ²¹ may be the same or different from each other, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom or a halogen Atom).

The organoaluminum oxy compound (B-1) used in the present invention may be a conventionally known aluminoxane (also referred to as alumoxane).
It may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-8687. Further, examples of the organic aluminum oxy compound include an organic aluminum oxy compound containing boron represented by the following general formula.

[0070]

Embedded image

In the formula, R ⁸ represents a hydrocarbon group having 1 to 10 carbon atoms. R ⁹ may be the same or different, and represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms. Compound (B-2) which forms an ion pair by reacting with the transition metal compound (A) used in the present invention.
(Hereinafter sometimes referred to as "ionized ionic compound")
Japanese Patent Publication No. 1-501950, Japanese Patent Publication No. 1-5
02036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321
No. 106, a Lewis acid, an ionic compound,
Borane compounds and carborane compounds are included. Further, a heteropoly compound and an isopoly compound can also be mentioned.

Examples of the Lewis acid include a magnesium-containing Lewis acid, an aluminum-containing Lewis acid, a boron-containing Lewis acid, and among them, a boron-containing Lewis acid is preferable. The ionic compound is a salt composed of a cationic compound and an anionic compound. The anion functions to cationize the transition metal compound by reacting with the transition metal compound and to stabilize the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion and an organic aluminum compound anion, and those which are relatively bulky and stabilize transition metal cation species are preferable. Such ionized ionic compounds can be used as a mixture of two or more.

The organoaluminum compound (B-3) used in the present invention is an aluminum compound substituted with a hydrocarbon group having 1 to 12 carbon atoms, a halogen atom, an alkoxy group, a siloxy group, an amide group or a hydrogen atom. It is. These organoaluminum compounds can be used in combination of two or more. The olefin polymerization catalyst used in the present invention is selected from the above transition metal compound (A), an organic aluminum oxy compound (B-1), an ionized ionic compound (B-2) and an organic aluminum compound (B-3). When the transition metal compound (A) is a transition metal compound containing a ligand having a cyclopentadienyl skeleton formed from at least one compound (B), the compound and an organic aluminum oxy compound ( It is formed from (B-1) and / or an ionized ionic compound (B-2) and, if necessary, an organoaluminum compound (B-3).

The olefin polymerization catalyst used in the present invention includes a transition metal compound (A), an organic aluminum oxy compound (B-1), an ionized ionic compound (B-2) and an organic aluminum compound (B-3). A solid catalyst comprising at least one component supported on a particulate carrier; a particulate carrier; a transition metal compound (A); an organoaluminum oxy compound (B-1) (or an ionized ionic compound (B-2)) ) And an olefin polymer produced by the prepolymerization, and if necessary, a prepolymerization catalyst comprising an organoaluminum compound (B-3).

In the polymerization, the above transition metal compound (A) is usually used in an amount of about 0.00005 to 0.1 mmol, preferably about 0.0001, in terms of transition metal atom per liter of polymerization volume. Used in an amount of .about.0.05 mmol. The organoaluminum oxy compound (B-1) generally has an aluminum atom per mole of a transition metal atom,
About 1 to 10,000 mol, preferably 10 to 5,000 mol
It is used in a molar amount.

The ionized ionic compound (B-2) has a boron atom of usually about 0.5 to 1 mol of the transition metal atom.
It is used in such an amount that it becomes ５００500 mol, preferably 1-100 mol. The organoaluminum compound (B-3) is usually used in an amount of about 0 to 200 mol, preferably about 0 to 100 mol, per 1 mol of aluminum atoms in the organoaluminum oxy compound (B-1). Used as needed. It is used in an amount of usually 0 to 1000 mol, preferably about 0 to 500 mol, per 1 mol of boron in the ionized ionic compound (B-2).

When hydrogen is used, 10 ^-5 to 1 mol, preferably 10 ^-4 , per 1 mol of the monomer used for the polymerization is used.
It is used in such an amount that it becomes 10 ^-1 mol. The copolymerization of the olefin and the polar group-containing monomer can be carried out by any of liquid phase polymerization methods such as suspension polymerization and solution polymerization, gas phase polymerization method and high pressure method. In the liquid phase polymerization method, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; benzene, toluene, Inert hydrocarbon media such as aromatic hydrocarbons such as xylene; halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane are used. Further, the olefin itself can be used as the solvent. These may be used in combination.

The polymerization temperature is determined when the suspension polymerization is carried out.
Is usually in the range of −50 to 100 ° C., preferably 0 to 90 ° C.
It is desirable to use
Is usually in the range of 0 to 300 ° C, preferably 20 to 250 ° C.
It is desirable to use
Means that the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 1
It is desirable to be in the range of 00 ° C. In addition, the high pressure method has been implemented.
When applying, the polymerization temperature is usually 50 to 1000 ° C., preferably
Preferably, it is in the range of 100 to 500 ° C.
The polymerization pressure is usually from normal pressure to 100 kg / cm.^Two, Preferred
Normal pressure ~ 50kg / cm^Two Under the conditions of the high pressure method
In the case, usually 100 to 10,000 kg / cm ^Two , Preferred
Or 500-5000kg / cm^Two Condition. Heavy
The reaction can be performed in batch, semi-continuous, or continuous
Can also be performed. Further, the polymerization was performed under different reaction conditions.
It is also possible to perform the processing in two or more stages.

The molecular weight of the obtained olefin polymer can be adjusted by adjusting the amount of hydrogen or by changing the polymerization temperature and the polymerization pressure. Next, a Z part is produced from the X part of the copolymerized polar group-containing monomer in the polar group-containing olefin copolymer obtained as described above by anionic polymerization, ring-opening polymerization or polycondensation.

As a method for producing a Z part from an X part of a copolymerized polar group-containing monomer by anionic polymerization, ring-opening polymerization or polycondensation, for example, in the presence of a polar group-containing olefin copolymer and a proton extracting agent, Or an anion polymerization of a polar monomer in the presence of a polar group-containing olefin copolymer, a proton extracting agent and an active hydrogen compound.

Examples of the polar monomer include the above-mentioned (meth) acrylates, (meth) acrylonitriles, acrylamides, vinylpyridines, N-substituted maleimides, vinyl ketones, styrene derivatives and the like. No. Among these polar monomers, compounds having two or more ethylenically unsaturated bonds in one molecule are:
Polymerization by itself gives a highly crosslinked polymer, but copolymerization with a polar group-containing ethylenically unsaturated monomer having only one ethylenically unsaturated bond results in one ethylenically unsaturated bond. The main chain of a polymer of a polar group-containing ethylenically unsaturated monomer having only one main chain can be crosslinked.

Among these polar monomers, preferred monomers include monoesters of monohydric alcohols and acrylic acid or methacrylic acid, dihydric alcohols having one end protected by an ether bond, and acrylic monomers. Monoesters with acid or methacrylic acid, polyhydric esters in which acrylic acid or methacrylic acid is esterified with all hydroxy groups of dihydric or higher polyhydric alcohols, acrylonitrile, methacrylonitrile, N, N- Substituted monoacrylamides, vinyl or isopropenyl substituted pyridines, N-aromatic substituted maleimides, vinyl ketones and the like.

More preferred are monoesters of monohydric alcohols and acrylic acid or methacrylic acid, and monoesters of dihydric alcohols having one terminal protected by an ether bond and acrylic acid or methacrylic acid. And polyhydric esters in which acrylic acid or methacrylic acid is esterified with all hydroxy groups of dihydric or higher polyhydric alcohols, acrylonitrile, methacrylonitrile, N, N-disubstituted monoacrylamides and the like. .

Examples of the polar monomer include the above-mentioned alkylene oxide compounds. These polar monomers can be used alone or in combination of two or more. When two or more polar monomers are used in combination, the above polar monomer excluding the alkylene oxide compound (hereinafter sometimes referred to as “ethylenically unsaturated monomer”) is combined with an alkylene oxide compound. Is preferred.

When a plurality of polar monomers are combined and copolymerized, a method using a plurality of ethylenically unsaturated monomers, a method using a single ethylenically unsaturated monomer and a plurality of alkylene oxide compounds A method using a plurality of ethylenically unsaturated monomers and a single alkylene oxide compound, a method using a plurality of ethylenically unsaturated monomers and a plurality of alkylene oxide compounds, a method of adding these to a polymerization vessel, A method of sequentially using the polymerization vessel or a method of sequentially repeating addition may be employed.

When a plurality of polar monomers are simultaneously used and copolymerized, a polymer segment composed of a copolymer having relatively high randomness is obtained, depending on the difference in reactivity between the compounds. When two or more monomers are sequentially polymerized, a polymer segment composed of a block copolymer containing two or more blocks is obtained. By repeating such sequential use, a polymer segment composed of a more complicated copolymer can be obtained.

In particular, it is preferable to sequentially use an ethylenically unsaturated monomer and an alkylene oxide compound to produce a polymer segment composed of a block copolymer composed of a plurality of these monomers. In this case, the alkylene oxide compound is more preferably propylene oxide or ethylene oxide, and further preferably propylene oxide.

Examples of the active hydrogen compound include hydrogen fluoride, an active hydrogen compound having active hydrogen on a carbon atom, an active hydrogen compound having active hydrogen on an oxygen atom, an active hydrogen compound having active hydrogen on a nitrogen atom, An active hydrogen compound having an active hydrogen on a sulfur atom is exemplified. Examples of the active hydrogen compound having an active hydrogen on a carbon atom include hydrogen cyanide; ethyl acetate, cyclohexyl propionate, isopropyl butyrate, methyl isobutyrate, tert-butyl isobutyrate, hexyl caproate, butyl laurate, methyl stearate, Monovalent carboxylic acid esters such as ethyl oleate, methyl phenylacetate, methyl cyclohexanecarboxylate, 1,2-bis (2-propylcarbonyloxy) ethane, 1,2,3-tris (2-propylcarbonyloxy) propane Dimethyl malonate, dimethyl methyl malonate, diethyl succinate, 2,
3-dimethyl butyl succinate, methyl adipate, ethyl suberate, methyl butanetetracarboxylate, 1,2-bis (2-methoxycarbonylethoxy) ethane, 1,2-bis (2-ethoxycarbonylpropoxy) ethane, 1 , 2-bis (2-ethoxycarbonylpropylmercapto) ethane,
Polyvalent carboxylic esters such as N, N, N ', N'-tetrakis (2-butoxycarbonylpropyl) ethylenediamine; ethyl acetoacetate, cyclopentyl acetoacetate, methyl carbamoylacetate, ethyl 2-cyclohexylcarbonylacetate, butyl benzoylacetate Ketocarboxylic acid esters such as acetonitrile, 2-cyanopropane, malononitrile, methylmalononitrile, 1,3-dicyanopropane, adiponitrile and the like nitriles; acetone, methylethylketone, diisopropylketone, dicyclohexylketone, acetophenone and isopropylphenylketone and the like Ketones are exemplified.

Examples of active hydrogen compounds having active hydrogen on oxygen include water; methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol,
sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, n-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzyl Alcohol, 1-phenylethyl alcohol, triphenylcarbinol, cinnamyl alcohol, perfluoro-tert-butyl alcohol, α-hydroxyisopropyl phenyl ketone, α-hydroxycyclohexyl phenyl ketone, α-hydroxyisopropyl naphthyl ketone, α-hydroxyiso Monohydric alcohols such as methyl butyrate; ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3 -Butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-
Polyhydric alcohols such as cyclohexanediol, trimethylolpropane, glycerin, diglycerin, pentaerythritol, dipentaerythritol; aromatic hydroxy compounds such as phenol, cresol, xylenol, 2-naphthol, 2,6-dihydroxynaphthalene, bisphenol A And the like.

Examples of the active hydrogen compound having an active hydrogen on a nitrogen atom include methylamine, ethylamine,
n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, cyclohexylamine, benzylamine, β
-Phenylethylamine, aniline, o-toluidine, m-
Aliphatic or aromatic primary amines such as toluidine and p-toluidine; dimethylamine, methylethylamine, diethylamine, di-n-propylamine, ethyl-n-butylamine, methyl-sec-butylamine, dipentylamine, dicyclohexylamine, N Aliphatic or aromatic secondary amines such as -methylaniline or diphenylamine; ethylenediamine, di (2-aminoethyl) amine,
Primary or primary such as hexamethylenediamine, 4,4'-diaminodiphenylmethane, tri (2-aminoethyl) amine, N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine or di (2-methylaminoethyl) amine Polyvalent amines having a secondary amino group; saturated cyclic secondary amines such as pyrrolidine, piperidine, morpholine or 1,2,3,4-tetrahydroquinoline; 3-pyrroline, pyrrole, indole, carbazole, imidazole, pyrazole, Unsaturated cyclic secondary amines such as purine; cyclic polyamines containing a secondary amino group such as piperazine, pyrazine, 1,4,7-triazacyclononane; acetamide, propionamide, N-methylpropionamide Unsubstituted or N-monosubstituted acid amides such as N-methylbenzoic acid amide and N-ethylstearic acid amide; β- Cyclic amides such as propiolactam, 2-pyrrolidone, δ-valerolactam and ε-caprolactam; and imides of dicarboxylic acids such as succinimide, maleic imide and phthalimide.

Examples of the active hydrogen compound having an active hydrogen on a sulfur atom include monovalent compounds such as methanethiol, ethanethiol, n-butanethiol, tert-butanethiol, hexanethiol, decanethiol, cyclopentylmercaptan and cyclohexylmercaptan. Thiols; 1,2-ethanedithiol, 1,3-propanedithiol, 2,3-butanedithiol, 1,6-hexanedithiol,
Multivalent thiols such as 1,2,3-propanetrithiol, 2,3-di (mercaptomethyl) -1,4-butanedithiol, thiophenol, o-thiocresol, thionaphthol,
And aromatic mercapto compounds such as 2-benzenedithiol.

Examples of the active hydrogen compound include poly (alkylene oxide) having an active hydrogen at the terminal such as polyethylene oxide or polypropylene oxide.
: (Meth) acrylic esters, (meth) acrylonitriles, acrylamides, vinylpyridines, N-
Polymers obtained by anionic polymerization of substituted maleimides, vinyl ketones, styrene derivatives and other polymerization methods; Polymers obtained by ring-opening polymerization of lactones, lactams, lactides, cyclic siloxanes, etc .; Poly (meth) acrylates having active hydrogen in the chain, poly (meth) acrylonitrile, poly (acrylamide) s, poly (vinylpyridine) s, poly (N-substituted maleimides), poly Examples thereof include polymers such as (vinyl ketone) s, poly (styrene derivatives), polyesters, polyamides, polylactides, and polysiloxanes, and copolymers thereof.

Preferred among these active hydrogen compounds are hydrogen cyanide, monovalent carboxylic acid esters, polycarboxylic acid esters, water, monohydric alcohols, polyhydric alcohols, and monovalent thiols. Poly (alkylene oxides), poly ((meth) acrylates) having active hydrogen at the terminal and / or main chain
, Poly {(meth) acrylonitrile}, poly (acrylamide) s, poly (vinylpyridine) s, poly (N-
Substituted maleimides), poly (vinyl ketone) s or poly (styrene derivatives), and copolymers thereof.

These proton abstracting agents may be used alone or as a mixture of two or more. In the present invention, at least a polar monomer is anionically polymerized in the presence of a proton abstracting agent and an active hydrogen compound or in the presence of a proton abstracting agent. Ring-opening polymerization can also be performed by this method.

The following method can be used for extracting a proton from a proton-extracting agent or an active hydrogen compound to be used for polymerization to produce an anion. (1) A method using an alkali metal hydroxide or an alkali metal carbonate. (2) A method using an alkali metal such as an alkali metal, an alkali metal hydride, an alkali metal amide, and an alkali metal alkyl. (3) A method using a zinc compound. (4) A method using ammonium hydroxide. (5) A method using a phosphazenium salt.

The phosphazenium compound is described in EP0791
The compound can be synthesized by the method described on pages 12 to 13 of P.600 or a similar method. The method for producing the Z part by anionic polymerization from the X part of the polar group-containing monomer is not particularly limited as long as it can effectively contact at least the proton extracting agent and the polar monomer. It can also be carried out by a method of supplying the monomer intermittently or continuously.

The polymerization reaction can be carried out in a molten state of the polar monomer, but can also be carried out in a liquid phase using an appropriate solvent. In this case, the liquid phase may be homogeneous or suspended.
As the solvent used here, for example, n-hexane, n-
Aliphatic or alicyclic hydrocarbons such as heptane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; aromatic halides such as chlorobenzene and dichlorobenzene; diethyl ether, diphenyl ether, tetrahydrofuran, tetrahydropyran,
Ethers such as 1,4-dioxane, ethylene glycol dimethyl ether and diethylene glycol diethyl ether; aprotic polar solvents such as dimethylformamide, dimethyl sulfoxide, sulfolane or N, N'-dimethylimidazolidinone;

[0098] The amount of the proton abstracting agent is not particularly limited, usually, relative polar monomer 1 mol, 1 × 10 ^-6 to 1
× 10 ^-1 mol, preferably 1 × 10 ^{-4 to} 3 × 1
0 ^-1 mol of range. The temperature of the polymerization reaction is not uniform depending on the type and amount of the proton-extracting agent and the polar monomer used, but is usually -50 ° C to 250 ° C, preferably -20 ° C to 150 ° C. . The pressure of the polymerization reaction is not uniform depending on the type and amount of the polar monomer to be used, the reaction temperature, and the like, but is usually 3.0 MPa (absolute pressure expressed in megapascals, the same applies hereinafter), and preferably 0.1 MPa or less.
01 to 1.5 MPa, more preferably 0.1 to 1.
0 MPa.

The reaction time of the polymerization reaction varies depending on the type and amount of the proton extracting agent and the polar monomer used, the reaction temperature and the like, but is usually within 50 hours, preferably 0.1 to 24 hours. Next, the method (b) will be specifically described. In the method (b), an α-olefin having 2 to 20 carbon atoms and a polar group-containing monomer represented by the above general formula (4) are copolymerized to produce a polar group-containing olefin copolymer, and then copolymerized. The X part of the polar group-containing monomer thus obtained is reacted with a terminal functional group of a polymer obtained by anionic polymerization, ring-opening polymerization or polycondensation.

The polar group-containing olefin copolymer can be produced in the same manner as in the above method (a). Polymer obtained by anionic polymerization, ring-opening polymerization or polycondensation (hereinafter sometimes referred to as "terminal functional group-containing polymer")
As the methyl methacrylate, ethyl methacrylate, butyl acrylate, acrylonitrile, segments obtained by anionic polymerization of one or two or more of acrylamide, lactone, lactide, siloxane,
Segments obtained by ring-opening polymerization of lactams, cyclic ethers, oxazolines, ethylene oxides, propylene oxides, etc. The resulting polymer is exemplified. Among them, a segment obtained by anionic polymerization of an acrylate or methacrylate derivative or a polymer obtained by ring-opening polymerization of ethylene oxide or propylene oxide is preferable.

Such a terminal functional group-containing polymer is prepared by, for example, adding the polar monomer used in the above method (a) to
There is a method in which a polar monomer is subjected to anionic polymerization, ring-opening polymerization or polycondensation in the presence of the above-mentioned proton abstracting agent or in the presence of the above-mentioned proton abstracting agent and the above-mentioned active hydrogen compound. Next, the polar group-containing olefin copolymer obtained as described above and the terminal polar group-containing polymer are copolymerized.

Next, the method (c) will be specifically described. In the method (c), an α-olefin having 2 to 20 carbon atoms and a macromonomer represented by the above general formula (5) are copolymerized. Examples of the α-olefin having 2 to 20 carbon atoms include the same as described above.

Examples of the macromonomer represented by the above general formula (5) include the following macromonomers.

[0104]

Embedded image

[0105]

Embedded image

Such a macromonomer is prepared by using, for example, the above-mentioned polar group-containing monomer and subjecting it to anionic polymerization, ring-opening polymerization or polycondensation from the polar group of the polar group-containing monomer in the same manner as in the above method (a). It can be produced by polymerizing the united segments. The copolymerization of the α-olefin having 2 to 20 carbon atoms with the macromonomer represented by the general formula (5) is performed, for example, by the method (a), wherein the α-olefin having 2 to 20 carbon atoms is Using an olefin polymerization catalyst used for copolymerization with the polar group-containing monomer represented by the general formula (4), an α-olefin having 2 to 20 carbon atoms according to the above method (a) and a general formula (4)
Is carried out under the same conditions as in the copolymerization with the polar group-containing monomer represented by

Thermoplastic Resin Composition The thermoplastic resin composition according to the present invention may be formed from two or more copolymers selected from the above-mentioned polar group-containing branched olefin copolymers. It may be formed of a branched olefin-containing copolymer and a thermoplastic resin other than the polar group-containing branched olefin copolymer. (Thermoplastic resin) In the present invention, as the thermoplastic resin, polyolefin, polyamide, polyester, polyacetal, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polymethacrylate, polycarbonate, polyphenylene oxide, polyvinyl chloride, polyvinylidene chloride, One type of thermoplastic resin selected from polyvinyl acetate, ethylene- (meth) acrylate copolymer, and diene rubber is preferably used.

As the polyolefin, polyethylene,
Olefin homopolymer such as polypropylene, poly-1-butene, polymethylpentene, polymethylbutene, ethylene-α-olefin random copolymer, ethylene-propylene-diene terpolymer, propylene-ethylene random copolymer , Propylene-α-olefin random copolymer, olefin copolymers such as propylene-ethylene-α-olefin terpolymer and the like, among which polyethylene, polypropylene, ethylene-α-olefin random copolymer, Preferred are an ethylene-propylene-diene terpolymer, a propylene-ethylene random copolymer, and a propylene-α-olefin random copolymer. When the polyolefin is a polyolefin obtained from an olefin having 3 or more carbon atoms, it may be an isotactic polymer or a syndiotactic polymer.

As the catalyst used for producing the polyolefin, any known catalyst such as a Ziegler-Natta type catalyst or a metallocene catalyst may be used. Examples of the polyamide include aliphatic polyamides such as nylon-6, nylon-66, nylon-10, nylon-12, and nylon-46, and aromatic polyamides produced from aromatic dicarboxylic acids and aliphatic diamines. -6 is preferred.

Examples of the polyester include aromatic polyesters such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, polycaprolactone, and polyhydroxybutyrate, and polyethylene terephthalate is preferred. Examples of the polyacetal include polyformaldehyde (polyoxymethylene), polyacetaldehyde, polypropionaldehyde, polybutyraldehyde, and the like, with polyformaldehyde being particularly preferred.

The polystyrene may be a homopolymer of styrene, or a binary copolymer of styrene with acrylonitrile, methyl methacrylate, α-methylstyrene, etc., for example, an acrylonitrile-styrene copolymer. . As the ABS, a structural unit derived from acrylonitrile is contained in an amount of 20 to 35 mol%, a structural unit derived from butadiene is contained in an amount of 20 to 30 mol%, and a structural unit derived from styrene is contained. 40-6
Those containing in an amount of 0 mol% are preferably used.

As the polymethacrylate, polymethyl methacrylate (PMMA) is preferable. As polycarbonate, bis (4-hydroxyphenyl) methane,
Examples thereof include those obtained from 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, and the like. Polycarbonates obtained from -bis (4-hydroxyphenyl) propane are preferred.

The polyphenylene oxide is preferably poly (2,6-dimethyl-1,4-phenylene oxide). The polyvinyl chloride may be a homopolymer of vinyl chloride or a copolymer with vinylidene chloride, acrylate, acrylonitrile, propylene, or the like.

As the polyvinylidene chloride, a copolymer of vinyl chloride, acrylonitrile, (meth) acrylic ester, allyl ester, unsaturated ether, styrene, etc., containing 85% or more of vinylidene chloride units is usually used. The polyvinyl acetate may be a homopolymer of vinyl acetate or a copolymer with ethylene and vinyl chloride. Among these, an ethylene-vinyl acetate copolymer is preferred.

Examples of the ethylene- (meth) acrylate copolymer include ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer.
Methyl methacrylate copolymer and ethylene-ethyl methacrylate copolymer are preferred. Examples of the diene rubber include conjugated polydienes such as polybutadiene, polyisoprene, and an elastomer type styrene-butadiene copolymer also known as SBR (styrene-butadiene rubber). In these, at least a part of the double bond in the molecule may be hydrogenated.

The above thermoplastic resins can be used alone or in combination of two or more. Among these thermoplastic resins, it is preferable to use polyolefin, polyester, polyamide, and polystyrene. The thermoplastic resin composition according to the present invention can be produced by mixing a polar group-containing branched olefin copolymer and a thermoplastic resin with, for example, a ribbon blender, a tumbler blender, a Henschel blender, or the like.

Further, the thermoplastic resin composition according to the present invention comprises:
For example, a kneader such as a co-kneader, a Banbury mixer, a Brabender, a single-screw extruder, a twin-screw extruder, a twin-screw surface renewer, or a twin-screw multi-disc is used to prepare a polar group-containing branched olefin copolymer and a thermoplastic resin. It can also be produced by melt-kneading using a melt-kneading device such as a horizontal stirrer such as a device or a vertical stirrer such as a double helical ribbon stirrer.

Ingredients The branched olefin copolymer containing a polar group and the thermoplastic resin composition according to the present invention comprise an inorganic filler, an organic filler,
A crystal nucleating agent, a heat stabilizer, a weather stabilizer, an antistatic agent, a coloring agent, a lubricant, a flame retardant, an anti-blooming agent and the like may be contained as long as the object of the present invention is not impaired.

(Inorganic filler) Examples of the inorganic filler include 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 beads,
Calcium silicate, montmorillonite, bentonite,
Examples include graphite, aluminum powder, and molybdenum sulfide.

Among these, a layered compound is preferable, and a clay mineral having swelling and cleavage 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 top of a tetrahedral layer of silica, and a type having a tetrahedral layer of silica such as 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. Examples of the former two-layer structure type include a kaolinite group and an antigolite group, and examples of the latter three-layer structure type include a smectite group, a vermiculite group, and a 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.

[0122] 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.

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

(Crystal Nucleating Agent) As the crystal nucleating agent, various conventionally known nucleating agents can be used without any particular limitation. Examples of the crystal nucleating agent include the following aromatic phosphate ester salts, benzylidene sorbitol, aromatic carboxylic acids, and rosin-based nucleating agents. Examples of the aromatic phosphate salt include a compound represented by the following general formula (A).

[0126]

Embedded image

(In the formula, R ¹¹ represents an oxygen atom, a sulfur atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹² and R ¹³ represent a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. , R ¹² and R ¹³ may be the same or different, and R ¹² may be combined with each other, R ¹³ may be combined with each other, or R ¹² and R ¹³ may be combined to form a ring. Represents a valence metal atom, and n is an integer of 1 to 3.) As the compound represented by the general formula (A), specifically,
Sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-
Bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-ethylidene -Bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-6-t-butylphenyl) phosphate, lithium-2,2 ' -Methylene-
Bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, calcium-bis [2,2'-
Thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4-ethyl-6-
t-butylphenyl) phosphate], calcium-bis [2,2′-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2′-thiobis (4,6 -Ji-
t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis- (4-t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis (4,6-di-
Methylphenyl) phosphate, sodium-2,2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6
-Di-methylphenyl) phosphate, sodium-2,2 '
-t-octylmethylene-bis (4,6-di-t-butylphenyl)
Phosphate, calcium-bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di -t-butylphenyl) phosphate], barium-bis [2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate], sodium-2,2′-methylene-bis (4 -Methyl-6-t-
Butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-5,6'-di-t-butyl
-2,2'-biphenyl) phosphate, calcium-bis [(4,4'-dimethyl-6,6'-di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2 '-Ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate,
Sodium-2,2'-methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-
2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, calcium-bis [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphophosphate], Magnesium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6-di-t-butyl) Phenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-
Di-t-butylfell) phosphate] and aluminum-tris [2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof. it can. Particularly, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate is preferred.

As the aromatic phosphoric acid ester salt, a compound represented by the following general formula (B) can be exemplified.

[0129]

Embedded image

(In the formula, R ¹⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, M represents a 1 to 3 valent metal atom, and n represents an integer of 1 to 3.) Specific examples of the compound represented by the general formula (B) include:
Sodium-bis (4-t-butylphenyl) phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) phosphate, sodium-bis (4-i-propylphenyl) phosphate Fate, sodium-bis (4-t-octylphenyl) phosphate, potassium-bis (4-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium-bis (4- t-
Butylphenyl) phosphate, lithium-bis (4-t
-Butylphenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosphate, and mixtures of two or more thereof. Particularly, sodium-bis (4-t-butylphenyl) phosphate is preferred.

Examples of benzylidene sorbitol include compounds represented by the following general formula (C).

[0132]

Embedded image

(In the formula, R ¹⁵ may be the same or different, and represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and m and n are each an integer of 0 to 5.) Specific examples of the compound represented by the general formula (C) include:
1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3
-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1, 3-p-ethylbenzylidene-
2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,2, 4-di (pn-propylbenzylidene) sorbitol, 1,3,2,4-
Di (pi-propylbenzylidene) sorbitol, 1,3,2,
4-di (pn-butylbenzylidene) sorbitol, 1,3,2,
4-di (ps-butylbenzylidene) sorbitol, 1,3,2,
4-di (pt-butylbenzylidene) sorbitol, 1,3,2,
4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,
3,2,4-di (p-methoxybenzylidene) sorbitol, 1,
3,2,4-di (p-ethoxybenzylidene) sorbitol, 1,
3-benzylidene-2-4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1 , 3-p-Chlorbenzylidene-
2,4-p-ethylbenzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-p-chlorobenzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidenesorbitol and 1, Examples thereof include 3,2,4-di (p-chlorobenzylidene) sorbitol and a mixture of two or more of these. In particular, 1,3,2,4-dibenzylidene sorbitol,
1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,
3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3-
P-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof are preferred.

Among the benzylidene sorbitols described above, a compound represented by the following formula (D) can be mentioned as a preferred example.

[0135]

Embedded image

(In the formula, R ¹⁵ may be the same or different and each represents a methyl group or an ethyl group.) As the aromatic carboxylic acid, aluminum hydroxydiparatanol represented by the following general formula (E) is used. -Butyl benzoate and the like.

[0137]

Embedded image

Examples of the rosin-based crystal nucleating agent include a metal salt of rosin acid, and the metal salt of rosin acid refers to a reaction product of rosin acid and a metal compound. Examples of rosin acids include natural rosins such as gum rosin, tall oil rosin, and wood rosin; various modifications such as disproportionated rosin, hydrogenated rosin, dehydrogenated rosin, polymerized rosin, and α, β-ethylenically unsaturated carboxylic acid-modified rosin Rosin; a purified product of the natural rosin and a purified product of the modified rosin can be exemplified. The unsaturated carboxylic acids used for preparing the α, β-ethylenically unsaturated carboxylic acid-modified rosin include, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, acrylic acid And methacrylic acid. Among these, at least one rosin acid selected from the group consisting of natural rosin, modified rosin, a purified product of natural rosin, and a purified product of modified rosin is preferable. Here, rosin acid is pimaric acid, sandaracopimaric acid, parastolic acid, isopimaric acid, abietic acid, dehydroabietic acid, neoabietic acid, dihydropimaric acid, dihydroabietic acid,
It contains a plurality of resin acids selected from tetrahydroabietic acid and the like.

Examples of the metal compound which reacts with rosin acid to form a metal salt include compounds which have a metal element such as sodium, potassium, magnesium and the like and which form a salt with rosin acid. Specific examples include chlorides, nitrates, acetates, sulfates, carbonates, oxides, hydroxides, and the like of the above-mentioned metals. Examples of other crystal nucleating agents include high melting point polymers, metal salts of aromatic carboxylic acids and aliphatic carboxylic acids, and inorganic compounds.

Examples of the high melting point polymer include polyvinyl cycloalkane such as polyvinyl cyclohexane and polyvinyl cyclopentane, poly 3-methyl-1-pentene, poly 3-
Examples thereof include methyl-1-butene and polyalkenylsilane. Examples of the metal salts of aromatic carboxylic acids and aliphatic carboxylic acids include aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and sodium pyrrolecarboxylate.

(Molding Method) The branched olefin copolymer containing a polar group and the thermoplastic resin composition according to the present invention are produced by calender molding, extrusion molding, injection molding, blow molding, press molding, stamping molding, etc. Can be. Sheet or film (unstretched) by extrusion
Can be molded into

The stretched film is obtained by stretching the above-mentioned extruded sheet or extruded film (unstretched) by, for example, a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method and a uniaxial stretching method. . In addition, an inflation film can be produced from the polar group-containing branched olefin copolymer and the thermoplastic resin composition according to the present invention.

The filament can be produced, for example, by extruding a molten composition through a spinneret. Moreover, you may prepare by a melt blown method. The injection molded body can be manufactured by injection molding the composition into various shapes using a conventionally known injection molding apparatus under known conditions. The injection molded article comprising the polar group-containing branched olefin copolymer and the thermoplastic resin composition according to the present invention is hardly charged, and has rigidity, heat resistance, impact resistance, surface gloss, chemical resistance, abrasion resistance, and the like. It is excellent in trim materials for automobile interiors, exterior materials for automobiles, housings for home appliances,
It can be used widely in containers and the like.

A blow-molded article can be produced using a conventionally known blow-molding apparatus under known conditions. In injection blow-molding, the polar group-containing branched olefin copolymer of the present invention is used. Injecting a thermoplastic resin composition into a parison mold at a resin temperature of 100 ° C. to 300 ° C. to form a parison, and then holding the parison in a mold having a desired shape, followed by blowing air to mount the parison on the mold. Can produce a hollow molded article.

As the press-formed body, a mold stamping formed body can be mentioned. (Uses) The polar group-containing branched olefin copolymer and the thermoplastic resin composition according to the present invention can be used for various uses, for example, for the following uses. (1) Films and Sheets Films and sheets comprising the polar group-containing branched olefin copolymer or the thermoplastic resin composition according to the present invention have flexibility, transparency, tackiness, antifogging property, heat resistance, and separability. One of them is excellent. (2) Laminate As the laminate including at least one layer made of the polar group-containing branched olefin copolymer or the thermoplastic resin composition according to the present invention, for example, an agricultural film, a wrap film, a shrink film, Protective film,
Examples include separation membranes such as a plasma component separation membrane and a water selective pervaporation membrane, and selective separation membranes such as an ion exchange membrane, a battery separator, and an optical splitting membrane. (3) The polar group-containing branched olefin copolymer and the thermoplastic resin composition according to the present invention are microcapsules, P
It can be used for TP packaging, chemical valves, and drug delivery systems. (4) Modifier When the polar group-containing branched olefin copolymer or the thermoplastic resin composition according to the present invention is used as a resin modifier,
It has the effect of modifying impact resistance, fluidity, paintability, crystallinity, adhesiveness, transparency, etc.

When the polar group-containing branched olefin copolymer or the thermoplastic resin composition according to the present invention is used as a rubber modifier, it has the effect of improving weather resistance, heat resistance, adhesion, oil resistance and the like. . Rubbers include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), and chloroprene rubber (C
R), acrylonitrile-butadiene rubber (NBR),
Butyl rubber (IIR), ethylene-propylene rubber (EPM, EPDM), chlorosulfonated polyethylene (CSM), acrylic rubber (ACM, ANM, etc.), epichlorohydrin rubber (CO, ECO, etc.), silicone rubber (Q), Cross-linked rubber such as fluorine-based rubber (FKM, etc.);
Styrene, olefin, urethane, ester,
An amide-based, vinyl chloride-based thermoplastic rubber or the like can be used.

Lubricating oil soluble modifiers such as gasoline engine oil, diesel engine oil, marine engine oil, gear oil,
It can be used for lubricating oils such as machine oils, metal working oils, motor oils, machine oils, spindle oils, and insulating oils, as well as viscosity modifiers and freezing point depressants for these. When the polar group-containing branched olefin copolymer or the thermoplastic resin composition according to the present invention is used as a wax modifier, effects such as adhesiveness, fluidity, and strength are improved. As the wax, mineral wax such as montan wax, peat wax, ozokerite / ceresin wax, petroleum wax, synthetic wax such as polyethylene, Fischer-Tropsch wax, chemically modified hydrocarbon wax, substituted amide wax, vegetable wax, animal wax, etc. Is mentioned.

When used as a modifying agent for cement, there is an effect of modifying formability, strength and the like. As cement, lime, gypsum, magnesia cement and other air-hardened cements,
There are hydraulic cements such as Roman cement, natural cement, Portland cement, alumina cement, high sulfate slag cement, etc., and special cements such as acid resistant cement, refractory cement, water glass cement, dental cement and the like. (5) Viscosity adjuster, moldability improver The polar group-containing branched olefin copolymer and the thermoplastic resin composition according to the present invention include inks such as letterpress printing inks, lithographic printing inks, flexographic inks, gravure inks, and oils. It can be used as a viscosity modifier for inks and paints such as paints, cellulose derivative paints, synthetic resin paints, water-based baking paints, powdery water-based paints, lacquers, etc., and moldability improvers. (6) Building materials and civil engineering materials The polar group-containing branched olefin copolymer and the thermoplastic resin composition according to the present invention include, for example, floor materials, floor tiles, floor sheets, sound insulation sheets, heat insulation panels, vibration insulators, It can be used for building materials and civil engineering resins such as decorative sheets, baseboards, asphalt modifiers, gasket sealing materials, roofing sheets, waterproof sheets, etc., and moldings for building materials and civil engineering. (7) Vehicle interior / exterior material and gasoline tank The vehicle interior / exterior material comprising a polar group-containing branched olefin copolymer or a thermoplastic resin composition according to the present invention, a thermoplastic resin composition, and a gasoline tank have rigidity and impact resistance. Excellent in oil resistance, oil resistance and heat resistance. (8) Electric, electronic parts, etc. The polar group-containing branched olefin copolymer and the thermoplastic resin composition according to the present invention are an electric insulating material; an electronic component processing equipment; a magnetic recording medium, a binder for a magnetic recording medium, Circuit sealing materials, home appliance materials, container equipment such as microwave oven containers, microwave oven films, polymer electrolyte substrates, conductive alloy substrates, etc. Connector, socket, resistor, relay case switch coil bobbin, condenser, variable condenser case, optical pickup, optical connector,
Oscillator, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, housings, semiconductors, liquid crystal display parts,
Electric / electronic parts such as FDD carriage, FDD chassis, HDD parts, motor brush holder, parabolic antenna, computer related parts, etc .; VT
R parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, audio parts, audio equipment parts such as audio / laser disks (registered trademark) / compact disks, lighting parts, refrigerator parts, air conditioner parts, typewriters Used for home and office electrical product parts, office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, electromagnetic shielding materials, speaker cone materials, speaker vibrating elements, etc. represented by parts, word processor parts, etc. Can be. (9) Aqueous emulsion The aqueous emulsion containing the polar group-containing branched olefin copolymer or the thermoplastic resin composition according to the present invention can be an adhesive for polyolefin having excellent heat sealability. (10) Paint base The solvent dispersion containing the branched olefin copolymer containing a polar group or the thermoplastic resin composition according to the present invention has excellent dispersion stability in a solvent, and is used for bonding a metal or a polar resin to a polyolefin. Shows good adhesion. (11) Medical / Hygiene Material The polar group-containing branched olefin copolymer and the thermoplastic resin composition according to the present invention include a nonwoven fabric, a nonwoven fabric laminate, an electret, a medical tube, a medical container, an infusion bag, and a prefill. It can be used for medical supplies such as syringes and syringes, medical materials, artificial organs, artificial muscles, filtration membranes, food hygiene / health supplies; retort bags, freshness retaining films and the like. (12) Miscellaneous Goods The polar group-containing branched olefin copolymer and the thermoplastic resin composition according to the present invention include a desk mat, a cutting mat, a ruler, a pen barrel, a grip and a cap, grips such as scissors and a cutter, Stationery such as magnet sheets, pen cases, paper folders, binders, label seals, tapes, whiteboards, etc .: clothing, curtains, sheets, carpets, entrance mats, bath mats, buckets,
Household goods such as hoses, bags, planters, filters for air conditioners and exhaust fans, dishes, trays, cups, lunch boxes, funnels for coffee siphons, eyeglass frames, containers, storage cases, hangers, ropes, laundry nets, etc .: shoes , Goggles, skis, rackets, balls, tents, underwater glasses, foot fins, fishing rods, cooler boxes, leisure seats, sports nets and other sports equipment: toys such as blocks, cards, etc .: kerosene cans, drums, detergents and shampoos And other containers; signboards, pylons, plastic chains, and the like. (13) Filler Modifier The polar group-containing branched olefin copolymer and the thermoplastic resin composition according to the present invention include a filler dispersibility improver, an additive for preparing a filler having improved dispersibility, and the like. It can be suitably used for applications. (14) Compatibilizer The polar group-containing branched olefin copolymer and the thermoplastic resin composition according to the present invention can be used as a compatibilizer. When the polar group-containing branched olefin copolymer according to the present invention is used, a polyolefin and a polar group-containing thermoplastic resin can be mixed at an arbitrary ratio.
The polar group-containing branched olefin copolymer according to the present invention,
Since it has a polyolefin main chain and a side group having a polar group, components that were originally incompatible can be mixed, and the breaking point is lower than when no olefin copolymer containing a polar group is used. Elongation can be significantly improved.

[0149]

Industrial Applicability The branched olefin copolymer containing a polar group and the thermoplastic resin composition according to the present invention have excellent adhesiveness with a polar substance such as a metal or a polar resin, compatibility, surface hydrophilicity,
Excels in paintability, printability, antifogging properties, antistatic properties, oil resistance, biocompatibility, water dispersibility, solvent dispersibility, pigment dispersibility, filler dispersibility, as well as transparency, mechanical strength and moldability. Are better.

[0150]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In the examples, various physical properties were measured as follows. [Anti-fogging property] Preparation of film A polyethylene terephthalate (PET) sheet and a 100-μm-thick aluminum sheet whose center was cut into 15 cm x 15 cm squares were laid in this order on a press plate, and the center (cut-off part) Placed a 3.3 g sample (diblock copolymer). Next, a PET sheet, an aluminum sheet, and a press plate were further stacked in this order.

The sample sandwiched between the press plates was placed in a hot press at 200 ° C., and after preheating for about 7 minutes,
Pressurization (50 kg / cm ^2-
G) The depressurization operation was repeated several times. Then, 100kg /
The pressure was raised to cm ² -G, and the mixture was heated under pressure for 2 minutes. After depressurization, the press plate was taken out of the press machine, transferred to another press machine having a press-bonded portion kept at 0 ° C., pressurized and cooled at 100 kg / cm ² -G for 4 minutes, and then depressurized. I took it out. A diblock copolymer film was used for initial antifogging evaluation.

Evaluation of Initial Antifogging Property 70 cc of water was put into a 100 cc beaker, the upper surface thereof was covered with a sample film, the beaker was placed in a 50 ° C. constant temperature water bath, and left in a 20 ° C. constant temperature room. The degree of haze on the inner surface of the sample film was observed after 24 hours. Evaluation criteria; ○: at dripping state, water droplets is not observed △: partially × water droplets having a large particle is adhered to the film: substantially adhered to the entire surface [mechanical properties] Test pieces of fine water droplets film The graft copolymer obtained in Example was molded at a cylinder temperature of 200 ° C. and a mold temperature of 40 ° C. using a 55-t injection molding machine (IS55EPN manufactured by Toshiba Machine Co., Ltd.).

Flexural modulus (FM) According to ASTM C790, a test piece having a thickness of 1/8 inch was used, and the span between the spans was 51 mm and the bending speed was 20 mm /
It was measured under the condition of minutes. Rockwell hardness (HR) 2 mm thick x 120 vertical according to ASTM D785
The measurement was performed using a square plate having a size of 130 mm × 130 mm.

Pencil hardness : Measured at 23 ° C. using a 1 / 8-inch thick test piece in accordance with JIS K5401. Heat distortion temperature (HDT) In accordance with ASTM D648 (4.6 kg / cm ² ),
The measurement was performed using a 1/4 inch thick test piece.

[Water dispersibility] Preparation of aqueous dispersion 40 g of the obtained branched olefin copolymer containing a polar group
And maleic anhydride-grafted polypropylene (propylene / ethylene: 98/2 molar ratio, maleic anhydride content:
4.0% by weight, viscosity average molecular weight: 17,000, density:
0.919 g / cm ³ , melting point: 136 ° C, softening point: 14
3 ° C., melt viscosity (180 ° C.): 500 cps) 4 g,
After mixing with 1.2 g of potassium oleate at room temperature, the mixture was melted and kneaded for 5 minutes in a Labo Plastomill (setting temperature: 200 ° C.), and then 1.4 g of an 18.7% aqueous solution of potassium hydroxide was added. The mixture was melt-kneaded for 5 minutes. Subsequently, the content was taken out, and the solid emulsion was dispersed in hot water at 60 ° C. to obtain an aqueous resin dispersion.

Measurement of Dispersion Particle Size Measurement was performed using a Microtrack manufactured by Honeywell. Dispersion Stability The aqueous resin dispersion obtained in the example was placed in a sealable glass bottle and allowed to stand at room temperature, and after one month, it was confirmed whether or not an aqueous phase and a resin phase had separated.

[0157] ¹ According to H-NMR (2) / ( 3) Calculation equipment of: JEOL GFX400 type nuclear magnetic resonance apparatus outlook measuring nuclear: ¹ H Observation frequency: 400 MHz Pulse width: 45 ° repetition time: 5.0 seconds Number of integration: 8000 times Measurement temperature: 115 ° C. Measurement solvent: ortho-dichlorobenzene Measurement: 25 to 40 mg of the obtained polymer was dissolved in ortho-dichlorobenzene, and NMR measurement was performed under the above measurement conditions.

The chemical shift of the methylene group next to the unreacted alcohol is 3.50 ppm. Unreacted alcohol groups are converted to trifluoroacetates by reaction with trifluoroacetic acid-d1 (the chemical shift of the methylene group next to the alcohol shifts to 4.17 ppm). On the other hand, since the chemical shift of the methylene group adjacent to oxygen in the produced polymer appears at 3.35 to 3.65 ppm, (2) / (3) = (integrated intensity of 3.35 to 3.65 ppm) / ( (Integrated intensity of 4.17 ppm).

[0159]

Example 1 400 ml of toluene was charged into a 1000 ml-volume glass polymerization vessel which had been sufficiently purged with nitrogen, and nitrogen was allowed to flow at a rate of 20 liter / hour and kept at 90 ° C. for 10 minutes. To this was added 2.0 mmol of triisobutylaluminum, and then Unde represented by the following formula:
cene-ol (dried on activated alumina and distilled under reduced pressure)
1.88 mmol were added.

[0160]

Embedded image

Further, methylaluminoxane 1.100
The flow of nitrogen was stopped by adding mmol, and ethylene was flowed at a rate of 5 liter / hour. Finally, 0.008 mmol of dimethylsilylene (2,7-dimethyl-4,5 (2-methyl-benzo) -1-indenyl) (2,7-ditert-butylfluorenyl) zirconium dichloride and methylaluminoxane.2. And 10 mmol of a toluene slurry solution contacted at room temperature for 10 minutes.
After polymerization for 1 hour at ℃, a small amount of isobutyl alcohol was added to terminate the polymerization. Furthermore, concentrated hydrochloric acid aqueous solution 1m
l of isobutyl alcohol solution containing 1 l were added and heated at 75 ° C. under nitrogen. The polymer solution was added to a large excess of methanol to precipitate the polymer,
After drying under reduced pressure for a period of time, the polymer 12.2 was ethylene / side chain monomer (molar ratio = 99.2 / 0.8).
1 g was obtained.

An ethylene / side-chain monomer (molar ratio = 99.2 / 0.8) prepared by the above method was placed in a 1500 ml-volume autoclave equipped with a temperature measuring tube, a pressure gauge, a stirrer, and an alkylene oxide introducing tube. Copolymer 12.
0g, tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide {[(Me ₂ N) ₃ P = N] ₄ P ⁺ synthesized in the same manner as described on page 32 of EP 0791600. OH ^-} 31.0
mg and 800 g of tetralin. Thereafter, the content was heated to 125 ° C. and reacted at the same temperature for 12 hours while intermittently supplying 3.1 g of ethylene oxide so that the pressure was maintained at about 0.9 MPa (absolute pressure). Next, after unreacted ethylene oxide remaining at the same temperature was distilled off under reduced pressure, the content was cooled to room temperature, and the content was poured into 800 ml of methanol. The precipitated white solid was separated by filtration, and 20 ml of methanol was further added to the solid.
Heated to reflux for 0 minutes. This mixture was filtered while hot, and the solid obtained was dried at 60 ° C. under reduced pressure to obtain 10.1 g of a graft copolymer in which about 13 ethylene oxides were graft-polymerized with respect to one hydroxyl group.

Table 2 shows the physical properties of the obtained branched olefin copolymer containing a polar group. The antifogging property of the film obtained from the polar group-containing branched olefin copolymer obtained as described above was evaluated as described above. Table 3 shows the results. The polymer was measured by ¹ H-NMR to find (2) / (3) = 100/0.

[0164]

Example 2 400 ml of toluene was charged into a 1000 ml glass polymerization vessel which had been sufficiently purged with nitrogen, and nitrogen was allowed to flow at a rate of 20 liter / hour and kept at 90 ° C. for 10 minutes. To this, 1.08 mmol of triisobutylaluminum was added, and then Undecene-ol (dried over activated alumina and distilled under reduced pressure) 0.90 mmol
1 was added. Further, methylaluminoxane 1.10
0 mmol was added to stop the flow of nitrogen, and ethylene was
It was distributed at a rate of 0 liter / hour. Finally, dimethylsilylene (2,7-dimethyl-4,5 (2-methyl-benzo) -1-
A toluene slurry solution in which 0.008 mmol of indenyl) (2,7-ditert-butylfluorenyl) zirconium dichloride and 2.00 mmol of methylaluminoxane were contacted at room temperature for 10 minutes was added, polymerization was started, and the polymerization was started. After polymerization for 1 hour, a small amount of isobutyl alcohol was added to terminate the polymerization. Furthermore, 100 ml of isobutyl alcohol solution containing 1 ml of concentrated hydrochloric acid aqueous solution
Was added and heated at 75 ° C. under nitrogen. The polymer solution was added to a large excess of methanol to precipitate the polymer,
After drying under reduced pressure for 12 hours, 14.83 g of a polymer that was ethylene / side chain monomer (molar ratio = 99.75 / 0.25) was obtained.

Using 12.0 g of this polymer, Example 1
Was polymerized in the same manner as in Example 1 except that 15.1 g of ethylene oxide was used. 11.8 g of a graft copolymer obtained by graft polymerization of about 65 ethylene oxides per one hydroxyl group was obtained. Table 2 shows the physical properties of the obtained polar group-containing branched olefin copolymer.

The antifogging property of the film obtained from the polar group-containing branched olefin copolymer obtained as described above was evaluated as described above. Table 3 shows the results.

[0167]

Example 3 Example 1 was repeated, except that 5.0 g of propylene oxide was used instead of ethylene oxide.
Thus, 10.3 g of a graft copolymer obtained by graft polymerization of propylene oxide was obtained. Table 2 shows the physical properties of the obtained polar group-containing branched olefin copolymer.

The antifogging property of the film obtained from the polar group-containing branched olefin copolymer obtained as described above was evaluated as described above. Table 3 shows the results. As a result of measuring this polymer by 1 H-NMR,
(2) / (3) = 99/1.

[0169]

Example 4 Using the ethylene / side chain monomer (molar ratio = 99.75 / 0.25) polymer produced in Example 2, polymerization was carried out while intermittently supplying 3.1 g of ethylene oxide. A graft copolymer obtained by graft polymerization of about 13 ethylene oxides with respect to one hydroxyl group is obtained as 1
1.8 g were obtained.

Table 2 shows the physical properties of the obtained polar group-containing olefin copolymer. The antifogging property of the film obtained from the polar group-containing branched olefin copolymer obtained as described above was evaluated as described above. Table 3 shows the results.

[0171]

Fifth Embodiment In the first embodiment, α is further added to the charge.
7.75 g of hydroxypropyl phenyl ketone was added, the pressure was changed from 0.9 to 0.2, and 5.8 g of methyl methacrylate was used instead of ethylene oxide, and tetrahydrofuran was used instead of methanol. Was carried out in the same manner as in Example 1 to obtain 11.3 g of a graft copolymer in which about 20 methyl methacrylates were graft-polymerized with respect to one hydroxyl group.

Table 2 shows the physical properties of the obtained branched olefin copolymer containing a polar group. The mechanical properties of the polar group-containing branched olefin copolymer obtained as described above were evaluated as described above. Table 3 shows the results.

[0173]

Example 6 1-octene 1 was placed in a 2 liter stainless steel (SUS) autoclave, which had been sufficiently purged with nitrogen.
05 g, 895 ml of Mitsui hexane and 1.50 mmol of triisobutylaluminum were added. This SUS
Autoclave was heated to 150 ° C., 1.140 mmol of methylaluminoxane was added, and then undecene-1
-ol (dried on activated alumina and distilled under reduced pressure)
350 mmol were added. While maintaining 150 ° C,
It was pressurized with ethylene so that the total pressure was 30 kg / cm ² -G. On the other hand, 0.002075 mmol of dimethylsilylene (2-methyl-4,5-benzo-1-indenyl) (2,7-ditert-butylfluorenyl) zirconium dichloride was placed in a 20 ml glass flask sufficiently purged with nitrogen. A toluene slurry solution contacted with 0.4300 mmol of methylaluminoxane at room temperature for 10 minutes was pressurized with nitrogen, and 600 Nml of hydrogen was further pressurized. After press fitting, remove autoclave 1
The temperature was maintained at 150 ° C. for 0 minutes, and the pressure was maintained at the pressure immediately after injection by pressurizing ethylene. A small amount of isobutyl alcohol was added to terminate the polymerization. The polymer solution was added to a large excess of methanol to precipitate a polymer, which was dried under reduced pressure at 80 ° C. for 12 hours. As a result, 8.45 g of the polymer was obtained.
was gotten.

Using 8 g of this polymer, polymerization was carried out in the same manner as in Example 1 while intermittently supplying 3.1 g of ethylene oxide. A graft copolymer obtained by graft polymerization of about 13 ethylene oxides with respect to one hydroxyl group is obtained as 1
1.8 g were obtained. Table 2 shows the physical properties of the obtained polar group-containing branched olefin copolymer. The water dispersibility of the polar group-containing branched olefin copolymer obtained as described above was evaluated as described above. Table 3 shows the results.

[0175]

[Table 2]

[0176]

[Table 3]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kazumi Mizutani 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals Co., Ltd. (72) Inventor Seiji Ota 6-1 Waki, Wakimachi, Kuga-gun, Yamaguchi Prefecture -2 Mitsui Chemicals Co., Ltd. (72) Inventor Satoru Moriya 3 Chigusa Kaigan, Ichihara-shi, Chiba Mitsui Chemicals In-house F-term (reference) 4J027 AA01 AA08 AC02 AC03 AC04 BA02 BA03 BA04 CB08 4J100 AA03P AA04P AA05P AA06P AA07P AA08P AA09P AA09P AA15P AA18P AA19P AA21P AB07Q AD01Q AE26Q AL16Q AM14Q AQ01Q AS06Q BA02H BA03Q BA15H BC43Q BC54Q CA04 CA31 HA11 HA61

Claims (6)

[Claims] 1. A composition comprising a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) and, if necessary, a structural unit represented by the following general formula (3): A branched olefin copolymer containing a polar group, characterized by comprising: (Wherein, R ¹ represents a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms or a hydrogen atom, R ² represents a hydrocarbon group, and R ³ represents a hetero atom or a hetero atom. R represents 0 or 1, Z represents a polymer segment obtained by any of anionic polymerization, ring-opening polymerization, and polycondensation; X represents a hydroxyl group or an epoxy group; An integer q is 0, 1 or 2, and p
+ Q ≦ 3, and when p is 2 or 3, —O—Z may be the same or different from each other. In this case, when r is 0, —O—Z is bonded to the same or different atom of R ^2. When r is 1, —O—Z may be bonded to the same or different atom of R ³ , and when q is 2, X is X
May be the same or different from each other. In this case, when r is 0, X may be bonded to the same or different atom of R ² , and when r is 1, X is bonded to the same or different atom of R ³ X and —O—Z may be bonded to the same or different atoms of R ² when r is 0 in the case of p ≧ 1 and q ≧ 1, and when r is 1, X and —O—Z may be bonded to the same or different atoms of R ³ , m represents 0 or 1, and n represents 1 to 3
And when n is 2 or 3, Xs may be the same or different from each other. In this case, when m is 0, X may be bonded to the same or different atom of R ² , and m is In the case of 1, X may be bonded to the same or different atoms of R ³ . ). 2. The polar group-containing branched olefin copolymer according to claim 1, wherein in the general formula (2), r is 0 and Z is a polymer segment obtained by anionic polymerization. 3. A polymer segment obtained by ring-opening polymerization and polycondensation in the general formula (2).
5. The branched olefin copolymer containing a polar group according to the above. 4. The polar group-containing branched olefin copolymer according to claim 1, which has a molecular weight distribution of 3 or less. 5. Tαα in a ¹³ C-NMR spectrum
+ Tαβ to Tαβ intensity ratio (Tαβ / (Tαα +
The polar group-containing branched olefin copolymer according to any one of claims 1 to 4, wherein Tαβ)) is 1.0 or less. 6. A thermoplastic resin composition comprising the polar group-containing branched olefin copolymer according to claim 1. Description: