JP2002145946A - Polar group-containing olefin copolymer and thermoplastic resin composition containing the copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polar group-containing olefin copolymer having excellent adhesiveness to a metal or a polar resin, compatibility with a polar resin, flexibility, etc. SOLUTION: This polar group-containing olefin copolymer comprises constituent units of formulas (1) and (2) (R1 is a 1-18C aliphatic hydrocarbon group; R2 is a hydrocarbon group; R3 is a hetero atom or a hetero atom-containing group; r is 0 or 1; X is a hydroxy group, a carboxylic acid group, a carboxylic acid ester group, an acid anhydride group, an amino group, an amide group, an epoxy group or a mercapto group; p is 1-3; when p is 2 or 3, Xs may be mutually the same or different) and has >=10% degree of crystallization obtained by X-ray diffraction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polar group-containing olefin copolymer and a thermoplastic resin composition containing the copolymer, and more particularly, to an adhesive property with a metal or a polar resin,
The present invention relates to a polar group-containing olefin copolymer excellent in rigidity, heat resistance and the like, and a thermoplastic resin composition containing the copolymer.

[0002]

BACKGROUND OF THE INVENTION Generally, polyolefins are extruded because of their excellent moldability, heat resistance, mechanical properties, hygiene compatibility, water vapor permeability, etc., and good appearance of molded products. Widely used for packaging materials such as molded products and hollow molded products. However, since the polyolefin does not contain a polar group in the molecule, the adhesiveness to a polar resin such as nylon or EVOH, a metal, or the like is low, and there has been a problem that a multilayer molded body cannot be obtained with these materials.

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 the affinity with a polar substance has been widely used. In this case, since the cross-linking between polyolefins and the breaking of molecular chains occur in parallel with the graft reaction, the moldability of the obtained graft polymer may be poor.

Further, Japanese Patent Application Laid-Open Nos. 1-259012, 1-259012, 2-51510, 2-51511 and 3-1774 are disclosed.
No. 03 describes a method of copolymerizing an α-olefin and a polar group-containing monomer using a Ti catalyst or a V catalyst, but when these polymerization catalysts are used, the molecular weight distribution is wide. In some cases, the molecular structure was non-uniform due to a high inversion ratio or a high inversion fraction, and sufficient performance could not be obtained.

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 substance and excellent adhesiveness. The present invention has been completed.

[0006]

An object of the present invention is to provide a polar group-containing olefin copolymer excellent in adhesion, compatibility, rigidity and the like to a metal or a polar resin, and a thermoplastic resin composition containing the copolymer. It is an object.

[0007]

SUMMARY OF THE INVENTION The polar group-containing olefin copolymer according to 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). Characterized in that the determined crystallinity is 10% or more;

[0008]

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(Wherein, R ¹ represents a linear or branched aliphatic hydrocarbon group having 2 to 18 carbon atoms, R ² represents a hydrocarbon group, and R ³ represents a hetero atom or a hetero atom. And r represents 0 or 1, and X is selected from an alcoholic hydroxyl group, a phenolic hydroxyl group, a carboxylic acid group, a carboxylic acid ester group, an acid anhydride group, an amino group, an amide group, an epoxy group and a mercapto group. Represents a polar group, p
Is an integer of 1 to 3, and when p is 2 or 3, Xs 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 When r is 1, X may be bonded to the same or different atoms of R ³ . ).

[0010] The present invention in accordance polar group-containing olefin copolymer preferably has a molecular weight distribution of 3 or less, ¹³ C
For Tαα + Tαβ in the NMR spectrum
The intensity ratio of αβ (Tαβ / (Tαα + Tαβ)) is 1.0
The following is preferred. The thermoplastic resin composition according to the present invention is characterized by containing the above-mentioned olefin copolymer having a polar group.

[0011]

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

[0012]

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In the formula, R ¹ represents ^one group selected from linear or branched alkyl groups having 2 to 18 carbon atoms. Examples of the linear or branched alkyl group having 2 to 18 carbon atoms include 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 2 to 10 carbon atoms, particularly those having 2 to 6 carbon atoms are preferable.

R ² represents a hydrocarbon group such as a saturated or unsaturated aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group. Examples of the saturated or unsaturated aliphatic hydrocarbon group include a linear or branched hydrocarbon group having 1 to 20 carbon atoms, and 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.

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 group having 6 to 20 carbon atoms having a ring is preferable, and specific
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.

The valence of R ² is divalent when r is 1 and R ³ is bonded to R ² , r is 0 and p Xs are R
^When it is bonded to ² , it has a (p + 1) valence. 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 and a sulfur atom, and an oxygen atom and a nitrogen atom are preferable.

The group containing a hetero atom includes a group 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.

Specifically, a structure as shown in the following examples of the polar group-containing monomer can be mentioned. R ³ is a group in which the hetero atom or the carbon atom to which the hetero atom in R ³ is bonded is R 3
Preferably bonded with ^2, Examples of such ^{include, -R 2 -O-R-X} , -R 2 -C (= O) -R-X, -
R ² —C (ＯO) O—R—X, —R ² —OC (＝ O) O—R—
^{X, -R 2 -C (= O} ) NH-R-X, -R 2 -S-R-X
(However, R represents methylene, phenylene, or cyclohexylene).

When R ³ contains a carbon atom, the number of carbon atoms forming R ³ is preferably 1 to 20, more preferably 1
10 to 10, particularly preferably 1 to 5. X represents a polar group selected from alcoholic hydroxyl group, phenolic hydroxyl group, carboxylic acid, carboxylic acid ester, carboxylic acid anhydride group, amino group, amide group, epoxy group and SH group.

When X is an alcoholic hydroxyl group, the polar group-containing olefin copolymer has good paintability, surface hydrophilicity (anti-fogging property), antistatic property, and polar resin (urethane resin, epoxy resin, etc.). Adhesiveness, filler dispersibility, hygroscopicity, gas barrier properties (when high content), water absorption (when high content of alcoholic hydroxyl groups), water dispersibility, oil resistance (when high content of alcoholic hydroxyl groups) Excellent.

When X is a phenolic hydroxyl group, the polar group-containing olefin copolymer has an adhesive property with a polar resin (such as an aromatic polymer or a phenol resin) or a polar resin (such as an aromatic polymer or a phenol resin). Excellent compatibility with. When X is a carboxyl group, the polar group-containing olefin copolymer has adhesiveness to a metal, water dispersibility (particularly when a metal salt is used), pigment dispersibility, filler dispersibility, oil resistance (high carboxyl group). Content).

When X is a carboxylate group, the polar group-containing olefin copolymer is made of a polar resin (nylon,
Adhesion with EVOH, polar resin (nylon, EV
OH, etc.) and excellent surface hydrophilicity. When X is an epoxy group, the polar group-containing olefin copolymer has an adhesive property to a metal, an adhesive property to a polar resin (polyester, epoxy resin, nylon, EVOH, urea resin, etc.), and a polar resin (polyester, epoxy resin). Resin, nylon, EVOH, urea resin, etc.), pigment dispersibility, and coatability.

When X is an acid anhydride group, the polar group-containing olefin copolymer has an adhesive property to a metal, an adhesive property to a polar resin (nylon, EVOH, polyester, etc.), and a polar resin (nylon, EVOH, polyester). ), Pigment dispersibility, filler dispersibility, and water dispersibility (especially when a metal salt is used). When X is an amino group, is the polar group-containing olefin copolymer adhesive to polar resins (epoxy resin, polyketone, polyurethane, etc.), paintability, antibacterial? (In the case of ammonium salt), ion exchangeability (in the case of ammonium salt), hydrophilicity of the surface (especially in the case of ammonium salt), antistatic property (especially in the case of ammonium salt), pigment dispersibility, filler dispersibility ( Especially in the case of ammonium salt).

When X is an amide, the polar group-containing olefin copolymer is excellent in adhesion and compatibility with the polyamide. When X is a mercapto group, the polar group-containing olefin copolymer is excellent in adhesion to a late transition metal such as Fe, Cu, Co, Ni, Cd, and Zn. In addition, it has excellent compatibility and adhesion with polyamide, polyester and the like.

P represents an integer of 1 to 3, and p is 2 or 3
In this case, X may be the same or different. p is 2
Or 3 and when r is 0, X may be bonded to the same or different atom of R ² , and when p is 2 or 3 and r is 1, X is the same or different for R ³ It may be bonded to an atom. In the polar group-containing olefin copolymer according to the present invention, the structural unit (1) and the structural unit (2) are usually randomly bonded. (Composition of Copolymer) The polar group-containing olefin copolymer according to the present invention has a molar ratio ((1) :( 2)) of the structural unit (1) to the structural unit (2) of usually 99.99. : 0.01 ~
0.01: 99.99, preferably 99.95: 0.0
5 to 10:90, more preferably 99.9: 0.1 to
30:70.

The polar group-containing olefin copolymer according to the present invention may contain two or more structural units (2). In the present invention, the structural unit (1) and the structural unit (2)
As a preferred combination of the structural unit selected from the examples of the structural unit (1) shown in Table 1 below, and the structural unit (2)
And a combination with a structural unit selected from the above examples, specifically, 1-A, 1-B, 1-C, 1-D, 1-E,
1-F, 1-G, 1-H, 1-I, 1-J, 1-K, 1
-L, 1-M, 2-A, 2-B, 2-C, 2-D, 2-
E, 2-F, 2-G, 2-H, 2-I, 2-J, 2-
Combinations of K, 2-L and 2-M are mentioned. In the examples of the combination, numerals indicate examples of the structural unit (1), and alphabets indicate examples of the structural unit (2).

[0027]

[Table 1]

(Other Copolymer Components) The polar group-containing olefin copolymer of the present invention contains structural units other than the structural unit (1) and the structural unit (2) as long as the object of the present invention is not impaired. May be included. Here, examples of the structural unit that may be contained include a cyclic olefin excluding a polar group-containing monomer represented by the following general formula (2 ′), a non-conjugated polyene, a hydroxyl group-containing ethylenically unsaturated compound, and an amino group. And a structural unit derived from an ethylenically unsaturated compound containing an epoxy group, an ethylenically unsaturated compound containing an epoxy group, an aromatic vinyl compound, an unsaturated carboxylic acid and its derivative, 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% or less, based on all the structural units constituting the polar group-containing olefin copolymer. More preferably, it is 1.0 mol% or less. In the present invention, it is one of the preferable embodiments that the polar group-containing olefin copolymer does not contain other copolymer components as described above and is formed only from the structural unit (1) and the structural unit (2). In particular, when X is an alcoholic hydroxyl group, a phenolic hydroxyl group or an amino group, it is preferably formed only from the structural units (1) and (2). (Physical Properties of Copolymer) The olefin copolymer having a polar group according to the present invention has a crystallinity determined by X-ray diffraction of usually 10% or more, preferably 15 to 80%, more preferably 20 to 70%. In the range.

The weight-average molecular weight (Mw) of the polar group-containing olefin copolymer according to the present invention is usually 500 to 20.
000, preferably 1,000 to 1.5 million, more preferably 5,000 to 1.3 million, and a molecular weight distribution (Mw / M
n) is usually 3 or less, preferably 2.8 or less, more preferably 2.7 or less. Molecular weight distribution (Mw / Mn)
Is 3 or less, the polar group-containing olefin copolymer,
It is excellent in the orientation of the polar group at the interface with the polar substance, and is excellent in the adhesive property and compatibility with the polar substance.

Here, Mw and Mw / Mn are GPC
(Gel permeation chromatography)
Determined by data obtained at 140 ° C. in orthodichlorobenzene solvent. The polar group-containing olefin copolymer has a Tα in the ¹³ C-NMR spectrum.
The intensity ratio of Tαβ to α + Tαβ (Tαβ / (Tαα
+ Tαβ)) is 1.0 or less, preferably 0.8 or less,
More preferably, it is 0.5 or less.

When the strength ratio (Tαβ / (Tαα + Tαβ)) is 1.0 or less, the polar group-containing olefin copolymer is excellent in the orientation of the polar group at the interface with the polar substance. Here, Tαα and Tαβ in the ¹³ C-NMR spectrum
Is the peak intensity of CH _{2 in} the structural unit derived from an α-olefin having 4 or more carbon atoms, and means two types of CH ₂ having different positions with respect to the tertiary carbon as shown below. .

[0033]

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The Tαβ / (Tαα + Tαβ) intensity ratio can be determined as follows. ¹³ C-NMR spectrum of the polar group-containing olefin copolymer,
For example, it is measured using a JEOL-GX270 NMR measuring device manufactured by JEOL Ltd. The measurement was performed using hexachlorobutadiene / d6-benzene adjusted to a sample concentration of 5% by weight.
Using a mixed solution of 2/1 (volume ratio), 67.8 MH
z, 25 ° C., based on d6-benzene (128 ppm). The measured ¹³ C-NMR spectrum was analyzed by Lindemann Adams (Analysis Chemistry 43, p1245 (197
1)), JCRandall (Review Macromolecular Chemistry
Physics, C29, 201 (1989)).
The (Tαα + Tαβ) intensity ratio is determined.

The stereoregularity (isotacticity) of the polar group-containing olefin copolymer of the present invention is usually 20% or more, preferably 30 to 100%, more preferably 40 to 100%. (Production method) The polar group-containing olefin copolymer of the present invention comprises (A) a transition metal compound selected from Groups 3 to 10 of the periodic table (Group 3 also includes lanthanoids and actinoids); And (B-1) at least one compound selected from the group consisting of (B-1) an organoaluminum oxy compound, (B-2) a compound which reacts with the compound (A) to form an ion pair, and (B-3) an organoaluminum compound. And an α-olefin having 4 to 20 carbon atoms and a polar group-containing monomer copolymer represented by the following general formula (2 ′) in the presence of an olefin polymerization catalyst comprising:

The transition metal compound (A) used in the present invention
Known organic metal complexes 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.

[0037]

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(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, and represent a hydrogen atom, 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). )

[0039]

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(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. )

[0041]

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(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, 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. May be different, 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.). )

[0043]

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(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. )

[0045]

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(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. A hydrogen 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, and adjacent to each other among the groups represented by R ⁴¹ and R ⁴² 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.

[0048]

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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. Hei 1-501950, Tokuhyo Hei 1-5
02036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321
No. 106, etc., ionic compounds, borane compounds and carborane compounds. Further, heteropoly compounds and isopoly compounds can also be mentioned.

Examples of the Lewis acid include a magnesium-containing Lewis acid, an aluminum-containing Lewis acid, and a boron-containing Lewis acid. Of these, 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 comprises a hydrocarbon group having 1 to 12 carbon atoms and / or
Or an aluminum compound substituted with a halogen atom, an alkoxy group, a siloxy group, an amide group, or a hydrogen atom. These organoaluminum compounds may 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).

Examples of α-olefins having 4 to 20 carbon atoms include 1-butene, 2-butene, 1-pentene, 3-methyl
1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1
-Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene,
1-octene, 1-decene, 1-dodecene, 1-tetradecene,
Examples include 1-hexadecene, 1-octadecene, and 1-eicosene. Among these, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene is preferably one kind selected, and 1-butene and 4-methyl-1-pentene are particularly preferable. .

Examples of the polar group-containing monomer include a polar group-containing monomer represented by the following general formula (2 '). CH ₂ ＣＨCH—R ² — (R ³ ) _r — (X) _p (2 ′) (wherein R ² , R ³ , r, X and p each represent R in the above general formula (2) Synonymous with ² , R ³ , r, X and p.) Specific examples of such a polar group-containing monomer include:
4-penten-1-ol, 5-hexen-1-ol, 6-hepten-1-ol, 7-octen-1-ol, 8-nonen-1-ol, 9-decene-1-ol, 10- Undecene-1-ol, 11-
Ω-alkenyl alkols such as dodecene-1-ol;
5-hexen-2-ol, 6-hepten-2-ol, 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-
All, 10-undecene-3-ol, 11-dodecene-3-ol, 7-octen-4-ol, 8-nonen-4-ol, 9-decene-4-ol, 10-undecene-4-ol, Alcohols in which the hydrocarbon moiety is linear, such as 8-nonen-5-ol, 9-decene-5-ol, and 10-undecene-5-ol; 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-undecene-2-ol, 2,2-dimethyl-7-octene-1-
All, 3-ethyl-2-methyl-8-nonen-1-ol, 2,2,3
Alcohols in which the hydrocarbon moiety is branched, such as -trimethyl-9-decene-1-ol and 2,3,3,4-tetramethyl-10-undecene-2-ol; 9-decene-1,2 -Diol, 10-undecene-1,2-diol, 11-dodecene-1,2-diol, 1
Compounds wherein X is an alcoholic hydroxyl group in the above general formula (2 ′), such as diols such as 1-dodecene-1,2-diol and triols such as 10-undecene-1,2,3-triol; Hexenoic acid, 6-heptenoic acid, 7-octenoic acid,
Ω-alkenyl carboxylic acids such as 8-nonenoic acid, 9-decenoic acid, 10-undecenoic acid, 11-dodeceneic acid; 2-methyl-5-hexenoic acid, 2-methyl-6-heptenoic acid, 2-methyl-7 -Octenoic acid, 2-methyl-8-nonenoic acid, 2-methyl-9-decenoic acid, 2-
Methyl-10-undecenoic acid, 2-methyl-11-dodesenic acid, 2-
Ethyl-5-hexenoic acid, 2-ethyl-6-heptenoic acid, 2-ethyl-7-octenoic acid, 2-ethyl-8-nonenoic acid, 2-ethyl-9-
Decenoic acid, 2-ethyl-10-undecenoic acid, 2-propyl-5-
Hexenoic acid, 2-propyl-6-heptenoic acid, 2-propyl-7-
Octenoic acid, 2-propyl-8-nonenoic acid, 2-propyl-9-decenoic acid, 2-propyl-10-undecenoic acid, 2-butyl-5-hexenoic acid, 2-butyl-6-heptenoic acid, 2- Butyl-7-octenoic acid, 2-butyl-8-nonenoic acid, 2-butyl-9-decenoic acid, 2-
Alkenylcarboxylic acids having a linear hydrocarbon moiety such as butyl-10-undecenoic acid; 2-isopropyl-5-hexenoic acid, 2-isopropyl-6-heptenoic acid, and 2-isopropyl-7-
Octenoic acid, 2-isopropyl-8-nonenoic acid, 2-isopropyl-9-decenoic acid, 2-isopropyl-10-undecenoic acid, 2
-Isobutyl-5-hexenoic acid, 2-t-butyl-6-heptenoic acid, 2-isopropyl-3-methyl-7-octenoic acid, 2-methyl
3-isopropyl-8-nonenoic acid, 3-isobutyl-3-methyl-
The above-mentioned general formula (2 ′) such as alkenylcarboxylic acids having a branched hydrocarbon moiety, such as 9-decenoic acid, 2,2-dimethyl-10-undecenoic acid, and 2,3,3-trimethyl-11-dodeceneic acid. )
Wherein X is a carboxylic acid group, methyl 5-hexenoate, methyl 6-heptenoate, methyl 7-octenoate, 8-
Methyl nonenoate, 9-methyldecenoate, 10-methyl undecenoate, 11-methyl dodecenoate, ethyl 5-hexenoate, 6
-Ethyl heptenoate, ethyl 7-octenoate, ethyl 8-nonenoate, ethyl 9-decenoate, ethyl 10-undecenoate, 1
1-ethyl dodecenoate, isopropyl 5-hexenoate, isopropyl 6-heptenoate, isopropyl 7-octenoate, 8-
Isopropyl nonenate, 9-isopropyl decenoate, 10-
Isopropyl undecenoate, isopropyl 11-dodecenoate, butyl 5-hexenoate, butyl 6-heptenoate, butyl 7-octenoate, butyl 8-nonenoate, butyl 9-decenoate,
10-butyl undecenoate, 11-butyl dodecenoate, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-
Ω- such as decenoic acid, 10-undecenoic acid, 11-dodecenoic acid
Alkenyl carboxylic esters; methyl 2-methyl-5-hexenoate, methyl 2-methyl-6-heptenoate, 2-methyl-
7-ethyl octenoate, 2-methyl-8-methyl nonenoate, 2-
Methyl-9-butyl decenoate, 2-methyl-10-ethyl undecenoate, 2-ethyl-5-butyl hexenoate, ethyl 2-ethyl-6-heptenoate, 2-ethyl-7-isopropyl octenoate, 2- Ethyl-8-ethyl nonenoate, methyl 2-ethyl-9-decenoate, ethyl 2-ethyl-10-undecenoate, 2-propyl
Methyl-5-hexenoate, methyl 2-propyl-6-heptenoate, ethyl 2-propyl-7-octenoate, methyl 2-propyl-9-decenoate, ethyl 2-propyl-10-undecenoate, 2-
Alkenyl carboxylic acids whose hydrocarbon moiety is linear, such as methyl butyl-7-octenoate, methyl 2-butyl-8-nonenoate, methyl 2-butyl-9-decenoate, and methyl 2-butyl-10-undecenoate Esters: 2-isopropyl-5-butyl hexenoate, ethyl 2-isopropyl-6-heptenoate, methyl 2-isopropyl-7-octenoate, methyl 2-isopropyl-8-nonenoate, 2-isopropyl-9-decene Butylate, 2-isopropyl-10-methyl undecenoate, 2-isobutyl-5-
Methyl hexenoate, methyl 2-t-butyl-6-heptenoate, 2
In the above general formula (2 ′) such as alkenylcarboxylic acids having a branched hydrocarbon moiety such as ethyl 3-isopropyl-3-methyl-7-octenoate and propyl 3-isobutyl-3-methyl-9-decenoate In the examples of the compound in which X is a carboxylic acid ester, (2,7-octadienyl) succinic anhydride, pentapropenylsuccinic anhydride and the compound in which X is a carboxylic acid group, the carboxylic acid group is replaced with a carboxylic acid anhydride group. The above general formula (2 ′) such as a substituted compound
Wherein X is an acid anhydride group, ω-alkenylamines such as 5-hexenamine, 6-heptenamine, 7-octenamine, 8-nonenamine, 9-deceneamine, 10-undeceneamine and 11-dodeceneamine; 2 -Methyl-5-
Hexenamine, 2-methyl-6-heptenamine, 2-methyl-7-octenamine, 2-methyl-8-nonenamine, 2-methyl-9-deceneamine, 2-methyl-10-undeceneamine, 2-methyl- 11-dodeceneamine, 2-ethyl-5-hexenamine, 2-ethyl-6-heptenamine, 2-ethyl-7-octenamine, 2-ethyl-8-nonenamine, 2-ethyl-9-
Deceneamine, 2-ethyl-10-undeceneamine, 2-propyl-5-hexenamine, 2-propyl-6-heptenamine, 2-propyl-5-hexenamine, 2-propyl-6-heptenamine, 2-propyl- 7-octenamine, 2-propyl-8-nonenamine, 2-propyl-9-deceneamine, 2-propyl-10-undeceneamine, 2-butyl-5-hexenamine, 2-butyl-6-heptenamine, 2- Alkenylamines in which the hydrocarbon moiety is linear, such as butyl-7-octenamine, 2-butyl-8-nonenamine, 2-butyl-9-deceneamine, and 2-butyl-10-undeceneamine; 2-isopropyl
-5-hexenamine, 2-isopropyl-6-heptenamine, 2-isopropyl-7-octenamine, 2-isopropyl-8-nonenamine, 2-isopropyl-9-deceneamine,
2-isopropyl-10-undeceneamine, 2-isobutyl-5
-Hexenamine, 2-t-butyl-6-heptenamine, 2-isopropyl-3-methyl-7-octenamine, 2-methyl-3-
Isopropyl-8-nonenamine, 3-isobutyl-3-methyl
Alkenylamines in which the hydrocarbon moiety is branched, such as -9-deceneamine, 2,2-dimethyl-10-undeceneamine, and 2,3,3-trimethyl-11-dodeceneamine; N-methyl-5
-Hexenamine, N-methyl-6-heptenamine, N-methyl-7-octenamine, N-methyl-8-nonenamine, N-methyl-9-deceneamine, N-methyl-10-undeceneamine, N-methyl -11-dodeceneamine, N-ethyl-5-hexenamine, N-ethyl-6-heptenamine, N-ethyl-7-octenamine, N-ethyl-8-nonenamine, N-ethyl-9-
N-alkyl-ω-alkenylamines such as deceneamine, N-ethyl-10-undeceneamine, N-ethyl-11-dodeceneamine; N-methyl-6-hepten-2-amine, N-ethyl-7
-Octen-2-amine, N-methyl-8-nonen-2-amine, N-
Ethyl-9-decene-2-amine, N-methyl-10-undecene-2
-Amine, N-ethyl-8-nonen-3-amine, N-methyl-9-decene-3-amine, N-ethyl-10-undecene-3-amine, N-
N-alkylalkenylamines in which the hydrocarbon moiety is linear, such as ethyl-8-nonen-4-amine, N-methyl-9-decene-4-amine, N-ethyl-10-undecene-4-amine; N-methyl-2-methyl-5-hexenamine, N-ethyl-2-methyl-6-
Heptenamine, N-methyl-2-methyl-7-octenamine, N-ethyl-2-methyl-8-nonenamine, N-ethyl-2-
Methyl-9-deceneamine, N-methyl-2-methyl-10-undeceneamine, N-methyl-2-ethyl-7-octenamine, N-
Ethyl-2-ethyl-9-decenamine, N-methyl-2-ethyl-
N-alkylalkenylamines in which the hydrocarbon moiety is branched, such as 10-undeceneamine; N, N-dimethyl-5-hexenamine, N, N-dimethyl-6-heptenamine, N, N-
Dimethyl-7-octenamine, N, N-dimethyl-8-nonenamine, N, N-dimethyl-9-decenamine, N, N-dimethyl-10
-Undecenamine, N, N-dimethyl-11-dodeceneamine, N, N-diethyl-5-hexenamine, N, N-diethyl-6-
Heptenamine, N, N-diethyl-7-octenamine, N, N
N, N-dialkyl-ω-alkenylamines such as -diethyl-8-nonenamine, N, N-diethyl-9-deceneamine, N, N-diethyl-10-undeceneamine, N, N-diethyl-11-dodeceneamine , N, N-dimethyl-6-hepten-2-amine, N,
N-diethyl-7-octen-2-amine, N, N-dimethyl-8-nonen-2-amine, N, N-diethyl-9-decene-2-amine, N, N
-Dimethyl-10-undecene-2-amine, N, N-diethyl-8-
Nonen-3-amine, N, N-dimethyl-9-decene-3-amine,
N, N-diethyl-10-undecene-3-amine, N, N-diethyl-
Hydrocarbon moiety such as 8-nonene-4-amine, N, N-dimethyl-9-decene-4-amine, N, N-diethyl-10-undecene-4-amine is linear N, N-dialkyl Alkenylamines; N, N-dimethyl-2-methyl-5-hexenamine, N, N-diethyl-2-methyl-6-heptenamine, N, N-dimethyl-2-
Methyl-7-octenamine, N, N-diethyl-2-methyl-8-
Nonenamine, N, N-diethyl-2-methyl-9-deceneamine, N, N-dimethyl-2-methyl-10-undeceneamine, N, N
-Dimethyl-2-ethyl-7-octenamine, N, N-diethyl
2-ethyl-9-decenamine, N, N-dimethyl-2-ethyl-10
-Hydrocarbon moieties such as undeceneamine are branched
Compounds in which X is an amino group in the above general formula (2 ′), such as N, N-dialkylalkenylamines, 5-hexenamide, 6-heptenamide, 7-octenamide, 8-nonenamide, 9-deceneamide, 10- Undecenamide, 1
Ω-alkenylamides such as 1-dodeceneamide; 6-heptene-2-amide, 7-octen-2-amide, 8-nonene-2-
Amide, 9-decene-2-amide, 10-undecene-2-amide, 8-nonene-3-amide, 9-decene-3-amide, 10-undecene-3-amide, 11-dodecene-3-amide, 8-nonene-4-
Hydrocarbon moiety such as amide, 9-decene-4-amide, 10-undecene-4-amide, 11-dodecene-4-amide, 9-decene-5-amide, 10-undecene-5-amide is linear Alkenyl amides; N-methyl-5-hexenamide, N-methyl-6-heptenamide, N-methyl-7-octenamide, N-
Methyl-8-nonenamide, N-methyl-9-decenamide, N-
Methyl-10-undecenamide, N-methyl-11-dodesenamide, N-ethyl-5-hexenamide, N-ethyl-6-heptenamide, N-ethyl-7-octenamide, N-ethyl-8-nonenamide, N-ethyl-9-decenamide, N-ethyl-10-
Undeceneamide, N-ethyl-11-dodeceneamide, etc.
N-alkyl-ω-alkenylamides; N, N-dimethyl-5-
Hexenamide, N, N-dimethyl-6-heptenamide, N, N
-Dimethyl-7-octenamide, N, N-dimethyl-8-nonenamide, N, N-dimethyl-9-decenamide, N, N-dimethyl-
10-undecenamide, N, N-dimethyl-11-dodesenamide, N, N-diethyl-5-hexenamide, N, N-diethyl-6-
Heptenamide, N, N-diethyl-7-octenamide, N, N
N, N-dialkyl-ω-alkenylamides such as -diethyl-8-nonenamide, N, N-diethyl-9-deceneamide, N, N-diethyl-10-undeceneamide, N, N-diethyl-11-dodesenamide And 2-methyl-5-hexenamide, 2-methyl-
6-heptenamide, 2-methyl-7-octenamide, 2-methyl-8-nonenamide, 2-methyl-9-decenamide, 2-methyl-10-undecenamide, 2-ethyl-5-hexenamide, 2- Ethyl-6-heptenamide, 2-ethyl-7-octenamide, 2-ethyl-8-nonenamide, 2-ethyl-9-decenamide, 2-ethyl-10-undecenamide, 2-ethyl-11-
Dodecenamide, 2-propyl-5-hexenamide, 2-propyl-6-heptenamide, 2-propyl-7-octenamide, 2-propyl-8-nonenamide, 2-propyl-9-deceneamide, 2-propyl-10- Undecenamide, 2-propyl
-11-dodesenamide, 2-butyl-5-hexenamide, 2-
Hydrocarbon moieties such as butyl-6-heptenamide, 2-butyl-7-octenamide, 2-butyl-8-nonenamide, 2-butyl-9-decenamide, and 2-butyl-10-undeceneamide are branched. Certain alkenyl amides; N, N-dimethyl-2-
Methyl-5-hexenamide, N, N-diethyl-2-methyl-6-
Heptenamide, N, N-dimethyl-2-methyl-7-octenamide, N, N-diethyl-2-methyl-8-nonenamide, N, N-diethyl-2-methyl-9-decenamide, N, N-diethyl -2-methyl-10-undecenamide, N, N-dimethyl-2-ethyl-7-
N, N-dialkylalkenylamides in which the hydrocarbon moiety is branched, such as octenamide, N, N-diethyl-2-ethyl-9-deceneamide, N, N-dimethyl-2-ethyl-10-undecenamide And 6-heptene-1,2-diamide, 7-octene-1,
Alkenyl diamides such as 2-diamide, 8-nonene-1,2-diamide, 9-decene-1,3-diamide, 10-undecene-1,3-diamide, 11-dodeceneamide, 9-decene-1,2 In the above general formula (2 ′), such as alkenyltriamide such as 1,3-triamide and 10-undecene-1,2,3-triamide, X
Is an amide group, ω-alkenyl epoxide such as 5-hexene epoxide, 6-heptene epoxide, 7-octene epoxide, 8-nonene epoxide, 9-decene epoxide, 10-undecene epoxide and 11-dodecene epoxide And 2-methyl-5-hexene epoxide, 2-methyl-
Hydrocarbon moieties such as 6-heptene epoxide, 2-methyl-7-octene epoxide, 2-methyl-8-nonene epoxide, 2-methyl-9-decene epoxide and 2-methyl-10-undecene epoxide are branched compound X is an epoxy group in the above general formula such as are Jo ω- alkenyl epoxides _{(2 '), CH 2 =} CH-CH 2 -CH 2 -CH 2 -CH 2 -O
And compounds in which X is a mercapto group in the above general formula (2 ′) such as —Ph—SH.

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

[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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And the like. In addition to the above,
n-nonyl-1-ol, n-nonyl-1-carboxylic acid, n-nonyl
1-carboethoxy, 1,2-epoxy-nonyl, (6-hexen-1-yl) succinic anhydride, n-undecyl-1-ol, n-
Dodecyl-1-carboxylic acid, n-dodecyl-1-carbethoxy, 4-hexenyloxyphenol, 4-hexenyloxy-
Thiophenol, n-nonyl-1-carboxamide, n-nonyl-1-amino, n-nonyl-1-N-methylamino and the like.

The polar group-containing olefin copolymer according to the present invention comprises one kind of α-olefin selected from the above α-olefins in the presence of the above-mentioned olefin polymerization catalyst,
It can be produced by polymerizing at least one monomer selected from the above polar group-containing monomers under the following polymerization conditions. In the polymerization, the transition metal compound (A) is generally used in an amount of about 0.00005 to 0.1 mmol, preferably about 0.0001 to 0. Used in an amount of 05 mmol.

The organoaluminum oxy compound (B-1) is
The aluminum atom is usually used in an amount of about 1 to 10,000 mol, preferably 10 to 50,000 mol, per 1 mol of the transition metal atom.
It is used in an amount such that it becomes 00 mol. The ionized ionic compound (B-2) has a boron atom of usually about 0.5 to 500 mol, preferably 1 to 1 mol of the transition metal atom.
It is used in such an amount that it becomes １００100 mol.

The organoaluminum compound (B-3) is composed of one aluminum atom in the organoaluminum oxy compound (B-1).
It is used, if necessary, usually in an amount of about 0 to 200 mol, preferably about 0 to 100 mol, per mol. In addition, boron 1 in the ionized ionic compound (B-2)
It is generally used in an amount of 0 to 1000 mol, preferably about 0 to 500 mol, per mol.

When hydrogen is used, 10 ^-5 to 1 mol, preferably 10 ^-4 , per 1 mol of the monomer to be polymerized is used.
It is used in such an amount that it becomes 10 ^-1 mol. The copolymerization of the olefin with 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. In addition, 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. 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 olefin copolymer, and the above-mentioned polar group-containing olefin copolymer And a thermoplastic resin other than the polar group-containing 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 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.

The polymethacrylate is preferably polymethyl methacrylate (PMMA). 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.

As the polyphenylene oxide, poly (2,6-dimethyl-1,4-phenylene oxide) is preferable. 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) acrylate, 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 elastomeric 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 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:
Polar group-containing olefin copolymer and thermoplastic resin, for example, co-kneader, Banbury mixer, Brabender,
Melting using a kneading machine such as a single-screw extruder, a twin-screw extruder, a twin-screw surface renewal machine, or a vertical-mixing device such as a double-helical ribbon stirrer or a horizontal stirrer such as a double-screw multi-disc stirrer. It can also be produced by kneading.

Ingredients The polar group-containing olefin copolymer 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 colorant, Lubricants, flame retardants, blooming inhibitors and the like may be included in a range that does not impair the purpose of the present invention.

(Inorganic fillers) As inorganic fillers, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, Calcium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flake, glass beads,
Calcium silicate, montmorillonite, bentonite,
Examples include graphite, aluminum powder, and molybdenum sulfide.

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

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

The dispersion medium for swelling or cleaving the inorganic layered compound is, for example, in the case of a natural 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 formula (A).

[0086]

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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
Represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R ¹² and R ¹³ may be heterologous be homologous, R ¹² to each other, and the R ¹³ s or R ¹² and R ¹³ It may be linked to form a ring, M represents a metal atom having 1 to 3 valences, and n is an integer of 1 to 3. Specific examples of the compound represented by the formula (A) include sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate and 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 phosphate salt, there can be mentioned a compound represented by the following formula (B).

[0089]

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(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 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, sodium-bis (4-t-octylphenyl) phosphate Phosphate, potassium-bis (4-t-butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium-bis (4-t-butyl)
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.

The benzylidene sorbitol includes a compound represented by the following formula (C).

[0092]

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(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 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-benzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidenesorbitol, 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
-Chlorbenzylidene-2,4-benzylidene sorbitol,
1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidenesorbitol, 1,3-p-methylbenzylidene-2,4 -P-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof In particular, 1,3,2,4-dibenzylidenesorbitol, 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,
Preferred are 1,3,2,4-di (p-chlorobenzylidene) sorbitol and mixtures of two or more thereof.

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

[0095]

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(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 hydroxydiparat-t- represented by the following formula (E) is used. Butyl benzoate and the like can be mentioned.

[0097]

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The rosin-based crystal nucleating agent includes, for example, a metal salt of rosin acid. 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 having a metal element such as sodium, potassium and magnesium and forming a salt with the rosin acid. Specific examples include chlorides, nitrates, acetates, sulfates, carbonates, oxides, hydroxides, and the like of the above 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 salt of an aromatic carboxylic acid or an aliphatic carboxylic acid include aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, and sodium pyrrolecarboxylate.

(Molding Method) The polar group-containing olefin copolymer and the thermoplastic resin composition according to the present invention can be produced by calender molding, extrusion molding, injection molding, blow molding, press molding, stamping molding and the like. . It can be formed into a sheet or film (unstretched) by extrusion.

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. . Further, an inflation film can be produced from the polar group-containing olefin copolymer and the thermoplastic resin composition according to the present invention.
Filaments can be produced, for example, by extruding a molten composition through a spinneret. Also,
It may be prepared by a melt blown method.

An injection molded article can be produced by injection molding a composition into various shapes using a conventionally known injection molding apparatus under known conditions. The polar group-containing olefin copolymer according to the present invention, the injection molded article comprising the thermoplastic resin composition is hardly charged, rigidity, heat resistance, impact resistance,
It is excellent in surface gloss, chemical resistance, abrasion resistance, etc., and can be widely used in trim materials for automobile interiors, exterior materials for automobiles, housings and containers for home appliances, and the like.

The blow-molded article can be produced using a conventionally known blow-molding apparatus under known conditions. In the injection blow-molding, the polar group-containing olefin copolymer according to the present invention, Resin temperature 1
Injection into a parison mold at 00 ° C. to 300 ° C. to form a parison, followed by holding the parison in a mold having a desired shape, followed by blowing air, and mounting the parison on the mold to produce a hollow molded body. it can.

As the press molded body, a mold stamping molded body can be mentioned. (Uses) The polar group-containing 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) Film and Sheet Films and sheets comprising the polar group-containing olefin copolymer or the thermoplastic resin composition according to the present invention may be any of flexibility, transparency, tackiness, anti-fogging property, heat resistance and separability. Crab is excellent. (2) Laminate As the laminate including at least one layer comprising the polar group-containing olefin copolymer or the thermoplastic resin composition according to the present invention, for example, an agricultural film, a wrap film,
Examples of the separation film include a film for shrink, a film for protection, a plasma component separation membrane, a water selective permeation vaporization membrane, and the like, and a selective separation membrane such as an ion exchange membrane, a battery separator, and an optical splitting membrane. (3) The polar group-containing olefin copolymer and the thermoplastic resin composition according to the present invention can be used for microcapsules, PTP packaging, chemical valves, and drug delivery systems. (4) Modifier When the polar group-containing olefin copolymer or the thermoplastic resin composition according to the present invention is used as a resin modifier, impact resistance, fluidity, paintability, crystallinity, adhesion, and transparency are improved. There is an effect of improving properties and the like.

When the polar group-containing olefin copolymer or the thermoplastic resin composition according to the present invention is used as a rubber modifier, there are effects of modifying weather resistance, heat resistance, adhesiveness, oil resistance and the like. Rubbers include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), styrene / butadiene rubber (SBR), chloroprene rubber (CR),
Acrylonitrile / butadiene rubber (NBR), butyl rubber (IIR), ethylene / propylene rubber (EP
M, EPDM), chlorosulfonated polyethylene (CS
M), crosslinked rubbers such as acrylic rubbers (ACM, ANM, etc.), epichlorohydrin rubbers (CO, ECO, etc.), silicone rubbers (Q), fluorine rubbers (FKM, etc.); styrene, olefin, urethane And ester-type, amide-type and vinyl chloride-type thermoplastic rubbers.

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 olefin copolymer or the thermoplastic resin composition according to the present invention is used as a wax modifier, there are effects of improving adhesiveness, fluidity, strength and the like. As 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,
Plant wax, animal wax and the like.

When used as a modifier for cement, there is an effect of modifying moldability, strength and the like. As cement, lime, plaster, air-hardened cement such as magnesia cement,
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 olefin copolymer and the thermoplastic resin composition according to the present invention include letterpress printing ink, lithographic printing ink,
Inks such as flexo inks and gravure inks, oil-based paints, cellulose derivative paints, synthetic resin paints, aqueous baked-in paints, powdered water-based paints, and viscosity modifiers for inks and paints such as lacquer,
It can be used as a moldability improver. (6) Building materials and civil engineering materials The polar group-containing 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, decorative sheets. , Baseboard, asphalt modifying material, gasket sealing material,
It can be used for building materials and civil engineering resins such as roofing sheets and waterproof sheets, as well as moldings for building materials and civil engineering. (7) Vehicle interior / exterior material and gasoline tank The vehicle interior / exterior material and the gasoline tank comprising the polar group-containing olefin copolymer or the thermoplastic resin composition according to the present invention, the thermoplastic resin composition have rigidity, impact resistance, Oil resistance,
Excellent heat resistance. (8) Electric and electronic parts, etc. The polar group-containing olefin copolymer and the thermoplastic resin composition according to the present invention include an electric insulating material; an electronic component processing equipment; a magnetic recording medium, a binder for a magnetic recording medium, and an electric circuit. Encapsulation materials, home appliance materials, container materials 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, FDD carriages, FDD chassis, HDD parts, motor brushes Electrical and electronic parts such as holders, parabolic antennas, and computer-related parts; VTR parts, TV parts, irons, hair dryers, rice cooker parts,
Home and office electrical products such as microwave oven parts, audio parts, audio equipment parts such as audio / laser disk (registered trademark) and compact discs, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. , Office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, electromagnetic shielding materials, speaker cone materials, speaker vibration elements, and the like. (9) Aqueous emulsion The aqueous emulsion containing the polar group-containing 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 polar group-containing olefin copolymer or the thermoplastic resin composition according to the present invention has excellent dispersion stability in a solvent, and is excellent in bonding a metal or a polar resin to a polyolefin. Shows adhesion. (11) Medical / Hygiene Materials The polar group-containing 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, a prefill syringe, Medical supplies such as syringes, medical materials,
It can be used for artificial organs, artificial muscles, filtration membranes, food hygiene / health products; retort bags, freshness retaining films and the like. (12) Miscellaneous Goods The polar group-containing olefin copolymer and the thermoplastic resin composition according to the present invention include desk mats, cutting mats, rulers, pen barrels, grips and caps, grips such as scissors and cutters, and magnet sheets. , Pen case, paper folder, binder, label seal,
Stationery such as tapes and whiteboards: clothing, curtains, sheets, carpets, entrance mats, bath mats, buckets, hoses, bags, planters, filters for air conditioners and exhaust fans, dishes, trays, cups, lunch boxes, funnels for coffee siphons, Daily necessities such as glasses frames, containers, storage cases, hangers, ropes, laundry nets: shoes, goggles, skis, rackets, balls, tents, underwater glasses, fins, fishing rods, cooler boxes, leisure seats, sports Sports goods such as nets for toys: toys such as blocks, cards, etc .: containers such as kerosene cans, drums, bottles such as detergents and shampoos; signs, pylons, plastic chains, etc .; (13) Filler modifier The polar group-containing olefin copolymer and the thermoplastic resin composition according to the present invention can be used in applications such as filler dispersibility improvers and additives for preparing fillers having improved dispersibility. It can be suitably used. (14) Compatibilizer The polar group-containing olefin copolymer and the thermoplastic resin composition according to the present invention can be used as a compatibilizer. When the polar group-containing 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. Since the polar group-containing olefin copolymer according to the present invention has a polyolefin main chain and a side chain having a polar group, components which were originally incompatible with each other can be mixed, and the polar group-containing olefin copolymer can be mixed. The elongation at break can be remarkably improved as compared with the case where the olefin copolymer is not used.

[0109]

The polar group-containing olefin copolymer according to the present invention has excellent adhesiveness, compatibility and rigidity with polar substances such as metals and polar resins.

[0110]

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. [Coating property] Crosscut test According to the crosscut test method described in JIS K 5400, a crosscut test piece was prepared, and cellotape (trade name, manufactured by Nichiban Co., Ltd.) was used as the test piece. After sticking, it was quickly pulled in a direction of 90 ° to be peeled off, and the number of grids where the coating film remained was counted and used as an index of adhesion.

[Adhesiveness] Production of Film A 0.1 mm-thick aluminum sheet, a polyimide sheet and a 100 μm-thick aluminum sheet whose center was cut into a square of 20 cm × 20 cm were spread on a press plate in this order.
A 4.0 g sample (a polar group-containing olefin copolymer) was placed in the center (the cut-out portion). Next, a polyimide sheet, an aluminum sheet, and a press plate were further stacked in this order.

The sample sandwiched between the above press plates was placed in a hot press at 190 ° C., and after preheating for about 5 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 5 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 20 ° C., and pressurized and cooled at 100 kg / cm ² -G for 5 minutes. I took it out. A portion having a uniform thickness of about 150 to 170 μm of the obtained film (polar group-containing olefin copolymer film) was used for measuring the adhesive strength.

Measurement of Adhesion Strength to Al A polar group-containing olefin copolymer film was placed at 20 cm × 2
An aluminum sheet and a polar group-containing olefin copolymer film were bonded together under the same press conditions as in the above “Preparation of Film” by sandwiching two 0 cm square aluminum sheets (thickness: 50 μm). The obtained laminate was
It was cut into strips having a width of mm, and the adhesive interface between the aluminum sheet and the polar group-containing olefin copolymer film was peeled in the direction of 180 ° at a measurement temperature of 23 ° C. and 80 ° C., and the peel strength was measured.

Measurement of Adhesion Strength to PET A modified polyethylene film was formed into a 20 cm × 20 cm square homopolyethylene terephthalate (PET) film (thickness: 10 mm).
0 μm) The PET film and the modified polymer film were sandwiched between two sheets under the same press conditions as in “Preparation of Film” except that the press temperature was 280 ° C. and the set temperature of the cooling press was −8 ° C. Stuck together. The obtained laminate is
A strip having a width of 5 mm was cut, the adhesive interface between the PET film and the modified polymer film was peeled in the direction of 180 ° at a measurement temperature of 23 ° C. and 80 ° C., and the peel strength was measured.

[0115]

Example 1 400 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 0 ° C. for 10 minutes. To this, 0.6 mmol of triisobutylaluminum was added, and then undece represented by the following formula:
0.48 mmol of ne-1-ol was added.

[0116]

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Further, methylaluminoxane 1.100
11. Addition of mmol and stopping the flow of nitrogen.
It was distributed at a rate of 5 liters / hour. Finally, a toluene slurry solution in which 0.0020 mmol of dimethylsilylene (2-methyl-4-phenanthryl-1-indenyl) zirconium dichloride and 0.500 mmol of methylaluminoxane were contacted at room temperature for 10 minutes was added, and polymerization was started. After polymerization at 0 ° C. for 60 minutes under normal pressure, a small amount of isobutyl alcohol was added to terminate the polymerization. Further, an isobutyl alcohol solution containing 1 ml of a concentrated aqueous hydrochloric acid solution 10
0 ml was added and heated at 75 ° C. under nitrogen. The obtained polymer solution was added to a large excess of methanol to precipitate a polymer, and dried under reduced pressure at 80 ° C. for 12 hours to obtain 0.25 g of a polymer.

Table 2 shows the physical properties of the obtained polar group-containing olefin copolymer. Further, the coatability of the polar group-containing olefin copolymer obtained as described above was evaluated as described above. Table 3 shows the results.

[0119]

Example 2 1-butene and a polar group-containing monomer were obtained in the same manner as in Example 1 except that 1,2-epoxy-9-decene represented by the following formula was used in place of undecene-1-ol. Was polymerized.

[0120]

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Table 2 shows the physical properties of the obtained polar group-containing olefin copolymer. In addition, the polar group-containing olefin copolymer obtained as described above has an adhesive property (vs. PET).
Was evaluated as described above. Table 3 shows the results.

[0122]

Example 3 In place of undecene-1-ol, 1.35 mmol of undecylenic acid represented by the following formula and 1.5 mmol of triisobutylaluminum were used. -Butene was polymerized with a polar group-containing monomer.

[0123]

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Table 2 shows the physical properties of the obtained polar group-containing olefin copolymer. The polar group-containing olefin copolymer obtained as described above was evaluated for the adhesiveness (vs. Al) as described above. Table 3 shows the results.

[0125]

Example 4 1-butene was prepared in the same manner as in Example 1 except that (2,7-octadien-1-yl) succinic anhydride represented by the following formula was used in place of undecene-1-ol. A polar group-containing monomer was polymerized.

[0126]

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Table 2 shows the physical properties of the obtained polar group-containing olefin copolymer. The polar group-containing olefin copolymer obtained as described above was evaluated for the adhesiveness (vs. Al) as described above. Table 3 shows the results.

[0128]

[Table 2]

[0129]

[Table 3]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/18 C08L 23/18 101/00 101/00 101/06 101/06 (72) Inventor Jun Atsushi Imuta 580-32 Nagaura, Sodegaura-shi, Chiba F-term in Mitsui Chemicals, Inc. (reference) 4J002 AA012 BB171 BE011 BE041 BG011 BQ001 4J100 AA15P AD04Q AE26Q AJ01Q AQ01Q BA03Q BC43Q BC54Q BC55Q CA04 DA01 DA04 FA09 FA10

Claims (4)

[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):
A polar group-containing olefin copolymer having a degree of crystallinity determined by line diffraction of 10% or more; (Wherein, R ¹ represents a linear or branched aliphatic hydrocarbon group having 2 to 18 carbon atoms, R ² represents a hydrocarbon group, and R ³ represents a hetero atom or a group containing a hetero atom. And r represents 0 or 1, X represents an alcoholic hydroxyl group,
A polar group selected from a phenolic hydroxyl group, a carboxylic acid group, a carboxylic ester group, an acid anhydride group, an amino group, an amide group, an epoxy group and a mercapto group;
And when p is 2 or 3, 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 r is In the case of 1, X may be bonded to the same or different atoms of R ³ . ). 2. The polar group-containing olefin copolymer according to claim 1, which has a molecular weight distribution of 3 or less. 3. Tαα in ¹³ C-NMR spectrum
+ Tαβ to Tαβ intensity ratio (Tαβ / (Tαα +
3. The polar group-containing olefin copolymer according to claim 1, wherein Tαβ)) is 1.0 or less. 4. A thermoplastic resin composition comprising the polar group-containing olefin copolymer according to any one of claims 1 to 3.