JPH11286578A - Thermoplastic elastomer composition powder, powder molding using the same and molded form - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject powder with excellent flowability, capable of producing a molded form of complicated shape with substantial no chipping and resistance to whitening even if bent, by compounding specific fine powder in the ground product of an elastomer composition comprising a polyolefin-based resin and a rubbery polymer. SOLUTION: This thermoplastic elastomer composition powder is obtained by compounding 100 pts.wt. of the ground product of a thermoplastic elastomer composition having a complex dynamic viscosity (η*) of 1.5×10<5> p at 250 deg.C and a Newtonian viscosity index (n) of <=0.67 comprising (A) 100 pts.wt. of a polyolefin-based resin (pref. a propylene-ethylene copolymer resin) and (B) 10-250 pts.wt. of a rubbery polymer (e.g. conjugated diene-based one) with (C) 0.1-5 pts.wt. of fine powder with a primary particle size of <=300 nm, wherein the component B is such that, in the tan δ-temperature dependency curve afforded by the solid viscoelasticity measurement of a composition produced by kneading with the component A, a new single tan δ peak is presented at a temperature (-70 to 30 deg.C) differing from the respective tan δ peak temperatures for the components A and B.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic elastomer composition powder, a powder molding method using the powder, and a molded product obtained by powder molding the same. More specifically, the present invention provides a pulverized thermoplastic elastomer composition containing a polyolefin resin and a rubbery polymer as essential components, wherein a specific amount of a specific fine powder is mixed with a specific amount, Thermoplastic elastomer composition powder capable of producing a molded article having a complicated shape with almost no occurrence of pinholes or underfilling and giving a molded article which is hardly whitened even when bent, using the powder The present invention relates to a powder molding method and a molded article obtained using the powder.

[0002]

2. Description of the Related Art Conventionally, a sheet-like molded article having a complex uneven pattern such as a grain or a stitch on the surface has been used as a skin material for an automobile interior part or the like. As such a molded product, a molded product obtained by powder-forming a powder obtained by pulverizing an olefin-based thermoplastic elastomer has been proposed as an alternative to a conventional molded product of a vinyl chloride resin (see, for example, Japanese Patent Application Laid-Open No. H05-205,052). -1183 and JP-A-5-5050). However, the powder obtained by pulverizing such a thermoplastic elastomer has insufficient powder flow properties, so that when producing a molded article having a complicated shape, for example, a molded article having a narrow and high convex portion, the convex portion may be missing. There was a problem that meat and pinholes were generated.

[0003] Furthermore, a molded product obtained by powder molding a powder obtained by pulverizing such a thermoplastic elastomer may be whitened when it is bent. Also, when the molded body is taken out of the mold or when the molded body is preformed before bonding the molded body to the substrate, there is also a problem that the bent portion of the molded body is easily whitened. Was.

[0004]

Under these circumstances, an object of the present invention is to provide a pulverized thermoplastic elastomer composition containing a polyolefin resin and a rubbery polymer as essential components. Fine powder is blended in a specific amount, has excellent powder flow characteristics, can produce a molded article with a complicated shape with almost no pinholes or underfill, and hardly whitens even when bent The object of the present invention is to provide a thermoplastic elastomer composition powder capable of providing a molded article, a powder molding method using the powder, and a molded article obtained by using the powder.

[0005]

That is, the first invention of the present invention comprises the following (a) 100 parts by weight and (b) 10 parts by weight.
Of a thermoplastic elastomer composition having a complex dynamic viscosity η ^* (1) at 250 ° C. of 1.5 × 10 ⁵ poise or less and a Newton viscosity index n of 0.67 or less. The present invention relates to a thermoplastic elastomer composition powder obtained by mixing 0.1 to 5 parts by weight of the following (C) with respect to 100 parts by weight of the pulverized material. (A): polyolefin resin (b): a rubbery polymer, tan δ− obtained by solid viscoelasticity measurement of a composition obtained by kneading with (a).
In the temperature dependence curve, a new single tan δ is set at a temperature different from both the tan δ peak temperature in (a) and the tan δ peak temperature in (b) in the temperature range of −70 to 30 ° C.
Rubbery polymer giving peak (c): Fine powder having primary particle size of 300 nm or less

A second aspect of the present invention relates to a powder molding method using the thermoplastic elastomer composition powder of the first aspect.

[0007] A third aspect of the present invention relates to a molded article obtained by powder molding the thermoplastic elastomer composition powder of the first aspect.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) of the present invention is a polyolefin resin, and is at least one selected from one or more olefin polymers or copolymers having high crystallinity. Examples of the olefin include olefins having 2 to 8 carbon atoms, such as ethylene, propylene, 1-butene, 1-hexene, and 1-octene. Examples of (a) include polyethylene, polypropylene, poly (1-butene), and copolymers of propylene with other α-olefins (eg, 1-butene). When (a) is a propylene / ethylene copolymer resin or a propylene-1-butene copolymer resin, the thermoplastic elastomer composition of the present invention can provide a molded article having excellent heat resistance and flexibility. It is preferred in that respect. When a copolymer resin is used as (A), its crystallinity needs to be 50% or more, and preferably 60% or more. Here, the crystallinity refers to the ratio of the heat of fusion of the copolymer to the heat of fusion of a crystalline polyolefin homopolymer composed of only the olefin unit having the highest content in the copolymer resin. The heat of fusion is determined by the DSC method.

A copolymer obtained by copolymerizing two or more monomers selected from ethylene and an α-olefin having 3 to 8 carbon atoms in two or more stages can also be used. For example, a copolymer obtained by homopolymerizing propylene in the first step and copolymerizing propylene with ethylene or an α-olefin other than propylene in the second step can be used.

From the viewpoint of the strength of the molded product obtained by the powder molding method, the melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kgf in accordance with JIS K-7210 (a) is usually 20-500g / 10
Min, preferably in the range of 50 to 300 g / 10 min, particularly preferably in the range of 100 to 300 g / 10 min.

The component (b) of the present invention is a rubbery polymer and has a tan δ-temperature dependency curve obtained by a solid viscoelasticity measurement of a composition obtained by kneading with (a).
It is a rubbery polymer that gives a new single tan δ peak at a temperature different from both the tan δ peak temperature in (a) and the tan δ peak temperature in (b) in the temperature range of -70 to 30 ° C.

(B) a conjugated diene rubbery polymer and a hydrogenated conjugated diene rubbery polymer which is a hydrogenated product thereof, containing an ethylene unit and an α-olefin unit having 4 to 20 carbon atoms; Ethylene / α-olefin copolymer having a content of α-olefin unit of 50% by weight or more, propylene / butene copolymer having specific physical properties, propylene / α-olefin / ethylene copolymer having specific physical properties And copolymers.

The conjugated diene rubbery polymer used as (b) is a conjugated diene polymer rubber or a conjugated diene copolymer rubber.

The conjugated diene polymer rubber includes at least one
It is a polymer rubber obtained by polymerizing or copolymerizing a kind of conjugated diene. Examples of the conjugated diene include conjugated dienes having 4 to 8 carbon atoms such as butadiene, isoprene, pentadiene and 2,3-dimethylbutadiene.

Examples of the conjugated diene polymer rubber include polybutadiene, polyisoprene, polypentadiene, butadiene-isoprene copolymer and the like.

The conjugated diene copolymer rubber is a copolymer rubber of a conjugated diene and a monomer other than the conjugated diene as described above. Examples of the monomer other than the conjugated diene include a vinyl aromatic compound, a vinyl ester compound, an ethylenically unsaturated carboxylic acid ester compound, and a vinyl nitrile compound. Among them, a vinyl aromatic compound is preferable.

The vinyl aromatic compound has one of the vinyl groups.
The 2- or 3-position may be substituted with an alkyl group such as a methyl group. Examples of the vinyl aromatic compound include a vinyl aromatic compound having 8 to 12 carbon atoms such as styrene, p-methylstyrene, and α-methylstyrene. Examples of the vinyl ester compound include vinyl acetate. Examples of the ethylenically unsaturated carboxylic acid ester compound include methyl methacrylate, ethyl methacrylate,
Examples include methyl acrylate and butyl acrylate. Acrylonitrile as vinyl nitrile compound,
Methacrylonitrile and the like are exemplified.

Examples of the conjugated diene copolymer rubber include butadiene-styrene copolymer rubber and isoprene-
Conjugated diene-vinyl aromatic compound copolymer rubber such as styrene copolymer rubber, butadiene-isoprene-styrene copolymer rubber, butadiene-p-methylstyrene copolymer rubber, conjugated such as butadiene-vinyl acetate copolymer Conjugated diene-ethylenically unsaturated carboxylic acid ester copolymer rubbers such as diene-vinyl ester compound copolymer rubber, butadiene-methacrylic acid copolymer rubber, butadiene-methyl acrylate copolymer, butadiene-
Examples include conjugated diene-vinyl nitrile compound copolymer rubbers such as acrylonitrile copolymer.

The hydrogenated conjugated diene rubber is a hydrogenated conjugated diene polymer rubber or a hydrogenated conjugated diene copolymer rubber obtained by hydrogenating the above conjugated diene polymer rubber or conjugated diene copolymer rubber. In addition, examples of such hydrogenated conjugated diene rubber include hydrogenated conjugated diene rubber.

Such a conjugated diene copolymer rubber or hydrogenated conjugated diene copolymer rubber is disclosed in, for example,
It can be easily manufactured by the methods described in JP-A-36244, JP-A-3-72512, JP-A-7-118335, JP-A-56-38338, JP-A-61-60739 and the like. it can.

The conjugated diene-based copolymer rubber or hydrogenated conjugated diene-based copolymer rubber has a content of monomer units other than conjugated diene of 50% by weight or less, preferably 20% by weight or less. This is preferable in that a molded article having excellent flexibility can be obtained. If the content exceeds 50% by weight, a molded article obtained by molding the thermoplastic elastomer composition tends to be whitened when bent.

When a hydrogenated conjugated diene rubber is used as (b), the ratio of the number of hydrogenated conjugated diene units having a side chain having 2 or more carbon atoms to the number of hydrogenated conjugated diene units is as follows: Although it depends on the type of the conjugated diene monomer used in the polymerization, it is usually 50% or more, preferably 60 to 95%, more preferably 70 to 90%. Such a ratio can be determined by ¹ H-NMR measurement.

The MFR of the conjugated diene rubbery polymer and its hydrogenated product is preferably from 2 to 200 g / 10 min, more preferably from 5 to 100 g / 10 min, particularly preferably from 10 to 10 g / 10 min.
100 g / 10 min is preferable in that a molded article having excellent appearance and strength can be obtained by the powder molding method.

(B) An ethylene unit and carbon number 4
It is also possible to use an ethylene / α-olefin copolymer rubber containing from 20 to 20 α-olefin units and having a content of α-olefin units of 50% by weight or more. α
-As the olefin, 1-butene, 1-hexene, 1
Α-olefins having 4 to 8 carbon atoms such as -octene are preferably used. The ethylene / α-olefin copolymer rubber having an α-olefin unit content of 50% by weight or more includes 1,4-hexadiene, 1,6-octadiene, cyclopentadiene, and 2-methyl-2,5.
Monomers such as non-conjugated dienes such as -norbornadiene and 5-ethylidene-2-norbornene and vinyl aromatic compounds such as styrene, α-methylstyrene, 2,4-dimethylstyrene and p-methylstyrene are copolymerized. May be.

The ethylene / α-olefin copolymer having an α-olefin unit content of 50% by weight or more preferably has an α-olefin unit content of 50 to 90% by weight,
More preferably, it is in the range of 60 to 90% by weight. The content of the α-olefin unit is determined by a peak derived from the α-olefin unit determined by infrared absorption spectroscopy (for example, a peak of symmetric bending vibration of a terminal methyl group of a short-chain branch, or a methylene group in a branch). The peak can be determined from the absorbance of the group. The content of the α-olefin unit is described in, for example, the literature “Polymer Analysis Handbook, published by Kinokuniya Bookstore, edited by the Japan Society for Analytical Chemistry, Chapter 2, Section 2.2 (pp. 587-591), 19
1995 ”,“ Chemical Domain, Extra Number 140, Infrared, Raman,
Vibration [II] Present and Future Prospects, published by Nankodo, edited by Naotomichi Tsuboi et al., Characterization of Polyethylene by Infrared Absorption (pp. 73-81), 1983. Ethylene / α-olefin-based copolymers having an α-olefin unit content of 50% by weight or more are described, for example, in JP-A-3-163088 and JP-A-5-194641.
As disclosed in Japanese Unexamined Patent Publication (Kokai) No. HEI 10-205, it is obtained by polymerizing using a metal complex as an initiator in the presence of a cocatalyst.

Examples of metal complexes include zirconium complexes such as (tert-butylamido) dimethyl (η ⁵ -cyclopentadienyl) silane zirconium dichloride;
(Tert-butylamido) dimethyl (tetramethyl-
eta ⁵ - cyclopentadienyl) silane titanium dichloride, (anilide) (dimethyl) (tetramethyl-eta ⁵ -
Titanium complexes such as (cyclopentadienyl) silane titanium dichloride are included. These complexes are alumina,
It can be used by being supported on a carrier such as magnesium chloride or silica.

Examples of the cocatalyst include aluminum compounds such as methylaluminoxane, aluminum halide, aluminum alkyl halide, and trialkylaluminum; tris (pentafluorophenyl) borane; triphenylcarbeniumtetrakis (pentafluorophenyl) borane; Of boron-containing Lewis acids. The use of one compound as a cocatalyst is
A combination of two or more compounds can also be used.

When the content of such α-olefin unit is 5
The polymerization of the ethylene / α-olefin-based copolymer in an amount of 0% by weight or more is usually performed in a solvent. As the solvent,
For example, hydrocarbon solvents such as hexane, heptane, toluene, ethylbenzene and xylene are used. The polymerization is carried out in an atmosphere of an inert gas such as nitrogen, argon or hydrogen under atmospheric pressure or reduced pressure. The polymerization temperature is usually in the range of -30C to 250C.

When the content of the α-olefin unit is 5
The MFR of the ethylene / α-olefin-based copolymer that is 0% by weight or more is preferably 2 to 200 g / 10 minutes, more preferably 5 to 100 g / 10 minutes, and particularly preferably 10 to 100 g / 10 minutes.
It is preferably from 100 g / 10 min in that a molded article having excellent appearance and strength can be obtained by the powder molding method.

As the component (b), ASTM D2
Shore A hardness measured in accordance with No. 240 is 70 or less, and intrinsic viscosity with xylene solvent at 70 ° C.
a propylene / butene copolymer having an [η] of 0.3 dl / g or more, and a Shore A hardness of 70 or less as measured according to ASTM D2240, and an intrinsic viscosity with a xylene solvent at 70 ° C. [η] Is a propylene unit containing 0.3 dl / g or more, a propylene unit having 4 to 20 carbon atoms, an α-olefin unit and an ethylene unit.
-It is also possible to use an olefin / ethylene copolymer.

Shore A of such a propylene / butene copolymer and a propylene / α-olefin / ethylene copolymer was measured according to ASTM D2240.
Hardness needs to be 70 or less, but 60 or less,
More preferably, it is 50 or less. When the hardness exceeds 70, the flexibility of a molded article obtained by powder molding the olefin-based thermoplastic elastomer composition powder of the present invention tends to be inferior.

The intrinsic viscosity [η] of such a propylene / butene-based copolymer and a propylene / α-olefin / ethylene-based copolymer with a xylene solvent at 70 ° C. must be 0.3 dl / g or more. And 0.5d
It is preferably at least 1 / g. If the intrinsic viscosity is too low, a molded article obtained by molding the thermoplastic elastomer composition tends to have poor mechanical properties such as tensile strength and elongation at break. The intrinsic viscosity [η] refers to the viscosity of a xylene solution of the propylene / butene-based copolymer and the propylene / α-olefin / ethylene-based copolymer at various concentrations at 70 ° C. measured using an Ubbelohde viscometer. And is obtained from the following equation (1). Here, η _sp is the specific viscosity of the solution, and C is the mass concentration of the solution. The specific viscosity of the solution is determined by the following equation (2). η _sp = (η / η ₀ ) -1 (2) η and η ₀ are the viscosities of the solution and the solvent, respectively.

Such a propylene / butene copolymer and a propylene / α-olefin / ethylene copolymer have both a crystal melting peak and a crystallization peak as measured by a differential scanning calorimeter (DSC). Preferably, it does not have one. When such a condition is not satisfied, the flexibility of a molded product obtained by powder molding the olefin-based thermoplastic elastomer composition powder may be poor.

The value indicating the molecular weight distribution (value obtained by dividing the weight average molecular weight by the number average molecular weight) of the propylene / butene copolymer and the propylene / α-olefin / ethylene copolymer is 3 or less, and furthermore, Is preferably 2.5 or less. If the value exceeds 3 (the molecular weight distribution is wide), a molded article obtained by powder molding of the olefin-based thermoplastic elastomer composition powder may have a sticky feeling. The molecular weight distribution can be measured, for example, by the GPC method (gel permeation chromatography).

The 1-butene content in such a propylene-1-butene copolymer is preferably from 0.5 to 90 mol%, more preferably from 1 to 70 mol%. If the content is too small, the flexibility of a molded product obtained by powder molding the olefin-based thermoplastic elastomer composition powder of the present invention may be poor, while if the content is too large, the molded product may be damaged. May be inferior.

The content of propylene units and the content of α-olefin units in the propylene / α-olefin / ethylene copolymer preferably have the following relationship. y / (100−x) ≧ 0.3 More preferably, y / (100−x) ≧ 0.4, and further preferably, y / (100−x) ≧ 0.5. If the ratio is outside the above range, the flexibility of a molded product obtained by powder molding the olefin-based thermoplastic elastomer composition powder may be poor. In the above formula, x represents the molar content of propylene units in the copolymer, and y represents the molar content of α-olefin units having 4 to 20 carbon atoms in the copolymer.

The propylene content in the propylene / α-olefin / ethylene copolymer is preferably 90% or less, more preferably 80% when low-temperature resistance is required.
Or less, more preferably 70% or less, particularly preferably 60% or less.
%, Most preferably 50% or less. If the ratio is outside the above range, the low-temperature impact resistance of a molded product obtained by powder molding of the olefin-based thermoplastic elastomer composition powder may be poor.

The propylene / 1-butene copolymer and propylene / α-olefin / ethylene copolymer are 1,4-hexadiene, 1,6-octadiene,
Non-conjugated dienes such as cyclopentadiene, 2-methyl-2,5-norbornadiene and 5-ethylidene-2-norbornene, and styrene. α-methylstyrene, 2,4-
Vinyl aromatic compounds such as dimethylstyrene and p-methylstyrene may be copolymerized.

The arrangement of the propylene and / or 1-butene side chains in such a propylene / 1-butene copolymer and the propylene unit and / or α-olefin unit in the propylene / α-olefin / ethylene copolymer It is preferable that the side chain sequence has an atactic structure. When the sequence has an atactic structure, when the sequence of the side chain of the propylene chain in the copolymer is an atactic structure, the sequence of the side chain of the 1-butene or α-olefin chain in the copolymer is an atactic structure. If it is a structure,
The case where the arrangement of the side chain of the propylene / 1-butene complex chain in the copolymer or the propylene / α-olefin complex chain in the copolymer has an atactic structure is shown. The atactic structure is obtained, for example, when a homopolypropylene is polymerized using the catalyst system used for the polymerization of the propylene / 1-butene copolymer and the propylene / α-olefin / ethylene copolymer. The homopolypropylene thus obtained is defined by the following formula using the intensity [mm], [mr] and [rr] of each signal attributed to mm, mr and rr of propylene methyl carbon, which can be determined from the ¹³ C NMR spectrum. (1) It is confirmed from a structure having a value of 40 or more and 60 or less, preferably 43 or more and 57 or less, and more preferably 45 or more and 55 or less. F (1) = 100 × [mr] / ([mm] + [mr] + [r
r])

Similarly, the propylene / 1-butene copolymer and the propylene / α-olefin / ethylene copolymer also include propylene methyl carbon, 1-butene branched methylene carbon, and 1-butene branched terminal methyl carbon. When the value corresponding to F (1) obtained using the intensity of each signal attributed to mm, mr, and rr is within the above range, it can be confirmed that the structure is an atactic structure. When the propylene / 1-butene copolymer rubber and the propylene / α-olefin / ethylene copolymer do not have an atactic structure, their hardness is high, and the flexibility of the molded product obtained by using the thermoplastic elastomer composition powder is high. May be inferior in nature. In addition, mm, mr, rr such as methyl carbon derived from propylene unit, branched methylene carbon derived from 1-butene unit or α-olefin unit, and branched terminal methyl carbon derived from 1-butene unit or α-olefin unit.
Signal assignments are described, for example, in T.W. Asakura, M
acromolecules, Vol. 24, page 2334 (1
991), Kinokuniya Bookstore, New Edition Polymer Analysis Handbook (1995).

The propylene / 1-butene copolymer and
Propylene / α-olefin / ethylene copolymer is
Use the following (A) and the following (B) and / or (C)
Optimally manufactured in the presence of the olefin polymerization catalyst
obtain. (A): a transition metal complex represented by the following general formula [I](Where M¹Is the transition metal atom of Group 4 of the Periodic Table of the Elements
A represents an atom of Group 16 of the Periodic Table of the Elements,
J represents an atom belonging to Group 14 of the periodic table of the elements. Cp¹Is
A group having a cyclopentadiene-type anion skeleton is shown.
X¹, X^Two, R¹, R ^Two, R^Three, R^Four, R^FiveAnd R⁶Are each
Independently, hydrogen atom, halogen atom, alkyl group, arral
A kill group, an aryl group, a substituted silyl group, an alkoxy group,
Aralkyloxy group, aryloxy group or disubstituted amino
Represents a group. R¹, R^Two, R^Three, R^Four, R ^FiveAnd R⁶Is optional
They may combine to form a ring. (B): at least one selected from the following (B1) to (B3)
(B1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (B2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
All E¹, All E ^TwoAnd all E^ThreeIs the same
Or different. Z is a hydrogen atom or a halogen atom
Represents a child, and all Z may be the same or different
No. a is a number satisfying 0 <a ≦ 3, b is an integer of 2 or more
And c represents an integer of 1 or more. ) (C): The following (C1)
Any one of the boron compounds (C1) to (C3)¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-E represented by
Iodine compound, (C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-In table
(Where B is a boron atom in a trivalent state, Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated hydrocarbon
Group, substituted silyl group, alkoxy group or disubstituted amino group
And they may be the same or different.
G⁺Is an inorganic or organic cation, and L is a neutral Lewis
A base, (LH)⁺Is a Bronsted acid
You. )

Hereinafter, the above production method will be described in more detail.

The (A) transition metal complex will be described. In the general formula [I], the transition metal atom represented by M ¹ represents a transition metal element belonging to Group 4 of the Periodic Table of the Elements (IUPAC Revised Edition of Inorganic Chemical Nomenclature, 1989), for example, a titanium atom, a zirconium atom And a hafnium atom. Preferably it is a titanium atom or a zirconium atom.

The atom of Group 16 of the periodic table of the element represented by A in the general formula [I] includes, for example, an oxygen atom, a sulfur atom and a selenium atom, and is preferably an oxygen atom.

Examples of atoms belonging to Group 14 of the periodic table of the element represented by J in the general formula [I] include a carbon atom, a silicon atom, and a germanium atom.
Preferably it is a carbon atom or a silicon atom.

Examples of the group having a cyclopentadiene-type anion skeleton represented by the substituent Cp ¹ include, for example, η
⁵ - (substituted) cyclopentadienyl group, eta ⁵ - (substituted) indenyl group, eta ⁵ - and the like (substituted) fluorenyl group. Specific examples include, for example, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵
- dimethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - Echirushikuro Bae Ntajieniru group, eta ^5-n-propyl cyclopentadienyl group, eta ⁵ −
Isopropyl cyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-sec-butylcyclopentadienyl} group, eta ^{5-tert-Buchirushikuro} Bae Ntajieniru group, eta ^{5-n-Penchirushikuro} Bae Ntajieniru A group, η ⁵ -neopentylcyclopentadienyl group,
η ⁵ -n-hexylcyclopentadienyl group, η ⁵ -n-
Octylcyclopropane Bae Ntajieniru group, eta ⁵ - phenyl cycloalkyl Bae Ntajieniru group, eta ⁵ - Nafuchirushikuro Bae Ntajieniru group, eta ⁵ - trimethylsilylcyclopentadienyl Bae Ntajieniru group, eta ⁵ - triethylsilyl cycloalkyl Bae Ntajieniru group,
eta ^{5-tert-butyldimethylsilyl} cycloalkyl Bae Ntajieniru group, eta ⁵ - indenyl group, eta ⁵ - methylindenyl group, eta ⁵ - dimethyl indenyl group, eta ⁵ - ethyl indenyl group, eta ^5-n-propyl indenyl Nyl group, η ⁵ -isopropylindenyl group, η ⁵ -n-butylindenyl group, η ⁵
-Sec-butylindenyl group,? ⁵ -tert-butylindenyl group,? ^5- n-pentylindenyl group,? ⁵
-Neopentylindenyl group,? ^5- n-hexylindenyl group,? ^5- n-octylindenyl group,? ^5- n-
Decylindenyl group, η ⁵ -phenylindenyl group, η ⁵
- methylphenyl indenyl group, eta ⁵ - naphthyl indenyl group, eta ⁵ - trimethylsilyl indenyl group, eta ⁵ - triethylsilyl indenyl group, eta ^{5-tert-butyldimethylsilyl} indenyl group, eta ⁵ - tetrahydroindenyl group, eta ⁵ - fluorenyl group, eta ⁵ - methyl fluorenyl group, eta ⁵ - dimethyl fluorenyl group, eta ⁵ - ethyl fluorenyl group, eta ⁵ - diethyl fluorenyl group, eta ⁵ -n
- propyl fluorenyl group, eta ⁵ - di -n- propyl fluorenyl group, eta ⁵ - isopropyl fluorenyl group, eta ⁵
- diisopropyl fluorenyl group, eta ^{5-n-butyl-fluorenyl} group, eta ^{5-sec-butylfluorenyl} group,
η ⁵ -tert-butylfluorenyl group, η ⁵ -di-n-
Butylfluorenyl group, eta ⁵ - di -sec- butyl-fluorenyl group, eta ⁵ - di -tert- butyl-fluorenyl group, eta ^{5-n-pentyl-fluorenyl} group, eta ⁵ - Neopentyl fluorescens N-yl, η ⁵ -n-hexylfluorenyl, η ⁵ -n-octylfluorenyl, η ⁵ -n-decylfluorenyl, η ⁵ -n-dodecylfluorenyl, η ^5- phenyl fluorenyl group, eta ⁵ - di - phenyl fluorenyl group, eta ⁵ - methylphenyl fluorenyl group, eta ⁵ - naphthyl fluorenyl group, eta ⁵ - trimethylsilyl fluorenyl group, eta ⁵ - bis - trimethylsilyl fluorenyl group, eta ⁵ - triethylsilyl fluorenyl group, such as eta ^{5-tert-butyldimethylsilyl-fluorenyl} group and the like, preferably eta ⁵ - cyclopentadienyl group, eta ⁵ - Mechirushiku Pentadienyl, η ⁵ -
tert- butyl cyclopentadienyl group, eta ⁵ - fluorenyl group - tetramethylcyclopentadienyl group, eta ⁵ - indenyl group, or eta ^5.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^{As the} halogen atom for ⁵ or R ⁶ , a fluorine atom,
Examples thereof include a chlorine atom, a bromine atom, and an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The alkyl group for ⁵ or R ⁶ has 1 to 1 carbon atoms.
Preferred are 20 alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n- Hexyl group,
n-octyl group, n-decyl group, n-dodecyl group, n-
Examples thereof include a pentadecyl group and an n-eicosyl group, and more preferably a methyl group, an ethyl group, an isopropyl group, and a t-group.
tert-butyl or amyl.

All of these alkyl groups may be substituted with halogen atoms such as fluorine, chlorine, bromine and iodine. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl group, iodomethyl group, diiodomethyl group,
Triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl , Dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,
Perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group,
Perchloropentadecyl group, perchloroeicosyl group,
Perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl, perbromoeicosyl and the like.

All of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The aralkyl group for ⁵ or R ⁶ has 7 carbon atoms.
~ 20 aralkyl groups are preferred, for example, benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) methyl,
(2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl Phenyl) methyl group, (4,6
-Dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4 , 5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) ) Methyl, (2,3,5,6-tetramethylphenyl) methyl, (pentamethylphenyl) methyl, (ethylphenyl) methyl, (n-propylphenyl) methyl,
(Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl)
Methyl group, (n-hexylphenyl) methyl group, (n-
Octylphenyl) methyl group, (n-decylphenyl)
Methyl group, (n-dodecylphenyl) methyl group, (n-
Tetradecylphenyl) methyl group, naphthylmethyl group,
Examples include an anthracenylmethyl group, and more preferably a benzyl group.

These aralkyl groups are all halogen atoms such as fluorine, chlorine, bromine and iodine, alkoxy such as methoxy and ethoxy, aryloxy such as phenoxy and benzyloxy. It may be partially substituted with an aralkyloxy group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^{As the} aryl group for ⁵ or R ^6, C ^{6 to} C 6
Preferred are 20 aryl groups such as phenyl, 2
-Tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group,
2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,
3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group,
3,4,5-trimethylphenyl group, 2,3,4,5-
Tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-
Propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert
-Butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, Examples include an anthracenyl group, and more preferably a phenyl group.

These aryl groups are all halogen atoms such as fluorine, chlorine, bromine and iodine, alkoxy such as methoxy and ethoxy, aryloxy such as phenoxy and benzyloxy. It may be partially substituted with an aralkyloxy group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The substituted silyl group represented by ⁵ or R ⁶ is a silyl group substituted by a hydrocarbon group, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Sec-butyl group, tert-
Examples thereof include an alkyl group having 1 to 10 carbon atoms such as a butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group and a cyclohexyl group, and an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group and the like. A disubstituted silyl group having 2 to 20 carbon atoms,
Trimethylsilyl group, triethylsilyl group, tri-n-
Propylsilyl group, triisopropylsilyl group, tri-
n-butylsilyl group, tri-sec-butylsilyl group,
Tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-
n-pentylsilyl group, tri-n-hexylsilyl group,
Examples thereof include a trisubstituted silyl group having 3 to 20 carbon atoms such as a tricyclohexylsilyl group and a triphenylsilyl group, and a trimethylsilyl group, a tert-butyldimethylsilyl group, or a triphenylsilyl group is preferable.

In each of these substituted silyl groups, the hydrocarbon group is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, or an aryloxy group such as a phenoxy group. Alternatively, it may be partially substituted with an aralkyloxy group such as a benzyloxy group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The alkoxy group for ⁵ or R ⁶ has 1 carbon atom
~ 20 alkoxy groups are preferred, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-
Butoxy group, n-pentoxy group, neopentoxy group, n
-Hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadeoxy group, n-icosoxy group and the like, and more preferably methoxy group, ethoxy group or tert-butoxy group.

All of these alkoxy groups include halogen atoms such as fluorine, chlorine, bromine and iodine, alkoxy such as methoxy and ethoxy, aryloxy such as phenoxy and benzyloxy. It may be partially substituted with an aralkyloxy group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The aralkyloxy group for ⁵ or R ⁶ is preferably an aralkyloxy group having 7 to 20 carbon atoms, for example, a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, a (4-methylphenyl) methoxy group. Methylphenyl) methoxy group, (2,3-dimethylphenyl)
Methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2
(6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl)
A methoxy group, a (2,3,5-trimethylphenyl) methoxy group, a (2,3,6-trimethylphenyl) methoxy group, a (2,4,5-trimethylphenyl) methoxy group,
A (2,4,6-trimethylphenyl) methoxy group,
(3,4,5-trimethylphenyl) methoxy group,
(2,3,4,5-tetramethylphenyl) methoxy, (2,3,4,6-tetramethylphenyl) methoxy, (2,3,5,6-tetramethylphenyl) methoxy, (penta (Methylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n
-Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-
Examples thereof include an (octylphenyl) methoxy group, a (n-decylphenyl) methoxy group, a (n-tetradecylphenyl) methoxy group, a naphthylmethoxy group, and an anthracenylmethoxy group, and more preferably a benzyloxy group.

Each of these aralkyloxy groups is
Partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. You may.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^The aryloxy group for ⁵ or R ⁶ is preferably an aryloxy group having 6 to 20 carbon atoms, for example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3- Dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5
-Dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group,
2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,
4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy Group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy Group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like.

Each of these aryloxy groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group,
An aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group may be partially substituted.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^The disubstituted amino group in ⁵ or R ⁶ is an amino group substituted with two hydrocarbon groups, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, isobutyl group, n-pentyl group, n
A hexyl group, a cyclohexyl group or the like having 1 to 1 carbon atoms
10 to 6 carbon atoms such as an alkyl group and a phenyl group
And an aralkyl group having 7 to 10 carbon atoms. Examples of such a disubstituted amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, Di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino Groups, a diphenylamino group, a bistrimethylsilylamino group, a bis-tert-butyldimethylsilylamino group and the like, and preferably a dimethylamino group or a diethylamino group.

The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R
⁶ may be optionally bonded to form a ring.

Preferably, R ¹ is an alkyl group, an aralkyl group, an aryl group or a substituted silyl group.

Preferably, X ¹ and X ² are each independently a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group, and more preferably a halogen atom.

Examples of the transition metal complex (A) include methylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride and methylene (cyclopentadienyl) (3-tert-butyl-2). -Phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Methylene (cyclopentadienyl) (3-phenyl-2
-Phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2 -Phenoxy) titanium dichloride, methylene (cyclopentadienyl)
(3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-2-
Phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5)
-Methyl-2-phenoxy) titanium dichloride,
Methylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene ( Methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5)
-Methoxy-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-t
tert-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) ( 3-tert-butyl-
2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3- tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tert
-Butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) Titanium dichloride, methylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-
Phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-ter
t-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert- Butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl- 5-methoxy-
2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert
-Butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl -2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy ) Titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-)
Methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (fluorenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (Fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert- Butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene Pentadienyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Isopropylidene (cyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyldimethyl Silyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl)
(3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentane) Dienyl) (3,5-
Dimethyl-2-phenoxy) titanium dichloride,
Isopropylidene (methylcyclopentadienyl) (3
-Tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3 -Phenyl-2-
Phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5- Methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-
2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (t
tert-butylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy)
Titanium dichloride, isopropylidene (tert
-Butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-trimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2)
-Phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-
tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) ( 3-tert
-Butyl-2-phenoxy) titanium dichloride,
Isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-phenyl-2
-Phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-te
rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopenta Dienyl) (3-tert-butyl-5-methoxy-2
-Phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3- te
rt-butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-
Phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-) Phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-
Butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3,5- Dimethyl-2-
Phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene ( Fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-
tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3,5 -Dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl)
(3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl)
(3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentane) Dienyl) (3
5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl- 5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (tert -Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (t
tert-butylcyclopentadienyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium Dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5 -Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-
5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert- Butyl-2-
Phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3- tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3- t
tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-
2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl)
(3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3,5
-Dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-ter
t-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-ter
t-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl)
(3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-te
rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-
5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-ter
t-butyl-5-chloro-2-phenoxy) titanium dichloride and the like, compounds obtained by changing titanium to zirconium or hafnium, dibromide to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), -A compound obtained by changing n-butoxide or diisopropoxide, (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (n-butylcyclopentadienyl), (tert) -Butyldimethylsilylcyclopentadienyl) or a compound changed to (indenyl), (3,5-dimethyl-2-phenoxy) is converted to (2-phenoxy), (3-methyl-2-phenoxy), (3, 5-di-tert-butyl-2-phenoxy), (3-f -5-methyl-2-phenoxy), (3-tert- butyldimethylsilyl-2-
A transition metal complex in which J in the general formula [I] is a carbon atom, such as a compound changed to (phenoxy) or (3-trimethylsilyl-2-phenoxy); and dimethylsilyl (cyclopentadienyl) (2-phenoxy) titanium Dichloride, dimethylsilyl (cyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadiyl) Enyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) ) (3,5-di -tert- butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3
-Phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) ( 3-tert-
Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) ( 2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride , Dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-2-phenoxy)
Titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-di-tert-butyl- 2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyldimethylsilyl- 5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl)
(5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-
Methoxy-2-phenoxy) titanium dichloride,
Dimethylsilyl (methylcyclopentadienyl) (3-
tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-diamyl-2-phenoxy)
Titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n- Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy)
Titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-2-
Phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (5-methyl-3
-Trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-
Butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) ( 2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-dimethyl-2-
Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) ) (3,5-
Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) ) (3-te
rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (te
rt-butylcyclopentadienyl) (5-methyl-3
-Trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-diamyl-2-
Phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethyl) Cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) ( 3,5-di-te
rt-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3- tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2)
-Phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-ter
t-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclo Pentadienyl) (3
5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride,
Dimethylsilyl (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopenta Dienyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) )
(5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclo) Pentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-diamyl-2-phenoxy) ) Titanium dichloride, dimethylsilyl (indenyl)
(2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-methyl-2-phenoxy)
Titanium dichloride, dimethylsilyl (indenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-t
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (5-methyl-3-phenyl- 2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-
Butyldimethylsilyl-5-methyl-2-phenoxy)
Titanium dichloride, dimethylsilyl (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-chloro-
2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-methyl- 2
-Phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) ( 3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (5-methyl- 3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-
tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl)) (1-naphthoxy) -2-yl) titanium dichloride and the like, and (cyclopentadienyl) of these compounds is (dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclo (Pentadienyl), (isopropylcyclopentadienyl), (se
c-butylcyclopentadienyl), (isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl), (methylindenyl), or (phenylindenyl) The modified compound, (2-phenoxy) is replaced with (3
-Phenyl 2-phenoxy), (3-trimethylsilyl-2-phenoxy), or a compound changed to (3-tert-butyldimethylsilyl-2-phenoxy), dimethylsilyl changed to diethylsilyl, diphenylsilyl, or dimethoxysilyl General compounds such as a compound obtained by changing titanium to zirconium or hafnium, a compound obtained by changing dichloride to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide or diisopropoxide [ Transition metal complexes wherein J in I] is an atom belonging to Group 14 of the periodic table of elements other than carbon atoms.

The transition metal complex represented by the general formula [I] can be synthesized, for example, by the following method.

First, an alkoxybenzene compound having a halogenated ortho position and a cyclopentadiene compound substituted with a halogenated Group 14 atom are reacted in the presence of an organic alkali metal or magnesium metal. Makes the group having a cyclopentadiene skeleton and the group having an alkoxybenzene skeleton a first group
A compound having a structure linked by Group 4 atoms is obtained. Then, after treating the compound with a base, the compound is reacted with a halide, hydrocarbon, or hydrocarbon oxy compound of a transition metal to synthesize a transition metal complex represented by the general formula [I]. it can.

The (B) aluminum compound will be described. As the aluminum compound (B), the following (B1)
And (B3) are at least one aluminum compound. (B1) the general formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B2) general formula {-Al (E ²⁾ -O-} cyclic aluminoxane (B3) having a structure represented by _b the formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
Linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² , and E ³ are each a hydrocarbon group, and all E ¹ , all E ^2, and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. And c represents an integer of 1 or more.) E ¹ , E ² , or E ³
Is preferably a hydrocarbon group having 1 to 8 carbon atoms, and more preferably an alkyl group.

Specific examples of the organoaluminum compound (B1) represented by the general formula E ¹ _a AlZ _3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, hexylaluminum dichloride Dimethylal Examples thereof include dialkylaluminum hydrides such as minium hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride.

Preferably, it is a trialkylaluminum, more preferably, triethylaluminum or triisobutylaluminum.

[0073] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 In a linear aluminoxane (B3) having the structure shown,
Specific examples of E ² and E ³ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group,
Examples thereof include an alkyl group such as an isobutyl group, a normal pentyl group, and a neopentyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ²
And E ³ is a methyl group or an isobutyl group, and b is 2
-40 and c are 1-40.

The above aluminoxane can be made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum or the like) in a suitable organic solvent (benzene or aliphatic hydrocarbon or the like) is brought into contact with water. In addition, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt (for example, copper sulfate hydrate or the like) containing water of crystallization can be exemplified.

The (C) boron compound will be described. As the boron compound (C), (C1) a compound represented by the general formula BQ ¹ Q ²
A boron compound represented by Q ³ , (C2) a general formula G ⁺ (B
^{Q 1 Q 2 Q 3 Q 4} ) - boron compound represented by, (C3) the general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - using either a boron compound represented by be able to.

General formula BQ¹Q^TwoQ^ThreeBoration represented by
In the compound (C1), B is boron in a trivalent valence state
Atom, Q¹~ Q^ThreeRepresents a halogen atom, a hydrocarbon group,
A hydrogenated hydrocarbon group, a substituted silyl group, an alkoxy group or
Disubstituted amino groups, which are the same or different
May be. Q¹~ Q^ThreeIs preferably a halogen atom,
A hydrocarbon group containing 1-20 carbon atoms, 1-20
Halogenated hydrocarbon groups containing carbon atoms, from 1 to 20 carbon atoms
Substituted silyl groups containing 1 to 20 carbon atoms
An alkoxy group or an amino containing 2 to 20 carbon atoms
And more preferred Q¹~ Q^ThreeIs a halogen atom, 1 to
A hydrocarbon group containing 20 carbon atoms, or 1-20
It is a halogenated hydrocarbon group containing a carbon atom. More preferred
Or Q ¹~ Q^FourIs at least one fluorine source
A fluorinated hydrocarbon group having 1 to 20 carbon atoms containing
And particularly preferably Q¹~ Q^FourIs at least 1 each
Fluorinated carbon atoms having 6 to 20 carbon atoms containing two fluorine atoms
It is a reel group.

Specific examples of compound (C1) include tris (pentafluorophenyl) borane, tris (2,3,
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic or organic cation, and B is boron in a trivalent valence state. an atom, Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above (C1).

[0079] formula ^{G + (BQ 1 Q 2 Q} 3 Q 4) - Examples of G ⁺ as an inorganic cation in the compound represented by, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ^{+ in} which a cation or the like is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Examples thereof include triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and most preferably triphenylmethyltetrakis (pentafluorophenyl) borate.

The formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In the boron compound represented (C3), L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, B is boron atom in the trivalent valence state ,
Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

[0082] formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - is a Brønsted acid in the compound represented by (L-
Specific examples of H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.
As (BQ ¹ Q ² Q ³ Q ⁴ ) ^{-, the same} as those described above can be mentioned.

Specific examples of these combinations include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Examples thereof include tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. Most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) is used. Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

In the copolymerization, an olefin polymerization catalyst comprising the transition metal complex (A) represented by the general formula [I] and the above (B) and / or the above (C) is used.
When an olefin polymerization catalyst comprising two components (A) and (B) is used, the cyclic aluminoxane (B2) and / or the linear aluminoxane (B3) may be used as (B).
Is preferred. Another preferred embodiment of the olefin polymerization catalyst is an olefin polymerization catalyst comprising the above (A), (B) and (C). In this case, the (B) may be the aforementioned (B1) ) Easy to use.

The amount of each component used is usually such that the molar ratio of (B) / (A) is 0.1 to 10000, preferably 5 to 200.
It is desirable to use each component so that the molar ratio of 0, (C) / (A) is 0.01 to 100, preferably 0.5 to 10.

The concentration when each component is used in a solution state or a suspension state in a solvent is appropriately selected depending on conditions such as the performance of an apparatus for supplying each component to the polymerization reactor. , Usually 0.01 to 500 μmol / g,
More preferably, 0.05 to 100 μmol / g, still more preferably, 0.05 to 50 μmol / g, (B)
Usually, in terms of Al atom, 0.01 to 10000 μmol /
g, more preferably 0.1 to 5000 μmol /
g, more preferably 0.1 to 2000 μmol / g,
(C) is usually from 0.01 to 500 μmol / g, preferably from 0.05 to 200 μmol / g, and more preferably from 0.05 to 100 μmol / g. desirable.

In the polymerization reaction, for example, an aliphatic hydrocarbon such as butane, pentane, hexane, heptane or octane, an aromatic hydrocarbon such as benzene or toluene, or a halogenated hydrocarbon such as methylene dichloride is used as a solvent. Alternatively, slurry polymerization, gas-phase polymerization in a gaseous monomer, or the like is possible, and either continuous polymerization or batch polymerization is possible. Polymerization temperature is -50 ° C
To 200 ° C., but especially -20 ° C. to 10 ° C.
The temperature is preferably in the range of 0 ° C, and the polymerization pressure is from normal pressure to 60 kg /
cm ² G is preferred. The polymerization time is generally appropriately determined depending on the type of the catalyst to be used and the reactor, but can range from 1 minute to 20 hours. Further, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

The above (A) and (B) and / or (C) may be mixed in advance and then injected into the reactor, or each may be independently injected from another injection pipe,
A method of mixing in a reactor may be used. In the case of a multiple reaction zone method, the reaction may be injected into the first reaction zone at once, or may be split into other reaction zones and injected.

In the thermoplastic elastomer composition of the present invention, (B) tends to have a property of being finely dispersed in the amorphous phase of (A) in units of several tens to several hundreds of nm.
Observed by a transmission electron microscope (TEM).

The (b) of the present invention is obtained by kneading the tan δ-
In the temperature dependence curve, the tan δ peak temperature in (a) and the tan δ in (b) were within a temperature range of −70 to 30 ° C.
A new single ta at a temperature different from any of the peak temperatures
It is a rubbery polymer giving an nδ peak. Here, “single” means having the only maximum value in the approximate temperature range. The peak temperature of the new tan δ peak is
The temperature may be different from both the tan δ peak temperature of (a) and the tan δ peak temperature of (b), but it is usually lower than the peak temperature of the olefin-based resin. In addition,
Since this behavior is not observed when kneading of (b) and (a) is insufficient, kneading is performed at a kneading strength of a relatively weak kneading strength of about 1 × 10 ² sec ⁻¹ or more.

The measurement of the solid viscoelasticity can be performed using a usual solid viscoelasticity measuring device.

The thermoplastic elastomer composition of the present invention comprises:
It contains 100 parts by weight of (A) and 10 to 250 parts by weight of (B), and preferably contains 100 parts by weight of (A) and 40 to 200 parts by weight of (B).
If the content of (b) is too small, the flexibility of the obtained molded product is inferior, while if it is too large, the obtained molded product has a sticky feeling.

The thermoplastic elastomer composition of the present invention comprises:
In addition to the essential components (a) and (b), (d) α
-Ethylene having an olefin unit content of less than 50%
An α-olefin-based copolymer may be contained. In addition, (D) shows the temperature range of -70 to 30 ° C in the tan δ-temperature dependency curve obtained by the solid viscoelasticity measurement of the composition obtained by kneading (A) and (D). Ta
It does not have the property of giving a new single tan δ peak at a temperature different from both the n δ peak temperature and the tan δ peak temperature in (d).

In the case where (d) is contained, the powder moldability of the thermoplastic elastomer powder and the whitening resistance when the molded product obtained by powder molding the powder is bent are not reduced. A molded article having excellent cold resistance and cost performance is provided.

The α-olefin unit content of (d) is 50
% Of ethylene / α-olefin-based copolymer is a copolymer of ethylene and α-olefin, a copolymer of ethylene, α-olefin and non-conjugated diene, and has almost no crystallinity. It is a polymer or a polymer having a crystallinity of less than 50%. Here, the crystallinity refers to the ratio of the heat of fusion of the copolymer to the heat of fusion of the crystalline polyethylene homopolymer in the copolymer resin. The heat of fusion is determined by the DSC method. Here, as the α-olefin, propylene, 1-butene, 3-methyl-1
An α-olefin having 3 to 10 carbon atoms such as butene, dicyclopentadiene, 5-
Ethylidene-2-norbornene, 1,4-hexadiene, 1,5-cyclooctadiene, 2-methylene-5-
Examples thereof include non-conjugated dienes having 5 to 15 carbon atoms such as norbornene. Such ethylene / α-olefin copolymers include, for example, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / propylene copolymer
Propylene / 5-ethylidene-2-norbornene copolymer (hereinafter referred to as “EPDM”). Such an ethylene / α-olefin-based copolymer may be crosslinked.

The α-olefin unit content in the ethylene / α-olefin-based copolymer having an α-olefin unit content of less than 50% is preferably 5 to 40% by weight, more preferably 10 to 35% by weight. And the ethylene unit content is usually from 60 to 95% by weight, preferably from 65 to 95% by weight.
~ 90% by weight. The α-olefin unit content and the ethylene unit content can be determined by ¹³ C-NMR method, infrared absorption spectroscopy, or the like. When a molded article is produced by a powder molding method using the thermoplastic elastomer composition powder of the present invention, the ethylene / α-olefin-based copolymer may be produced from an ASTM D- The Mooney viscosity {ML _{1 + 4} (100 ° C.)} measured at 100 ° C. according to 927-57T is preferably in the range of 10 to 350, more preferably 15 to 300.

When (d) is used, the amount of (d) is
(A) 250 parts by weight or less for 100 parts by weight;
Preferably it is 20 to 200 parts by weight. If the amount of (d) is excessive, the resulting molded article may have a sticky feeling.

The thermoplastic elastomer composition of the present invention comprises:
Complex dynamic viscosity η ^* (1) at 250 ° C. is 1.5 × 1
It must be less than 0 ⁵ poise, and 1 × 10 ² to 8
The range of × 10 ³ poise is preferable, and 3 × 10 ^{2 to} 5
It is preferably in the range of × 10 ³ poise.

Here, the complex dynamic viscosity η ^* (ω) is the storage elastic modulus G ′ (ω) at a temperature of 250 ° C. and a vibration frequency ω.
And the loss elastic modulus G ″ (ω), the following equation (3)
Complex dynamic viscosity η ^* (1)
Is the complex dynamic viscosity at ω = 1 radian / second. η ^* (ω) = ｛[G ′ (ω)] ² + [G ″ (ω)] ² ｝ ^1/2 / ω (3)

If η ^* (1) exceeds the above upper limit, the melt fluidity of the thermoplastic elastomer composition is inferior, and the shear rate at the time of molding, such as a powder molding method, is usually as low as 1 second ^-1 or less. It tends to be difficult to produce a molded article by the molding method described above.

The thermoplastic elastomer composition of the present invention comprises:
It is necessary that the Newton viscosity index n is 0.67 or less, preferably in the range of 0.01 to 0.35, and more preferably in the range of 0.03 to 0.25.

Here, the Newtonian viscosity index n is the complex dynamic viscosity η ^* (1), the temperature is 250 ° C., and the vibration frequency ω =
Complex dynamic viscosity η ^* measured at 100 radians / second (1
00) is calculated by the following equation (4). n = {logη ^* (1) −logη ^* (100)} / 2 (4)

When the Newton's viscosity index n exceeds the above-mentioned upper limit, the mechanical strength of the obtained molded product becomes low.

As a method for obtaining the thermoplastic elastomer composition of the present invention, for example, the following method can be mentioned. That is, (a) and (b) and, if necessary, (d) may be melt-kneaded. In addition, after kneading or dynamically cross-linking all or several types selected from (a) and (b) and, if necessary, (d), the components not selected are also melt-kneaded. Can be. For example, the thermoplastic elastomer composition of the present invention in which (a) and / or (d) is cross-linked intramolecularly and / or intermolecularly, usually after dynamically cross-linking (a) and (d), And kneading after adding (b). Here, a single-screw extruder or a twin-screw extruder can be used for kneading. In addition, as for the compounding of various additives described later, for example, (A), (B), or (D) in which these additives are previously compounded,
It can be carried out by mixing the above components during kneading or dynamic crosslinking.

The dynamic crosslinking of the kneaded mixture can be carried out, for example, by kneading the kneaded mixture and a crosslinking agent under heating. As the crosslinking agent, usually, 2,5-dimethyl-2,5-di (tert-butylperoxyno) is used.
Organic peroxides such as hexane and dicumyl peroxide are used. The crosslinking agent is usually not more than 1 part by weight, preferably 0.1 to 100 parts by weight, per 100 parts by weight of the total of the components to be crosslinked among (A), (B) and, if necessary, (D).
0.8 parts by weight, more preferably 0.2 to 0.6 parts by weight. When an organic peroxide is used as a cross-linking agent, when dynamic cross-linking is performed in the presence of a cross-linking aid such as a bismaleimide compound, a thermoplastic elastomer composition that gives a molded article having excellent heat resistance can be obtained. Can be. In this case, the amount of the organic peroxide to be used is usually 0 per 100 parts by weight of the total of the components to be crosslinked among (a), (b) and, if necessary, (d). .8
Parts by weight or less, preferably 0.2 to 0.8 parts by weight, more preferably 0.4 to 0.6 parts by weight.

The amount of the crosslinking assistant used is usually 1.5 parts by weight or less, preferably 1.5 parts by weight, per 100 parts by weight of the total of (a), (b) and, if necessary, (d).
It is in the range of 0.2 to 1 part by weight, more preferably 0.4 to 0.8 part by weight. The crosslinking aid is preferably added before the addition of the crosslinking agent, and is usually added when the components to be crosslinked are preliminarily kneaded.

The crosslinking of (a), (b) and (d) is carried out by heating a component to be cross-linked, a cross-linking agent, and, if necessary, a cross-linking aid, while heating, a single-screw extruder or a twin-screw extruder. Kneading can be performed by using an extruder or the like while heating, for example, in a temperature range of 150 to 250 ° C.

The thermoplastic elastomer composition of the present invention comprises:
For example, heat stabilizers such as mineral oil-based softeners, phenol-based, sulfite-based, phenylalkane-based, phosphite-based, amine-based, and amide-based anti-aging agents, weather-resistant stabilizers, antistatic agents, metallic soaps, waxes And other various additives.

Further, in the tan δ-temperature dependence curve obtained by measuring the solid viscoelasticity of the composition obtained by kneading with (a), two tan tans in a temperature range of −70 to 30 ° C.
Polymer component giving δ peak, for example, rubbery polymers such as conjugated diene copolymer rubber, natural rubber, butyl rubber, chloroprene rubber, epichlorohydrin rubber, acrylic rubber, etc., ethylene-acrylic acid copolymer having such properties ,
Ethylene-vinyl acetate copolymer and saponified product thereof, ethylene-methyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-
Other polymer components such as glycidyl methacrylate-vinyl acetate copolymer may be contained.

These additives and other polymer components are:
(I), (b) and (d) may be used by being contained in advance, or may be blended by kneading or the like during or after the above-mentioned kneading or dynamic crosslinking.

The thermoplastic elastomer composition containing the mineral oil-based softener is excellent in melt fluidity and can give a molded article excellent in flexibility. Even if an oil-extended olefin-based copolymer containing the mineral oil-based softener in (d) in advance is used, the above-described kneading and dynamic crosslinking can be easily performed.

In order to produce the thermoplastic elastomer composition of the present invention which satisfies the physical properties indicated by the complex dynamic viscosity and the Newtonian viscosity index, the degree of the above-mentioned kneading and dynamic crosslinking, The type and amount of each component constituting the plastic elastomer composition, the type and amount of the cross-linking agent or cross-linking aid in dynamic crosslinking, the type and amount of additive, and the like are appropriately selected. Above all, the shear rate in kneading and dynamic crosslinking greatly affects the above physical properties, and it is preferable to perform kneading and dynamic crosslinking at a shear rate of 1 × 10 ³ sec ⁻¹ or more.

The thermoplastic elastomer composition powder of the present invention is produced by adding (c) a fine powder having a primary particle size of 300 nm or less to the pulverized thermoplastic elastomer obtained by the above method. You.

As a method for pulverizing the thermoplastic elastomer composition, there is a freeze pulverization method. The freeze pulverization method is a method of cooling the thermoplastic elastomer composition to a temperature lower than its glass transition temperature, preferably -70 ° C or lower, more preferably -90 ° C or lower, and pulverizing the thermoplastic elastomer composition while keeping the cooled state. It is also possible to pulverize the thermoplastic elastomer composition at a temperature higher than its glass transition temperature, but the particle size of the obtained pulverized product is not uniform, and powder molding obtained by adding a fine powder is performed. Tends to be difficult to perform.

In order to pulverize the thermoplastic elastomer composition while keeping it in a cooled state, the pulverization efficiency is high,
The pulverization is preferably performed by a method that generates less heat. For example, a mechanical pulverization method using an impact pulverizer such as a ball mill is used. The powder of the thermoplastic elastomer composition in this method is usually sized to pass through a Tyler standard sieve 24 mesh (mesh size 700 μm × 700 μm), preferably 28 mesh (mesh size 590 μm × 5).
90 μm), and more preferably 3 μm.
2 mesh (aperture 500 μm × 500 μm), particularly preferably 42 mesh (aperture 355 μm × 355 μm)
m).

Examples of (c) used in the present invention include powdered pigments, inorganic oxides, vinyl chloride resins for pastes, metal salts of fatty acids, and the like. The primary particle size of (c) is 300 nm
Or less, and preferably 200 nm or less, and more preferably 5 nm to 150 nm. When the primary particle size exceeds 300 nm, the powder flowability of the obtained thermoplastic elastomer powder is not sufficiently improved, and the molded product obtained by powder molding causes defects such as underfill and pinholes. Here, the primary particle size is defined as a value obtained by taking a photograph of (c) with a transmission electron microscope (TEM),
It is a value obtained by measuring the particle diameter by selecting about 0 particles and dividing the diameter of these particles by the number of particles.

Examples of powder pigments include organic pigments such as azo, phthalocyanine, sullen and dye lakes, oxides such as titanium oxide, molybdate chromate, selenium sulfide compounds, ferrocyan compounds, carbon black and the like. Are used.

The primary particle size of the powder pigment must be 300 nm or less.
What is carried on a powder having a size exceeding 10 nm and not more than 10 nm can also be used. In this case, the weight of (c) is
The weight of (e) carried is not included. As the carrier (e) used here, calcium carbonate, metal soap, magnesium oxide and the like are usually used. in this case,
The primary particle size of (e) is usually 10 μm or less, preferably 1 μm.
m to 5 μm. In this case, the weight ratio of the powder pigment to (e) is usually 20:80 to 80:20, preferably 2:80.
5:75 to 75:25.

As the inorganic oxide, alumina, silica,
Alumina silica and the like can be mentioned.

Most of alumina has a chemical formula of Al ₂
It is a fine powder composed of O ₃ units. Alumina has various crystal forms, and any of the crystal forms can be used. These are called α-alumina, β-alumina, γ-alumina, etc. depending on the crystal form. Alumina C (γ-alumina) manufactured by Degussa, AKP-G008 (α-alumina) manufactured by Sumitomo Chemical Co., Ltd.
And so on.

Most of silica has a chemical formula of SiO ₂
It is a fine powder composed of units. Crushing natural diatomaceous earth,
It is produced by a method such as decomposition of sodium silicate. OX50 manufactured by Degussa Corporation and the like can be mentioned. Alumina silica is an inorganic oxide containing the aforementioned alumina and silica as main components.

The surface of these inorganic oxides may be coated with dimethyl silicone oil or the like, or may be surface-treated with a trimethylsilyl group or the like.

These (c) are used alone or in combination of two or more having a primary particle size of 300 nm or less. For example, a powder pigment alone can be used, or a powder pigment and an inorganic oxide can be used in combination.

The amount of (C) is 0.1 to 5 parts by weight, preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the pulverized thermoplastic elastomer. When using a powder pigment supported on a carrier, the weight of the carrier is not included. If the amount of (c) is less than 0.1 parts by weight, good powder flow properties and powder moldability cannot be obtained.
When the amount exceeds 5 parts by weight, the heat fusion between the pulverized particles is reduced, and the strength of the obtained molded body tends to be poor.

The method for blending (C) with the pulverized thermoplastic elastomer is not particularly limited as long as (C) is a method of uniformly adhering to the pulverized thermoplastic elastomer. For example, there is a method of blending using a blender with a jacket, a high-speed rotary mixer, a Loedige mixer, or the like. Among them, a method of uniformly dispersing and preventing powder cohesion by applying a shearing force, such as a Henschel mixer or a super mixer, is preferred. The compounding is usually performed at room temperature.

The thermoplastic elastomer composition powder used in the present invention, in addition to (c), is based on 100 parts by weight of the pulverized thermoplastic elastomer composition.
(E) 0.1 to 5 parts by weight of a powder having a primary particle size of more than 300 nm and 10 μm or less may be blended. Here, (e) may be mixed with (e) at the same time as (c) above or after (c) is compounded,
After blending (e), (c) may be blended.

In this case, it is possible to obtain a thermoplastic elastomer composition powder which is more excellent in bulk specific gravity (packing properties) and coagulation resistance than when (c) is used alone.

Examples of (e) include the same powder pigments, inorganic oxides, vinyl chloride resins for pastes, fatty acid metal salts, calcium carbonate, etc. as in (c). (E) is added in an amount of 0.1 to 5 parts by weight, preferably 0.2 to 4 parts by weight, based on 100 parts by weight of the pulverized thermoplastic elastomer. When the amount exceeds 5 parts by weight, the thermal fusion between the thermoplastic elastomer powders of the present invention is reduced, and the strength of the obtained molded article tends to be poor. In this case, the weight ratio between (c) and (e) is usually 20:80 to 80:
20, preferably 25:75 to 60:40.

The above-mentioned thermoplastic elastomer composition powder can be applied to various powder molding methods such as a powder slush molding method, a fluid immersion method, an electrostatic coating method, a powder spraying method, and a powder rotational molding method. For example, the powder slush molding method is performed as follows.

First step: a step of applying a fluorine-based and / or silicon-based release agent on the molding surface of the mold. When performing powder molding with the thermoplastic elastomer composition powder of the present invention, when removing from the mold in the sixth step, since the adhesion force with the mold inner surface is strong, when the forcible removal is attempted, the obtained molded body is May break. Therefore, although not essential, it is preferable to coat the inner surface of the mold in advance with a spray such as a silicone spray or a fluorine spray. Examples of the silicone spray include KF96SP (diluted organic solvent) manufactured by Shin-Etsu Silicone Co., Ltd.
Examples of the fluorine-based spray include Daifree GA-6010 (diluted with organic solvent) and ME-413 (diluted with water) manufactured by Daikin.

Second step: On the molding surface of the mold heated above the melting temperature of the thermoplastic elastomer composition powder,
Step of Supplying a Thermoplastic Elastomer Composition Powder The thermoplastic elastomer composition powder is supplied at a temperature equal to or higher than the melting temperature of the composition, usually 160 to 320 ° C., preferably 21 to
It is supplied onto a molding surface of a mold heated to 0 to 300 ° C.
In this method, the mold is, for example, a gas heating furnace system,
Heating is performed by a heating medium oil circulation method, a dipping method in heat medium oil or hot fluidized sand, a high-frequency induction heating method, or the like. The heating time for heat-fusing the thermoplastic elastomer composition powder is appropriately selected according to the size and thickness of the target molded article.

Third step: a step of heating the thermoplastic elastomer composition powder on the molding surface of the second step for a predetermined time and fusing powders having at least their surfaces fused to each other. Heating is carried out for a predetermined time so that the powders whose surfaces have at least been melted are fused together.

Fourth step: a step of collecting the unfused powder after a lapse of the predetermined time in the third step. After the lapse of the predetermined time, the unfused powder is collected.

Fifth step: If necessary, a step of further heating the mold on which the molten thermoplastic elastomer composition powder is placed. If necessary, the molten thermoplastic elastomer composition powder is placed on the mold. Heat the mold further.

Sixth step: After the fifth step, the mold is cooled, and the molded body formed thereon is removed from the mold. The mold is cooled, and the molded body formed thereon is cooled. Remove from mold.

Further, by adding the above-mentioned lubricant internally during the production of the thermoplastic elastomer composition, there is an effect of reducing the load required for removing the molded body in the sixth step. In this case, the first step described above can be omitted. The amount of the lubricant is usually 5 parts by weight or less, preferably 0.1 to 2 parts by weight, per 100 parts by weight of the thermoplastic elastomer composition. Lubricant added 5
If the amount is more than the weight part, there may be a problem that the strength of the obtained molded body is reduced and the mold surface is contaminated.

The molded article of the present invention obtained from the powder of the thermoplastic elastomer composition of the present invention has a feature that even if it has a complicated shape, there are no problems such as underfilling and pinholes, and it is difficult to whiten even when bent. .

The thermoplastic elastomer composition powder of the present invention containing a foaming agent is powder-molded and further foamed to produce a foamed molded article.

The foaming agent may be contained in the powder or pellets in advance, or may be coated on the surface of the thermoplastic elastomer composition powder by a rotary mixer such as the aforementioned Henschel mixer.
The foaming agent may be blended after obtaining the thermoplastic elastomer composition powder by the above-described method, or may be blended simultaneously with the fine powder used in the present invention.

As the foaming agent, a pyrolytic foaming agent is usually used. Examples of such a pyrolytic foaming agent include azo compounds such as azodicarbonamide, 2,2'-azobisisobutyronitrile, and diazodiaminobenzene, benzenesulfonyl hydrazide, benzene-1,3-sulfonyl hydrazide, p- Sulfonyl hydrazide compounds such as toluenesulfonyl hydrazide, N, N'-dinitrosopentamethylenetetramine, N, N'-dinitroso-
Examples include nitroso compounds such as N, N'-dimethylterephthalamide, azide compounds such as terephthalazide, and carbonates such as sodium bicarbonate, ammonium bicarbonate and ammonium carbonate. Among them, azodicarbonamide is preferably used. The compounding of the blowing agent is usually performed at a temperature equal to or lower than the decomposition temperature of the blowing agent. Further, the thermoplastic elastomer composition powder of the present invention may contain a foaming aid and a cell regulator together with the foaming agent.

The molded article obtained by molding the powder of the thermoplastic elastomer composition of the present invention is useful as a skin material, and a two-layer molded article having a foam layer laminated on one surface side is used as the skin material. May be used. Such a two-layer molded body can be integrally produced by a powder molding method (see Japanese Patent Application Laid-Open No. 5-473, etc.), or a separately produced foam is added to the molded body obtained above with an adhesive or the like. It can also be manufactured by a method of bonding.

In order to produce a two-layer molded product by a powder molding method, for example, a mold which may have a complicated pattern on its molding surface is heated to a temperature not lower than the melting temperature of the thermoplastic elastomer composition powder. The above-mentioned thermoplastic elastomer composition powder is supplied onto the molding surface of the mold, and after the powders are thermally fused to each other to obtain a sheet-like molten material on the molding surface, an extra portion that has not been thermally fused is obtained. The powder is removed, and then the thermoplastic elastomer powder containing a foaming agent is added to the sheet-like melt (whether (c) a fine powder is compounded or not). Can be used.) And the powders are thermally fused to each other to obtain a sheet-like molten material on the molding surface. Then, excess powder that has not been thermally fused is removed, and then further heating is performed. do it By bubbles it is sufficient to form a foam layer.

Further, it is also possible to obtain a composite molded article composed of a non-foamed layer, a foamed layer and a non-foamed layer by a powder molding method. In this case, the non-foamed layers may be the same or different.

Examples of the foaming agent include the same pyrolytic foaming agents as described above. Examples of the polymer component in the thermoplastic polymer composition containing such a foaming agent include vinyl chloride resins, polyolefins, and olefins. And other thermoplastic elastomers. JP-A-7-228720 discloses a thermoplastic polymer composition containing a foaming agent.
The polyethylene-based foamable composition used in Japanese Patent Application Laid-Open No. H10-260, can also be used. The fine powder used in the present invention may be blended with the powder of the polyethylene-based foamable composition.

Further, a polyurethane foam can be used as the foam layer. In this case, since the adhesiveness between the thermoplastic elastomer composition of the present invention and polyurethane tends to be inferior, the adhesiveness is usually improved by pre-treating the adhesive surface of the molded article with a primer such as chlorinated polyethylene. Can be.

[0146] The polyurethane foam is fixed at a predetermined position with a predetermined gap between the above-mentioned molded article and a core material to be described later. A mixed solution of polyol and polyisocyanate is injected into the gap, and the polyurethane foam is pressurized. It is molded by foaming.

[0147] Such a molded article or a two-layer molded article is suitable as a skin material laminated on a thermoplastic resin core material. For example, the molded article is a multi-layered product comprising a thermoplastic resin core material laminated on one surface side. It can be used for a molded article, and the two-layer molded article can be used for a multilayer molded article in which a thermoplastic resin core is laminated on the foam layer side.

As the thermoplastic resin in the thermoplastic resin core material, for example, a polyolefin such as polypropylene or polyethylene, or a thermoplastic resin such as an ABS (acrylonitrile-butadiene-styrene copolymer) resin is used. Among them, a polyolefin such as polypropylene is preferably used.

In such a multilayer molded article, for example, a thermoplastic resin melt is supplied to one surface side of the molded article and pressurized, or the thermoplastic resin melt is supplied to the foam layer side of the two-layer molded article, and the molding is performed. It can be easily manufactured by a pressing method.

The thermoplastic resin melt is a thermoplastic resin that is heated to a temperature higher than its melting temperature and is in a molten state. The supply of the thermoplastic resin melt may be before the pressurization or may be simultaneous with the pressurization. The pressurization may be performed by using a mold or the like, or may be performed by the supply pressure of the thermoplastic resin melt. Examples of such a molding method include an injection molding method, a low-pressure injection molding method, and a low-pressure compression molding method.

Specifically, for example, when the above-mentioned molded body is used as a skin material, the molded body is supplied between a pair of opened molds, and then one side of the molded body and this After supplying or supplying the thermoplastic resin melt between one of the opposing molds, both molds may be clamped, and in the case of using a two-layer molded body as the skin material, an open pair is used. After supplying the two-layer molded body between the molds, and then supplying or while supplying the thermoplastic resin melt between the foamed layer of the molded body and one of the molds opposed thereto, the two molds are supplied. You only have to clamp the mold. Here, the opening / closing direction of the two dies is not particularly limited, and may be a vertical direction or a horizontal direction.

When a molded article or a two-layer molded article produced by using the above-mentioned powder molding die is used as the skin material,
The powder molding die can be used as one of the dies in the production of the multilayer molded body while holding the molded body or the two-layer molded body on the molding surface. According to this method,
Since the molded article or the two-layer molded article on which the pattern of the mold has been transferred is supplied between the molds without being separated from the mold, the pattern formed on the surface of the molded article is hardly destroyed, and the desired multilayer molding is performed. You can get the body.

The thermoplastic resin melt may be supplied after both molds have been clamped. However, a multilayer molded article in which the molded article or the two-layer molded article as the skin material has a small displacement and the degree of pattern transfer is improved. It is preferable that both dies be clamped during or after supply while both dies are not closed.
The method of supplying the thermoplastic resin melt is not particularly limited. For example, the thermoplastic resin melt can be supplied from a resin passage provided in one of the molds facing the molded product or the two-layer molded product.
Alternatively, the supply nose of the molten resin may be inserted between the two dies to supply the molten resin, and thereafter, the supply nose may be retracted outside the system to close both the dies.

As the pair of dies, a pair of male and female dies in which the outer peripheral surface of one die and the inner peripheral surface of the other die can slide can be used. In this case, by keeping the clearance between the sliding surfaces of the two dies approximately equal to the thickness of the molded article or the two-layer molded article, a multilayer molded article having an extra skin material at its end can be obtained. By folding this extra skin material on the back surface of the multilayer molded body, a multilayer molded body whose end is covered with the skin material layer can be obtained.

[0155]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

The evaluation of the thermoplastic elastomer composition and the molded article was performed by the following method.

[1] Complex dynamic viscosity η ^* (1) and Newton's viscosity index n Dynamic analyzer (RD) manufactured by Rheometrics
S-7700), the storage elastic modulus G ′ (ω) and the loss elastic modulus G ″ (ω) were measured at the vibration frequency ω = 1 radian / sec or 100 radian / sec, and the above-mentioned calculation formula (3) was used. ) Was used to calculate the complex dynamic viscosity η ^* (1) and η ^* (100). The measurement was performed in a parallel plate mode, an applied strain of 5%, and a sample temperature of 250 ° C. Also, η ^* (1) and η
^{* Using} (100), the Newtonian viscosity index n was determined by the above-mentioned equation (4).

[2] Ratio of the number of hydrogenated conjugated diene units having a side chain having 2 or more carbon atoms to the number of all hydrogenated conjugated diene units in (b) using o-xylene-d10 as a solvent 1.6 mg / m used
It was determined by measuring the ¹ H-NMR spectrum (400 MHz) at ¹ concentration.

[3] Solid Viscoelasticity A solid viscoelasticity measurement device Leo Vibron (DDV-II-EA type) of Orientec Kogyo KK was used, and a tensile mode was used. 2cm x 5cm (3.5mm between chucks)
cm) × 0.1 mm thick sample was prepared by press molding, and the temperature was raised at a rate of 2 ° C. within a range of −150 ° C. to 130 ° C.
/ Min, the sample was vibrated at an excitation frequency of 110 Hz and an excitation amplitude of 16 μm, and the peak temperature and intensity of the tan δ peak were determined.

[4] Bulk specific gravity of thermoplastic elastomer composition powder In accordance with JIS K-6721, 100 ml of thermoplastic elastomer powder was sampled and weighed, and the bulk specific gravity was calculated. The measurement was performed at 23 ° C.

[5] Powder Fluidity of Thermoplastic Elastomer Composition Powder 100 ml of the thermoplastic elastomer powder collected in the above [4] was put into a bulk specific gravity measuring device described in JIS K-6721, and the damper was pulled out to remove the powder. The time (the number of seconds) at which all of the powder was dropped from when it began to fall was measured. The measurement was performed at 23 ° C.

[6] Evaluation of molded article In the obtained molded article, three projections A (height 7 mm, width 25 mm) and B (height 11 mm, width 25 m) shown in FIG.
m) and C (having a height of 15 mm and a width of 25 mm) at each edge were visually checked for the presence of pinholes and underfills, and evaluated according to the following four grades. 1: Pinholes and underfill were formed on all of the convex portions A, B, and C. 2: There is no pinhole or underfill in the convex portion A, but the convex portions B and C
Pinholes and underfills were formed at the edges of. 3: The projections A and B have no pinholes or underfill, but the projections C
Pinholes and underfills were formed at the edges of. 4: No pinhole or underfill was formed on any of the protrusions A, B, and C.

[7] Bending Whitening A 1 mm thick molded sheet obtained by the powder slush molding method described below is cut into 1 cm × 5 cm, and bent at a bending load of 500 g or 1 kg. After one minute, the load is removed. The width was evaluated based on the following criteria based on the width of the whitened portion. 1: The width of the whitened portion is 2 mm or more 2: The width of the whitened portion is 1 mm or more and less than 2 mm 3: The width of the whitened portion is less than 1 mm 4: The whitened portion is not recognized

[(B) Rubbery Polymer Used] In the following examples, (B) is a hydrogenated product of a butadiene-styrene copolymer [styrene unit content: 10% by weight, hydrogenation rate: 99%
%, Η ^* (1) = 8.3 × 10 ³ poise, n = 0.16,
MFR = 10 g / 10 min, the ratio of hydrogenated conjugated diene units having a side chain having 2 or more carbon atoms to all hydrogenated conjugated diene units is 81%, the peak temperature of tan δ peak is −17 ° C., and the intensity is 1.5] was used. In addition, as (a), the aforementioned propylene-ethylene random copolymer resin (peak temperature of tan δ peak is −7 ° C., strength is 0.12, ethylene unit content = 5% by weight, MFR = 2
28 g / 10 min). These are represented by the ratios in Table 1,
Labo Plast Mill (Toyo Seiki Co., Ltd., Model 30C150)
The mixture was kneaded at 180 ° C. and 50 rpm for 10 minutes to obtain a composition (the total amount charged into the mill was 84 g).
The peak temperature and intensity of the tan δ peak of the composition obtained by the solid viscoelasticity measurement were determined. The resulting composition is
A new single tan δ peak was given at a temperature different from both the tan δ peak temperature in (a) and the tan δ peak temperature in (b) in the temperature range of -70 to 30 ° C. Table 1 shows the peak temperature and intensity of the tan δ peak of these compositions.

[0165]

[Table 1]

Example 1 [Production of thermoplastic elastomer composition powder] Propylene / ethylene copolymer resin [Ethylene unit content: 5% by weight, MFR = 228 g / 10 min, peak temperature of tan δ peak at -7 ° C, strength Is 0.12] 100 parts by weight,
(B) hydrogenated butadiene-styrene copolymer [styrene unit content 10% by weight, hydrogenation rate 99%, η ^*
(1) = 8.3 × 10 ³ poise, n = 0.16, MFR
= 10 g / 10 min, the ratio of the hydrogenated conjugated diene unit having a side chain having 2 or more carbon atoms to the total hydrogenated conjugated diene unit is 71%, and the peak temperature of the tan δ peak is −1.
7 ° C., strength 1.5) 100 parts by weight, and ethylene / propylene copolymer rubber [SPO V01 manufactured by Sumitomo Chemical Co., Ltd.]
41, propylene unit content 27% by weight, MFR = 1g
/ 10 min] by kneading 50 parts by weight using a twin-screw kneader at a shear rate of 1.2 × 10 ³ sec ^{-1 at} a temperature of 200 ° C. to obtain a composition [η ^* (1) = 2.7 × 10 ³ poise. , N = 0.07], which was cut using a cutting machine to obtain a granular material. The granules were cooled to -120 ° C. using liquid nitrogen, and then pulverized while maintaining the cooling state to obtain a pulverized thermoplastic elastomer composition [Tyler standard sieve 42 mesh (mesh size 355 μm).
mx 355 µm). To 100 parts by weight of the pulverized thermoplastic elastomer composition obtained above, alumina (alumina C, γ-alumina manufactured by Degussa Co., Ltd., primary particle size 13
nm) using a super mixer (5L super mixer SVM-5, manufactured by Kawada Seisakusho),
The mixture was mixed at 23 ° C. and 1500 rpm for 5 minutes to obtain a thermoplastic elastomer composition powder.

[Production of molded product by powder slush molding method] The obtained thermoplastic elastomer powder (3) is charged into a container (2), and then the container (2) and a mold (1) for slush molding are added. Were fixed to each other so that their peripheral portions were in close contact with each other, and integrated (FIG. 1). Here the mold (1)
As shown in FIG. 2, three concave portions (depths of 7 mm, 11 mm, and 15 mm, and widths of 25 m
m), and the entire surface of the molding die had a leather grain pattern. The temperature of the mold (1) was 260 ° C. Thereafter, the integrated mold and the container were immediately rotated 180 ° about the rotation axis (4) using a uniaxial rotation device (not shown).
Rotate to feed the thermoplastic elastomer powder (3) onto the mold surface of the mold,
By reciprocating two times in a range of 5 °, the thermoplastic elastomer powder was adhered and melted on the mold surface. After that, it was rotated again by 180 °, and the excess thermoplastic elastomer powder that was not attached and melted was collected in the container (2).
Next, the mold (1) with the thermoplastic elastomer powder attached and melted on the mold surface is removed from the container (2), heated in an oven at 260 ° C. for 1 minute, cooled, and demolded. Thus, a molded body (5) was obtained. This molded body (5) has a thickness of 1.0 mm, and has three projections A (height 7 mm, width 25 mm) and B (height 11 mm, width 25 m).
m) and C (height: 15 mm, width: 25 mm), and the grain pattern on the surface of the mold was accurately transferred over the entire surface. FIG. 3 shows a cross-sectional view of the molded body (5). Table 2 shows the properties of the thermoplastic elastomer composition powder and the evaluation results of the molded product.

Examples 2 to 4 Instead of alumina having a primary particle size of 13 nm, silica (manufactured by Nippon Aerosil Co., Ltd., grade 380, primary particle size 7 nm) was used.
Silica (manufactured by Degussa, OX50, primary particle size 40 nm),
Alumina (Sumitomo Chemical Co., Ltd., AK-50, α-alumina,
A thermoplastic elastomer composition powder was obtained in the same manner as in Example 1 except that the primary particle size was 200 nm).
A molded article was obtained. Table 2 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Examples 5 to 7 1.5 parts by weight of alumina having a primary particle size of 13 nm was added.
A thermoplastic elastomer composition powder was obtained in the same manner as in Example 1 except that the amount was changed to 2.0 parts by weight and 3 parts by weight, to obtain a molded article. Table 3 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Comparative Example 1 A thermoplastic elastomer composition powder was obtained in the same manner as in Example 1 except that alumina having a primary particle size of 13 nm was not blended to obtain a molded product. Table 4 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Comparative Examples 2 to 4 Instead of alumina having a primary particle size of 13 nm, alumina (AK-20, α-alumina, manufactured by Sumitomo Chemical Co., Ltd., primary particle size of 50) was used.
0 nm), alumina (AK-12, α-, manufactured by Sumitomo Chemical Co., Ltd.)
Alumina, primary particle diameter 800 nm), alumina (AK-10, α-alumina, manufactured by Sumitomo Chemical Co., Ltd., primary particle diameter 10)
The same procedure as in Example 1 was carried out except that the thickness of the thermoplastic elastomer composition was changed to obtain a molded product. Table 4 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Examples 8 and 9 Instead of alumina having a primary particle size of 13 nm, a black pigment (black pigment manufactured by Sumika Color Co., Ltd., 40 parts by weight of a fine powder pigment having a primary particle size of 100 nm was replaced with a primary particle size of 1.8 μm). Supported on 60 parts by weight of calcium carbonate), 1.0 part by weight, 2.0 parts by weight
Parts by weight (that is, the amount of the fine powder added was 0.1 wt.
Except for 4 parts by weight and 0.8 parts by weight), a thermoplastic elastomer composition powder was obtained in the same manner as in Example 1 to obtain a molded article. Table 5 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Example 10 Instead of alumina having a primary particle diameter of 13 nm, alumina (manufactured by Degussa, alumina C, γ-alumina, primary particle diameter of 13 nm) was used.
nm) and a black pigment (black pigment PV-801 manufactured by Sumika Color Co., Ltd., fine powder pigment 4 having a primary particle diameter of 95 nm)
0 parts by weight of calcium carbonate 60 having a primary particle size of 1800 nm
Except for using 1.0 part by weight (that is, 0.4 part by weight of fine powder added) of the thermoplastic elastomer composition powder, the same operation as in Example 1 was carried out. Thus, a molded product was obtained. Table 6 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Example 11 The same operation as in Example 1 was carried out except that the blending amount of the black pigment was changed to 2.0 parts by weight (that is, the added amount of the fine powder was 0.8 parts by weight). Thus, a thermoplastic elastomer composition powder was obtained to obtain a molded article. Table 6 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Example 12 In Example 10, 75 parts by weight of a brown pigment (manufactured by Sumika Color Co., Ltd., fine powder having a primary particle size of 150 nm) was used.
One supported on 25 parts by weight of 800 nm calcium carbonate. That is, except that the addition amount of the fine powder was changed to 0.75 parts by weight), a thermoplastic elastomer composition powder was obtained by the same operation as in Example 1 to obtain a molded article. Table 6 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.
Shown in

Examples 13 and 14 Instead of alumina having a primary particle size of 13 nm, a primary particle size of 40 was used.
1.0 parts by weight of silica (manufactured by Degussa, OX50) and a black pigment (black pigment, manufactured by Sumika Color Inc., primary particle diameter 100)
40 parts by weight of a fine powder pigment having a primary particle size of 1800 nm
Supported on 60 parts by weight of calcium carbonate)
Parts by weight (that is, 0.4 parts by weight of the fine powder is added), alumina (AKP-G008 manufactured by Sumitomo Chemical Co., Ltd.)
1.0 part by weight of α-alumina, primary particle size 100 nm) and a black pigment (black pigment, manufactured by Sumika Color Co., Ltd., primary particle size 100)
40 parts by weight of a fine powder pigment having a primary particle size of 1800 nm
Of a thermoplastic elastomer composition was obtained in the same manner as in Example 1 except that 60 parts by weight of calcium carbonate was used. Table 6 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.
Shown in

Example 15 Instead of alumina having a primary particle size of 13 nm, a primary particle size of 40 nm was used.
1.0 part by weight of silica (manufactured by Degussa Corporation, OX50) and 2.0 parts by weight of alumina silica having a primary particle diameter of 3.0 μm (grade JC-30, manufactured by Mizusawa Chemical Co., Ltd.) were used. Except for the above, the same operation as in Example 1 was performed to obtain a thermoplastic elastomer composition powder, and a molded article was obtained. Table 8 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.
Shown in

Comparative Example 5 EPDM [ML _{1 + 4} (100 ° C.) = 242, propylene unit content = 28% by weight, iodine value = 12] 25 parts by weight of a mineral oil-based softening agent [trade name, manufactured by Idemitsu Kosan Co., Ltd.] Diana Process PW-380] 25 parts by weight, oil-extended EPDM
Rubber [Sumitomo Chemical Co., Ltd., trade name Esplen E670F, M
L _{1 + 4} (100 ° C.) = 53]. Then, 50 parts by weight of a propylene / ethylene random copolymer resin [ethylene unit content = 5% by weight, MFR = 90 g / 10 min] and a crosslinking assistant [bismaleimide compound, Sumitomo Chemical Co., Ltd., trade name Sumifine] BM] and 0.6 parts by weight,
The mixture was kneaded with a Banbury mixer for 10 minutes to obtain a master batch for crosslinking (hereinafter, referred to as MB).
This M. B. Was pelletized using an extruder and a cutting machine. This M. B. Of the organic peroxide [2,3-dimethyl-2,5-di (t-butylperoxyno) hexane, manufactured by Sanken Kako Co., trade name: Samperox APO] to 100 parts by weight of the pellet In addition, using a twin-screw extruder, the mixture was kneaded at a shear rate of 1.2 × 10 ³ sec ^{-1 at} a temperature of 200 ° C. and dynamically crosslinked to obtain a thermoplastic elastomer. Then
Extruding this thermoplastic elastomer from a twin screw extruder,
It was cut into pellets using a cutting machine. The complex dynamic viscosity η ^* (1) of this thermoplastic elastomer is 1.5 × 10
^{The 3} poise, Newton viscosity index n was 0.25.
The obtained thermoplastic elastomer had two tan δ
It had a peak and no new single peak appeared at a temperature different from any of the peak temperatures. The peak temperature of each tan δ peak is −7 ° C. (the intensity is 0.12), and −45 ° C.
(The strength was 0.10). After cooling to −120 ° C. using liquid nitrogen, the granules are pulverized while maintaining the cooling state, and pulverized thermoplastic elastomer composition (passing through a 32 mesh Tyler standard sieve (500 μm × 500 μm opening)). Obtained. A thermoplastic elastomer composition powder was obtained in the same manner as in Example 1 except that this ground product was used, and a molded article was obtained. Table 7 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

[0179]

[Table 2]

[0180]

[Table 3]

[0181]

[Table 4]

* Comparative Example 1: The powder flowability of the thermoplastic elastomer composition powder was extremely poor, and the bulk specific gravity and the powder flowability could not be measured. JIS K-67
Even when the slit of the device described in No. 21 was struck with a wire, the powder did not fall. ** Comparative Examples 2-3: The powder flowability of the thermoplastic elastomer composition powder was extremely poor, and the powder flowability could not be measured with good reproducibility. However, JIS K-67
When the slit of the device described in No. 21 was pierced with a wire, the powder dropped and the bulk specific gravity could be measured.

[0183]

[Table 5]

[0184]

[Table 6]

[0185]

[Table 7]

[0186]

[Table 8]

[0187]

As described above, according to the present invention, a specific amount of a specific fine powder is blended with a pulverized thermoplastic elastomer composition containing a polyolefin resin and a rubbery polymer as essential components. A thermoplastic elastomer composition that has excellent powder flow characteristics, can produce a molded article having a complicated shape with almost no pinholes or underfill, and can give a molded article that is hardly whitened even when bent. A powder, a powder molding method using the powder, and a molded product obtained using the powder could be provided.

[Brief description of the drawings]

FIG. 1 is a conceptual cross-sectional view of a container containing a thermoplastic elastomer powder and a mold for slush molding.

FIG. 2 is a front view of a mold for slush molding.

FIG. 3 is a sectional view of a molded body.

[Description of Signs] 1 Mold for slush molding 2 Container 3 Thermoplastic elastomer powder 4 Rotation shaft 5 Molded body A Molded body convex part B Molded substance convex part C Molded substance convex part

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08J 3/12 CEQ C08J 3/12 CEQA CES CESA C08K 3/22 C08K 3/22 3/36 3/36 C08L 23/02 C08L 23 / 02 23/16 23/16 // B29K 9:00 23:00 105: 04 B29L 9:00 31:58

Claims (22)

[Claims] 1. The following (A) 100 parts by weight and (B) 10
-250 parts by weight, a complex elastomer having a complex dynamic viscosity η ^* (1) at 250 ° C of 1.5 × 10 ⁵ poise or less and a Newton viscosity index n of 0.67 or less. A thermoplastic elastomer composition powder comprising 0.1 to 5 parts by weight of the following (C) based on 100 parts by weight of the pulverized material. (A): Polyolefin-based resin (B): In a tan δ-temperature dependency curve obtained by a solid viscoelasticity measurement of a composition obtained by kneading with (A), a temperature range of −70 to 30 ° C. A) a rubbery polymer that gives a new single tan δ peak at a temperature different from both the tan δ peak temperature of (b) and the tan δ peak temperature of (b): (c) a fine powder having a primary particle size of 300 nm or less 2. The pulverized thermoplastic elastomer composition according to claim 1, wherein (a) 100 parts by weight, and (b) 10 to 2 parts.
50 parts by weight and the following (d) 250 parts by weight or less,
Complex dynamic viscosity η ^* (1) at 250 ° C. is 1.5 × 1
0 ⁵ poise or less and a thermoplastic elastomer composition powder according to claim 1, wherein Newtonian viscosity index n is a pulverized thermoplastic elastomer composition is 0.67 or less. (D): an ethylene / α-olefin copolymer having an α-olefin unit content of less than 50% by weight 3. The thermoplastic elastomer composition powder according to claim 1, wherein (b) is a conjugated diene-based rubbery polymer or a hydrogenated product thereof. 4. The thermoplastic elastomer composition powder according to claim 3, wherein the conjugated diene-based rubbery polymer is a copolymer of a conjugated diene and another monomer. 5. The thermoplastic elastomer composition powder according to claim 4, wherein the other monomer is a vinyl aromatic compound, a vinyl ester compound, an ethylenically unsaturated carboxylic acid ester compound or a vinyl nitrile compound. 6. (B) is an ethylene unit and having 4 to 4 carbon atoms.
2. The thermoplastic elastomer composition powder according to claim 1, which is an ethylene / α-olefin-based copolymer containing 20 α-olefin units and having a content of α-olefin units of 50% by weight or more. (B) the Shore A hardness measured according to ASTM D2240 is 70 or less;
The intrinsic viscosity [η] with xylene solvent at ℃ is 0.3d
The thermoplastic elastomer composition powder according to claim 1, which is a propylene / butene copolymer having a l / g or more. (B) the Shore A hardness measured according to ASTM D2240 is 70 or less;
The intrinsic viscosity [η] with xylene solvent at ℃ is 0.3d
1 / g or more propylene unit, α having 4 to 20 carbon atoms
The thermoplastic elastomer composition powder according to claim 1, which is a propylene / α-olefin / ethylene copolymer containing an olefin unit and an ethylene unit. 9. The thermoplastic elastomer composition powder according to claim 1 is added to the thermoplastic elastomer composition powder according to claim 1 per 100 parts by weight of the thermoplastic elastomer composition before compounding according to claim 1 with the following (e) 0.1 to 5: The thermoplastic elastomer composition powder according to claim 1, which is blended in parts by weight. (E) Powder having a primary particle size of more than 300 nm and 10 μm or less 10. The thermoplastic elastomer composition powder according to claim 1, wherein (c) is a powder pigment, alumina, silica or alumina silica. 11. The thermoplastic elastomer composition powder according to claim 9, wherein (e) is alumina, silica, alumina silica or calcium carbonate. 12. A powder molding method using the thermoplastic elastomer composition powder according to claim 1. 13. The thermoplastic elastomer powder according to claim 1, wherein a fluorine-based and / or silicone-based release agent is applied on the molding surface of the mold.
3. The powder molding method according to 2. 14. The powder molding method according to claim 13, comprising the following steps. First step: A step of applying a fluorine-based and / or silicon-based release agent on a molding surface of a mold Second step: On a molding surface of a mold heated to a melting temperature of a thermoplastic elastomer composition powder or higher. A step of supplying the thermoplastic elastomer composition powder to the third step: heating the thermoplastic elastomer composition powder on the molding surface of the second step for a predetermined time, and fusing the powders whose surfaces are at least melted to each other. Step Fourth step: After a lapse of a predetermined time in the third step,
Step of recovering unfused powder Fifth step: If necessary, step of further heating the mold on which the molten thermoplastic elastomer composition powder is placed Sixth step: After the fifth step, Cooling the mold and removing the sheet formed on it from the mold 15. A molded product obtained by powder molding the thermoplastic elastomer composition powder according to claim 1. 16. A two-layer molded product comprising a foamed layer laminated on one surface side of the molded product according to claim 15. 17. A multilayer molded article comprising the thermoplastic resin core material laminated on one surface side of the molded article according to claim 15. 18. A multilayer molded article comprising the thermoplastic resin core material laminated on the foam layer side of the two-layer molded article according to claim 16. 19. The method for producing a multilayer molded article according to claim 17, wherein a thermoplastic resin melt is supplied to one surface side of the molded article according to claim 15 and pressurized. 20. A thermoplastic resin melt is supplied to the foamed layer side of the two-layered molded article according to claim 16 and pressurized.
A method for producing the multilayer molded article according to the above. 21. The method according to claim 15, wherein the pair of molds is opened.
After supplying the molded body described above, and then supplying or supplying the thermoplastic resin melt between one surface side of the molded body and one mold opposite to the molded body, both molds are clamped. The method according to claim 19. 22. The method according to claim 16, wherein the pair of molds is opened.
After supplying the molded body described above, and then supplying or supplying the thermoplastic resin melt between one surface side of the molded body and one mold opposite to the molded body, both molds are clamped. The method according to claim 20.