JPH11323034A - Thermoplastic elastomer composition powder, powder molding and molded product using the powder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic elastomer composition powder excellent in powder flow characteristics, capable of producing a molded product of a complicated shape scarcely causing pinholes, underfills, etc., and providing the molded product hardly whitening even when bent and excellent in further solvent resistance and to provide a method for powder molding and the molded product using the same powder. SOLUTION: This thermoplastic elastomer composition powder is obtained by including 100 pts.wt. of a polyolefin-based resin, 10-250 pts.wt. of a rubber-like polymer and 0.01-10 pts.wt. of a pigment and further compounding a fine powder having <=300 nm primary particle diameter in an amount of 0.1-5 pts.wt. based on 100 pts.wt. of a pulverized thermoplastic elastomer composition having <=1.5×10<5> P complex dynamic viscosity η* at 250 deg.C and <=0.67 Newtonian viscosity index (n) therein.

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 relates to a pulverized thermoplastic elastomer composition containing a polyolefin resin, a rubbery polymer and a pigment as essential components, a specific fine powder being mixed in a specific amount, It has excellent fluidity characteristics, can produce molded products of complicated shapes with almost no pinholes or underfills, and gives molded products that are not easily whitened even when bent and are also excellent in solvent resistance. The present invention relates to a thermoplastic elastomer composition powder to be obtained, a powder molding method using the powder, and a molded product obtained by 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.

Further, a molded product obtained by powder-molding a powder obtained by pulverizing such a thermoplastic elastomer may be whitened when bent, which is a problem when producing a molded product having a complicated shape. 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, the problem to be solved by the present invention is a polyolefin resin,
A pulverized thermoplastic elastomer composition containing a rubbery polymer and a pigment as essential components is blended with a specific fine powder in a specific amount, and has excellent powder flow characteristics, such as pinholes and underfill. A thermoplastic elastomer composition powder capable of producing a molded article having a complicated shape with almost no occurrence, hardly whitening even when bent, and giving a molded article excellent in solvent resistance, and a powder using the powder. Another object of the present invention is to provide a molding method and a molded article obtained by using the powder.

[0005]

That is, the first aspect of the present invention is as follows: (a) 100 parts by weight;
Containing 250 parts by weight and (c) 0.01 to 10 parts by weight, and having a complex dynamic viscosity η ^* (1) at 250 ° C. of 1.5
× 10 ⁵ poise or less and Newton viscosity index n
The thermoplastic elastomer composition powder is obtained by mixing 0.1 to 5 parts by weight of the following (d) with 100 parts by weight of a pulverized thermoplastic elastomer composition having a particle size of 0.67 or less. (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.
(C) Pigment (d) Fine powder having a primary particle size of 300 nm or less The second invention of the present invention is a thermoplastic elastomer composition of the first invention The present invention relates to a powder molding method using powder. The third invention of the present invention relates to a molded product obtained by powder-forming the thermoplastic elastomer composition powder of the first invention.

[0006]

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. In addition, from the viewpoint of the strength of the molded body obtained by the powder molding method, JISK-7 of (a)
The melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kgf in accordance with No. 210 is usually 20 to 5
00 g / 10 min, preferably 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 dependence 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) as a conjugated diene rubbery polymer and a hydrogenated conjugated diene rubbery polymer which is a hydrogenated product thereof,
An ethylene-α-olefin-based copolymer containing an ethylene unit and an α-olefin unit having 4 to 20 carbon atoms and having a content of the α-olefin unit of 50% by weight or more, a propylene-butene-based copolymer having specific physical properties Copolymers and propylene-α-olefin-ethylene copolymers having specific physical properties are exemplified. 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 is a polymer rubber obtained by polymerizing or copolymerizing at least one conjugated diene. Examples of conjugated dienes include, for example, butadiene, isoprene, pentadiene,
Conjugated dienes having 4 to 8 carbon atoms, such as 2,3-dimethylbutadiene. Examples of the conjugated diene polymer rubber include polybutadiene, polyisoprene, polypentadiene, butadiene-isoprene copolymer and the like. The conjugated diene-based 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 is the 1- or 2-position of the vinyl group.
Position may be substituted with an alkyl group such as a methyl group. Examples of vinyl aromatic compounds include styrene, p
And vinyl aromatic compounds having 8 to 12 carbon atoms such as -methylstyrene and α-methylstyrene. Examples of the vinyl ester compound include vinyl acetate.
As the ethylenically unsaturated carboxylic acid ester compound,
Examples thereof include methyl methacrylate, ethyl methacrylate, methyl acrylate, and butyl acrylate. Examples of the vinyl nitrile compound include acrylonitrile and methacrylonitrile. Examples of the conjugated diene copolymer rubber include butadiene-styrene copolymer rubber, isoprene-styrene copolymer rubber, and butadiene-
Conjugated diene-vinyl aromatic compound copolymer rubber such as p-methylstyrene copolymer rubber, conjugated diene-vinyl ester compound copolymer rubber such as butadiene-vinyl acetate copolymer, butadiene-methacrylic acid copolymer rubber ,
Examples include conjugated diene-ethylenically unsaturated carboxylic acid ester compound copolymer rubber such as butadiene-methyl acrylate copolymer, and conjugated diene-vinyl nitrile compound copolymer rubber such as butadiene-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-based rubber include hydrogenated products of the above-described conjugated diene-based rubber. Such conjugated diene-based copolymer rubber or hydrogenated conjugated diene-based copolymer rubber is disclosed in, for example, JP-A-2-3624.
4, JP-A-3-72512, JP-A-7-1
It can be easily produced by the methods described in JP-A-18335, JP-A-56-38338, JP-A-61-60739 and the like. The conjugated diene-based copolymer rubber or hydrogenated conjugated diene-based copolymer rubber has a content of a monomer unit other than the conjugated diene of 50% by weight or less, preferably 20% by weight or less. This is preferable in that a molded product excellent in the above properties 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 number of carbon atoms relative to the total number of hydrogenated conjugated diene units is 2
The proportion of the number of hydrogenated conjugated diene units having the above side chains varies depending on the type of the conjugated diene monomer used in the polymerization, but is usually 50% or more, preferably 60 to 95%. And 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-based copolymer rubber containing up 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-based 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-3-1630088, 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 and the like. 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. Such an α-olefin unit content is 50% by weight.
The polymerization of the ethylene-α-olefin-based copolymer described above is usually performed in a solvent. As the solvent, for example, a hydrocarbon-based solvent such as hexane, heptane, toluene, ethylbenzene, and xylene is used. The polymerization is carried out in an atmosphere of an inert gas such as nitrogen, argon and hydrogen. 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 having a propylene unit of 0.3 dl / g or more, an α-olefin unit having 4 to 20 carbon atoms, and an ethylene unit.
-It is also possible to use olefin-ethylene copolymers.

The Shore A of such a propylene-butene-based copolymer and propylene-α-olefin-ethylene-based 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 the propylene-butene-based copolymer and the propylene-α-olefin-ethylene-based copolymer in 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-based copolymer and a propylene-α-olefin-ethylene-based 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 content of 1-butene in such a propylene-1-butene copolymer is preferably 0.5 to 90 mol%, more preferably 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.

In the propylene-α-olefin / ethylene copolymer, the content of the propylene unit and the content of the α-olefin unit 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. Outside of this range, the olefin-based thermoplastic elastomer composition may have poor low-temperature impact resistance.

The propylene-1-butene copolymer and the 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 propylene and / or 1-butene side chains in such a propylene-1-butene copolymer and the propylene and / or α-olefin units 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 by using a catalyst system used for polymerization of a propylene-1-butene-based copolymer and a propylene-α-olefin-ethylene-based 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-based copolymer rubber and the propylene-α-olefin-ethylene-based copolymer do not have an atactic structure, their hardness becomes high, and the flexibility of a molded product obtained by using a thermoplastic elastomer composition powder is increased. 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-based copolymer,
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): Boration of any of the following (C1) to (C3)
Compound (C1) General formula BQ¹Q^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 manufacturing method will be described in more detail. (A) The 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).
Zirconium atom, hafnium atom and the like can be mentioned.
Preferably it is a titanium atom or a zirconium atom. Examples of atoms belonging to Group 16 of the periodic table of the element represented by A in Formula [I] include an oxygen atom, a sulfur atom, and a selenium atom, and are preferably an oxygen atom. Examples of atoms belonging to Group 14 of the periodic table of the element represented by J in Formula [I] include a carbon atom, a silicon atom, and a germanium atom, and are preferably 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. All of these aralkyl groups include 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 and 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
^{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. All of these aryl groups are a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methoxy group, an alkoxy group such as 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 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.
Any of these substituted silyl groups is a hydrocarbon group, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methoxy group, an alkoxy group such as 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 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 are 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 and 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 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. All of these aralkyloxy groups include 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, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

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

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, aralkyl, aryl or substituted silyl group. Preferably, X ¹ and X ² are each independently a halogen atom, an alkyl group, an aralkyl group,
It is an alkoxy group, an aryloxy group or a disubstituted amino group, 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.
That is, 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 metal magnesium to form a cycloalkyl compound. A compound having a structure in which a group having a pentadiene skeleton and a group having an alkoxybenzene skeleton are connected by a Group 14 atom is obtained. Then, after treating the compound with a base, by reacting with a transition metal halide, hydrocarbon, hydrocarbon oxy compound, etc.
The transition metal complex represented by the general formula [I] can be synthesized.

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, and more preferably, triethylaluminum or triisobutylaluminum.

[0045] 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 is 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 boron compound (C) 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. And Q ^{1 to} Q ⁴ are the same as Q ^{1 to} Q ³ in (C1) above.

The general 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 combinations of these include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, and triphenylmethyltetrakis (Pentafluorophenyl) borate, triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned.
Most preferred is 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).

The compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— is a Bronsted acid (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 combinations of these 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-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 from 0.1 to 10,000, preferably from 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 at 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.

The polymerization reaction is carried out, for example, by solvent polymerization using an aliphatic hydrocarbon such as butane, pentane, hexane, heptane, octane, an aromatic hydrocarbon such as benzene or toluene, or a halogenated hydrocarbon such as methylene dichloride 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. The polymerization temperature is -50 to
Although it can take a range of 200 ° C., in particular, −20 to 100 ° C.
The polymerization pressure is preferably from normal pressure to 60 kg / cm.
² G are preferred. In general, the polymerization time is appropriately determined depending on the type of the catalyst to be used and the reaction apparatus, but is preferably 1 minute to 2 minutes.
A range of 0 hours can be taken. 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 component (c) of the present invention is a pigment. (C) Pigments include organic pigments such as azo, phthalocyanine, sulene, and dye lakes, oxides such as titanium oxide, molybdate chromate, selenium sulfide compounds, ferrocyan compounds, and carbon black. Inorganic pigments are used. (C) As the pigment, any of a liquid substance and a powdery substance can be used. When a powdery material is used, the primary particle size is preferably 300 nm or less, more preferably 200 nm or less, and particularly preferably 150 nm or less, from the viewpoint of uniform coloring. When a powdery pigment is used, a pigment supported on a carrier such as calcium carbonate, metal soap, or magnesium oxide can also be used. In this case, the primary particle size of the carrier is usually 10
μm or less, preferably 1 μm to 5 μm. In this case, the weight ratio of the powder pigment to the carrier is usually 20:80 to 8
0:20, preferably 25:75 to 75:25.
As (c), a corresponding commercially available product can be used.

The thermoplastic elastomer composition of the present invention comprises:
(A) 100 parts by weight, (b) 10 to 250 parts by weight, and (c) 0.01 to 10 parts by weight,
Preferably, it contains (a) 100 parts by weight, (b) 40 to 200 parts by weight, and (c) 0.1 to 5 parts by weight. If the content of (b) is too small, the flexibility of the obtained molded product is inferior, while if the content is too large, the obtained molded product has a sticky feeling. If the content of (c) is too small, the concealing properties of the obtained molded article will be insufficient, while if the content is too large, the solvent resistance of the obtained molded article will decrease. When a powder pigment supported on a carrier is used as (c), the weight of the carrier is not included. When a pigment is contained in the thermoplastic elastomer composition, the obtained molded article has good concealing properties (uniform coloring properties).

The thermoplastic elastomer composition of the present invention comprises:
In addition to the essential components (a), (b) and (c),
(E) An ethylene-α-olefin-based copolymer having an α-olefin unit content of less than 50% may be contained.
Note that (e) falls within a temperature range of −70 to 30 ° C. in a tan δ-temperature dependency curve obtained by a solid viscoelasticity measurement of a composition obtained by kneading (a) and (e). Has no property of giving a new single tan δ peak at a temperature different from both the tan δ peak temperature of (e) and the tan δ peak temperature of (e). When (e) is contained, the cost performance can be improved without lowering the powder moldability of the thermoplastic elastomer powder and the whitening resistance when the molded product obtained by powder molding the powder is bent. Provides an excellent thermoplastic elastomer composition.

(E) The α-olefin unit content is 50%
The ethylene-α-olefin-based copolymer is less than
Copolymer of ethylene and α-olefin, ethylene, α
A polymer having little crystallinity, such as a copolymer of an olefin and a non-conjugated diene, or a crystallinity of 5
Less than 0% polymer. Here, the degree of crystallinity indicates the ratio of the heat of fusion of the copolymer to the heat of fusion of the crystalline polyethylene homopolymer. The heat of fusion is determined by the DSC method. Here, the α-olefin is an α-olefin having 3 to 10 carbon atoms such as propylene, 1-butene, and 3-methyl-1-butene, and the non-conjugated diene is dicyclopentadiene, 2-5-ethylidene norbornene, Examples thereof include non-conjugated dienes having 5 to 15 carbon atoms such as 1,4-hexadiene, 1,5-cyclooctadiene, and 2-methylene-5-norbornene.
Such ethylene-α-olefin copolymers include:
For example, an ethylene-propylene copolymer, an ethylene-butene copolymer, an ethylene-propylene-ethylidene norbornene copolymer (hereinafter, referred to as “EPDM”) and the like can be mentioned. 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 is produced from 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 (e) is used, the amount of (e) 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 (e) 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) means the storage elastic modulus G ′ (ω) and the loss elastic modulus G ″ at a temperature of 250 ° C. and a vibration frequency ω.
This is a value calculated by the following formula (3) using (ω), and the complex dynamic viscosity η ^* (1) is a complex dynamic viscosity at ω = 1 radian / sec. η ^* (ω) = ｛[G ′ (ω)] ² + [G ″ (ω)] ² ｝ ^1/2 / ω (3) When η ^* (1) exceeds the above upper limit, the thermoplastic elastomer The melt fluidity of the composition is inferior, and it tends to be difficult to produce a molded article by a molding method having a low shear rate at the time of molding, such as a powder molding method, usually 1 second ^-1 or less.

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 above complex dynamic viscosity η ^* (1), temperature 250 ° C., vibration frequency ω = 100
Complex dynamic viscosity η ^* (100) measured in radians / second
And a value calculated by the following calculation formula (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 body decreases.

As a method for obtaining the thermoplastic elastomer composition of the present invention, for example, the following method can be mentioned. That is, (a), (b) and (c) and (e) as needed may be melt-kneaded. Also, (a),
It can also be produced by kneading or dynamically cross-linking all or some of (b) and (c) and if necessary (e), and then kneading or dynamically kneading the unselected components. . For example, the thermoplastic elastomer composition of the present invention in which (a) and / or (e) is cross-linked intra- and / or inter-molecularly, usually after dynamically cross-linking (a) and (e). , And (b) and (c) are added and kneaded. Here, a single-screw extruder or a twin-screw extruder can be used for kneading. In addition, the compounding of various additives described below is
For example, these additives were previously blended (a),
It can be carried out by using (b), (c) or (e) or by mixing the above components during kneading or dynamic crosslinking.

The dynamic crosslinking of the kneaded mixture can be performed, 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 (e).
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 used is usually 0 per 100 parts by weight of the total of the components to be crosslinked among (a), (b) and, if necessary, (e). .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, (e) to be crosslinked.
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 cross-linking of (a), (b) and (e) is carried out by heating a component to be cross-linked, a cross-linking agent, and, if necessary, a cross-linking assistant, while heating the single-screw extruder or the twin-screw extruder. It can be performed by kneading under heating, for example, in a temperature range of 150 to 250 ° C. using an extruder or the like.

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 were measured in the 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 may be used by being previously contained in (a), (b), and (e), or may be used at the time of the above-mentioned kneading or dynamic crosslinking or after kneading. It may be blended. The thermoplastic elastomer composition containing the mineral oil-based softener is excellent in melt fluidity and can give a molded article excellent in flexibility. When an oil-extended olefin copolymer containing such a mineral oil-based softening agent in (e) 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 above-mentioned complex dynamic viscosity and Newtonian viscosity index, the above-mentioned degree of 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 pulverizing the thermoplastic elastomer obtained by the above-mentioned method and then adding (d) fine powder.

The pulverization method of the thermoplastic elastomer composition includes 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).

The fine powder used in the present invention comprises (d) 1
It is a fine powder having a secondary particle size of 300 nm or less. Examples of (d) used in the present invention include inorganic oxides, vinyl chloride resins for pastes, and fatty acid metal salts. However, in addition to the pigment as (c), (d) a powder pigment as a fine powder (preferably the same color as the (c) pigment)
May be appropriately added and used. In addition, when the whole amount of the powder pigment is blended with the pulverized thermoplastic elastomer composition without using (c), the solvent resistance is insufficient. The primary particle size of (d) needs to be 300 nm or less, 200 nm or less, and more preferably 5 nm to 15 nm.
It is preferably 0 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 means that a photograph of (d) is taken by a transmission electron microscope (TEM), about 1,000 particles are arbitrarily selected, and the diameters of the particles are measured. It is the value divided by the number of particles.

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

Almost all aluminas have the chemical formula 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. Silica is a fine powder that is mostly composed of SiO ₂ units of the chemical formula. Manufactured by methods such as pulverization of natural diatomaceous earth and 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. Examples of powder pigments include organic pigments such as azo, phthalocyanine, sullen and dye lakes, oxides such as titanium oxide, molybdic acid chromate, selenium sulfide compounds, ferrocyan compounds, and inorganic pigments such as carbon black. Is used. These (d) are used alone or in combination of two or more having a primary particle size of 300 nm or less. For example, an inorganic oxide alone can be used, or a powdered pigment and an inorganic oxide can be used in combination. When a powder pigment is used, a pigment supported on a carrier such as calcium carbonate, metal soap, or magnesium oxide can also be used. In this case, the primary particle size of the carrier is usually 10 μm or less, preferably 1 μm or less.
μm to 5 μm. In this case, the weight ratio of the powder pigment to the carrier is usually 20:80 to 80:20, preferably 2:80.
5:75 to 75:25. In the case where a powder pigment supported on a carrier is used as (d), the weight of the carrier is not included. The primary particle size of the carrier exceeds 300 nm
The case of 0 μm or less is included in (f) described later.
(D) The addition amount of the fine powder 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. If the amount is less than 0.1 part by weight, good powder flow characteristics 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 of blending (d) the fine powder with the pulverized thermoplastic elastomer is not particularly limited as long as (d) the fine powder is uniformly adhered to the pulverized thermoplastic elastomer. Not something. For example, a method of blending using a blender with a jacket, a high-speed rotary mixer, or the like can be used. 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.
In addition, the thermoplastic elastomer composition powder used in the present invention contains (d) 1 part with respect to 100 parts by weight of the pulverized thermoplastic elastomer composition in addition to (d) fine powder.
0.1 to 5 parts by weight of a powder having a secondary particle size of more than 300 nm and 10 μm or less may be blended. here,
(F) may be mixed with (F) at the same time as the above (D) or after (D),
After blending (f), (d) 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 (f) is used alone. Examples of (f) include inorganic oxides such as alumina, silica, and alumina-silica, calcium carbonate, vinyl chloride resins for pastes, and fatty acid metal salts similar to (d). The amount of (f) is 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 (f) and (d) is usually 20:80 to 80:20, preferably 25: 7.
5 to 60:40.

The above 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: a step of supplying the thermoplastic elastomer composition powder onto the molding surface of the mold heated to a temperature not lower than the melting temperature of the thermoplastic elastomer composition powder. As described above, the temperature is 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 for a predetermined time on the molding surface. For a period of time to fuse the powders, the surfaces of which have been melted at least. Fourth step: after a lapse of a predetermined time in the third step,
Step of Recovering Unfused Powder After the predetermined time has elapsed, the unfused powder is recovered. Fifth step: If necessary, a step of further heating the mold on which the molten thermoplastic elastomer composition powder is placed. If necessary, remove the mold on which the molten thermoplastic elastomer composition powder is placed. Further heat. 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 removed from the mold. Remove.

In addition, 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 article 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 thermoplastic elastomer composition powder of the present invention has no problems such as underfilling and pinholes even if it has a complicated shape, is hardly whitened even when bent, and has a solvent resistant property. It has the feature of being excellent in properties. In addition, the thermoplastic elastomer composition powder of the present invention containing a foaming agent is powder-molded and further foamed, whereby a foamed molded article can be produced.

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 method described above, or may be blended simultaneously with (d) 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. 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 article by the powder molding method, for example, after 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 melt on the molding surface, the excess is not thermally fused. The powder is removed, and then a thermoplastic elastomer powder containing a foaming agent on this sheet-like melt (whether (d) 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 form a composite molded article comprising a non-foamed layer / foamed layer / non-foamed layer by a powder molding method. In this case, the non-foamed layers may be the same or different.

Further, it is also possible to form a composite molded article comprising a non-foamed layer / foamed layer / 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 resin, polyolefin, and olefin. 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.

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. It is molded by foaming.

Such a molded article or a two-layer molded article is suitable as a skin material to be laminated on a thermoplastic resin core material. 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 material 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 side of the molded article and pressurized. 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 surface side of the molded body and the After supplying or supplying the thermoplastic resin melt between one of the opposing molds, the two molds may be clamped, and when a two-layer molded body is used 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, 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 the clamping of both the molds is completed. 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.

[0104]

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 following methods were used to evaluate the thermoplastic elastomer composition and the molded article. [1] Complex dynamic viscosity η ^* (1) and Newton 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, 0.6 mg / m
It was determined by measuring the ¹ H-NMR spectrum (400 MHz) at ¹ concentration. [3] Solid viscoelasticity A solid viscoelasticity measuring device, Levivibron (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, 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] is put into a bulk specific gravity measuring device described in JIS K-6721, the damper is pulled out, and the powder falls. From the start, the time (in seconds) at which all of the powder finished falling was measured. The measurement was performed at 23 ° C. [6] Evaluation of molded article In the obtained molded article, three convex portions 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 formed sheet obtained by the powder slush molding method described below is cut into 1 cm x 5 cm, and after bending at a bending load of 500 g or 1 kg, the load is removed one minute later, and the whitened portion is bent. Was evaluated according to the following criteria on the basis of the width. 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: No whitened portion is recognized [8] Solvent resistance According to the powder slush molding method described below. The obtained molded sheet having a thickness of 1 mm was cut into 15 cm × 5 cm. Diameter 6
A weight having a weight of 0 mm and a weight of 500 g is wrapped in a white cloth (flannel), immersed in white gasoline (Mobil Co., Ltd., unleaded red gasoline), and then reciprocated 10 times (1 reciprocation 1) on the molded sheet.
(Moving distance, one way, 50 mm). The solvent resistance was evaluated according to the following criteria. 1: The white cloth was significantly colored, and the molded sheet was significantly whitened (discolored). 2: The white cloth was slightly colored, and the molded sheet was slightly whitened (discolored). 3: The white cloth was slightly colored, but the formed sheet was not whitened (discolored). 4: The white cloth is not colored at all, and the molded sheet is whitened (color loss).
Did not.

[(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 the hydrogenated conjugated diene unit having a side chain having 2 or more carbon atoms to the total hydrogenated conjugated diene units is 71%, the peak temperature of the 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.

[0106]

Table 1 Temperature and intensity of the tan δ peak of the composition consisting of (a) and (b)

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, ethylene-propylene copolymer [manufactured by Sumitomo Chemical Co., Ltd., SPO V0141, propylene unit content 27% by weight, MFR = 1 g / 10
50 parts by weight) and a black pigment carrier (40 parts by weight of a fine powder pigment having a primary particle size of 100 nm, manufactured by Sumika Color Co., Ltd.)
Supported by 60 parts by weight of calcium carbonate having a secondary particle size of 1.8 μm] 2.5 parts by weight (that is, the substantial addition amount of the black pigment is 1.0 part by weight) using a twin-screw kneader at a shear rate of
The composition [η was kneaded at 2 × 10 ³ sec ^{-1 at} a temperature of 200 ° C.
^* (1) = 2.7 × 10 ³ poise, n = 0.07]
This was cut using a cutting machine to obtain a granular material. After cooling the granules to -120 ° C using liquid nitrogen, the granules are pulverized while keeping the cooling state, and pulverized thermoplastic elastomer composition [Tyler standard sieve 42 mesh (mesh size 355 μm ×
355 μm). Alumina (alumina C, γ-alumina, primary particle diameter 13 n, manufactured by Degussa Co., Ltd.) was added to 100 parts by weight of the pulverized thermoplastic elastomer composition obtained above.
m) Using a supermixer (5 L supermixer SVM-5, manufactured by Kawada Seisakusho), 2 parts by weight of 1.0 part by weight
The mixture was mixed at 3 ° 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.

Example 2 A thermoplastic elastomer composition was prepared in the same manner as in Example 1 except that silica (OX50, primary particle diameter: 40 nm, manufactured by Degussa) was used instead of alumina having a primary particle diameter of 13 nm. A product powder was obtained to obtain a molded product. Table 2 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Examples 3 to 4 The procedure of Example 1 was repeated, except that the addition amount of alumina having a primary particle diameter of 13 nm was changed to 1.5 parts by weight and 2.0 parts by weight, respectively. A powder was obtained to obtain a molded body. Table 2 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Example 5 The procedure of Example 1 was repeated, except that the addition amount of alumina having a primary particle diameter of 40 nm was changed to 0.7 part by weight, to obtain a thermoplastic elastomer composition powder, and to obtain a molded article. Was. Table 2 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Example 6 Instead of a black pigment carrier, a brown pigment carrier [manufactured by Sumika Color Co., Ltd., 40 parts by weight of a fine powder pigment having a primary particle size of 100 nm is 60 parts by weight of calcium carbonate having a primary particle size of 1.8 μm] 2.5 parts by weight (that is, the actual addition amount of the brown pigment is 1.0 part by weight) was obtained in the same manner as in Example 1 to obtain a thermoplastic elastomer composition powder and a molded article. Was. 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 diameter of 13 nm was not blended, and a molded product was obtained. Table 4 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Comparative Example 2 A pulverized thermoplastic elastomer composition [η ^* (1) = 2.7 ×) according to Example 1, except that no black pigment (fine powder pigment manufactured by Sumika Color Co., Ltd.) was used. 10 ³ poise, n = 0.
07] was obtained. A black pigment (black pigment manufactured by Sumika Color Co., Ltd., fine powder pigment 4 having a primary particle diameter of 100 nm)
0 parts by weight of calcium carbonate 60 having a primary particle size of 1.8 μm
Per 100 parts by weight of the propylene-ethylene copolymer resin (contained in the thermoplastic elastomer composition) (that is, the substantial amount of the black pigment is 1.0% by weight). Parts by weight) using a supermixer in the same manner as in Example 1 to obtain a thermoplastic elastomer composition powder. Table 4 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

Comparative Example 3 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, a propylene-ethylene random copolymer resin [ethylene unit content = 5% by weight, MFR = 90 g / 10 min] 100
1.2 parts by weight of a cross-linking aid [bismaleimide compound, manufactured by Sumitomo Chemical Co., Ltd., trade name Sumifine BM], 40 parts by weight of a black pigment carrier [manufactured by Sumika Color Co., Ltd .; Part supported on 60 parts by weight of calcium carbonate having a primary particle diameter of 1800 nm] 2.0 parts by weight (that is, 0.8 parts by weight of a black pigment is substantially added) and kneaded for 10 minutes using a Banbury mixer. Thus, a master batch for crosslinking (hereinafter, referred to as MB) was obtained. 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 4 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product. Example 7 Instead of alumina having a primary particle size of 13 nm, a primary particle size of 40 was used.
nm silica (OX50, manufactured by Degussa) and 2.0 parts by weight of alumina silica (grade JC-30, manufactured by Mizusawa Chemical Co., Ltd.) having a primary particle size of 3.0 μm. Was operated in the same manner as in Example 1 to obtain a thermoplastic elastomer composition powder, and a molded article was obtained. Table 5 shows the evaluation results of the thermoplastic elastomer composition powder and the molded product.

[0116]

[Table 2]

[0117]

[Table 3]

[0118]

[Table 4]

[0119]

[Table 5]

[0120]

As described above, according to the present invention, a specific fine powder is blended with a specific amount in a pulverized thermoplastic elastomer composition containing a polyolefin resin, a rubbery polymer and a pigment as essential components. It has excellent powder flow properties, can produce molded articles of complex shapes with almost no pinholes or underfills, and is hard to whiten even when bent, and has excellent solvent resistance It was possible to provide a thermoplastic elastomer composition powder capable of giving a molded article, a powder molding method using the powder, and a molded article obtained by using the powder.

[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.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Mold for slush molding 2 Container 3 Thermoplastic elastomer powder 4 Rotating shaft 5 Molded body A Molded convex part B Molded convex part C Molded convex part

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3/22 C08K 3/22 3/26 3/26 3/36 3/36 C08L 9/00 C08L 9/00 21/00 21 / 00 23/08 23/08 // B29K 21:00 23:00 B29L 7:00

Claims (22)

[Claims] 1. The following (A) 100 parts by weight, (B) 10
Containing 250 parts by weight and (c) 0.01 to 10 parts by weight, and having a complex dynamic viscosity η ^* (1) at 250 ° C. of 1.5
× 10 ⁵ poise or less and Newton viscosity index n
A thermoplastic elastomer composition powder comprising 0.1 to 5 parts by weight of the following (d) with respect to 100 parts by weight of a pulverized thermoplastic elastomer composition having a particle size of 0.67 or less. (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): pigment (d): 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, (c) 0.01 to 10 parts by weight, and (e) 250 parts by weight or less, and the complex dynamic viscosity η ^* (1) at 250 ° C. is 1.5 × 10 ⁵ poise or less. The thermoplastic elastomer composition powder according to claim 1, which is a pulverized thermoplastic elastomer composition having a Newton viscosity index n of 0.67 or less. (E): 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.
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
2. The thermoplastic elastomer 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 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 mixed with 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 (f) 0.1 to 5: The thermoplastic elastomer composition powder according to claim 1, which is blended in parts by weight. (F) 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 (d) is a powder pigment, alumina, silica or alumina silica. 11. The thermoplastic elastomer composition powder according to claim 9, wherein (f) 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.
Powder molding method according to 2 above 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.