JP2001002731A - Low molecular weight ethylene-based polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer containing a specific unsaturated bond at the one side terminal of the polymer chain and useful for the production of a releasing agent for a toner, a pigment-dispersing agent, and a lubricant for the molding of a vinyl chloride resin by polymerizing ethylene singly or ethylene with a specific α-olefin by using a specific catalyst. SOLUTION: The objective polymer having a vinyl type or a vinylidene type unsaturated bond at the one side terminal of the polymer chain consists of ethylene singly or ethylene and a 3-10C α-olefin and which satisfies (1) the content ratios of the ethylene unit and the α-olefin unit are 81-100 mol% and 0-19 mol% range, respectively, and (2) its intrinsic viscosity [η] measured at 135 deg.C in decalin is 0.01-1.7 dl/g, (3) its molecular weight distribution (Mw/Mn) measured by GPC is <=3 and (4) its number of vinyl groups M and number of vinilidene groups N per 1,000 carbon atoms measured by an infrared absorption method satisfy a relational formula: M+N>=14,000/Mw.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel low molecular weight ethylene-based polymer, and more particularly, to a polymer in which one end of a polymer chain is substituted with a predetermined functional group and its use.
More specifically, an ethylene polymer having a specific molecular weight and composition having a vinyl-type or vinylidene-type unsaturated bond at one end of a polymer chain, and a release agent, a pigment dispersant, and a vinyl chloride resin molding for the toner. It relates to the use for lubricants.

[0002]

BACKGROUND OF THE INVENTION (Low molecular weight ethylene polymer) Low molecular weight ethylene polymer belongs to the class of polyethylene (PE) oligomer. Polyethylene oligomer is also referred to as polyethylene wax, animal and plant based, mineral based,
It is roughly divided into petroleum refining system and synthetic system. As a polyethylene wax containing a functional group at one end of the polymer chain,
Mineral montanic acid waxes can be mentioned. However, since montanic acid wax is extracted and purified from natural lignite, the production cost is high. Further, in the case of montanic acid wax, the molecular weight is limited to about 800 (dimer), and the terminal of the polymer chain is mainly a carboxylic acid or an ester thereof, and those having other functional groups are not used. There were few kinds.

[0003] As a synthetic system capable of producing polyethylene wax at a low cost, there is a system using a metallocene catalyst. However, in such a system,
Although a vinyl group can be introduced at one end of the polymer chain, the use of a chain transfer agent such as hydrogen is required to reduce the molecular weight of the polymer. Since the terminal of the polymer formed by this chain transfer agent is saturated, there has been a problem that the number of vinyl groups at one end of the polymer chain which enables introduction of another functional group is extremely reduced.

[0004] As a synthetic system capable of producing polyethylene wax at a low production cost, there is also a system for thermally decomposing the synthesized polyethylene to reduce the molecular weight. However, in this case, the proportion of terminal vinyl groups produced was higher than in systems using metallocene catalyst systems, but was still insufficient.

In either of the general-purpose synthesis methods, the high-pressure radical method or the Ziegler-catalyzed method, there is almost no vinyl group at the terminal of the obtained polymer chain, and the terminal vinyl group is intentionally added to the polymer chain. It was difficult to introduce.

(Release Agent for Toner) A developer for electrophotography, so-called electrostatic toner, is used in electrostatic electrophotography to develop a latent image formed by charging and exposing to form a visible image. . The electrostatic toner contains charged fine powder obtained by dispersing a colorant such as carbon black and a pigment in a resin. As the electrostatic toner, a dry two-component toner using both a charged fine powder and a carrier such as iron powder and glass particles, a wet toner in which the charged fine powder is dispersed in an organic solvent such as isoparaffin, and a magnetic fine powder are dispersed. Dry one-component toner.

By the way, an image obtained by developing on a photoreceptor using an electrostatic toner is obtained after being transferred to paper or directly developed on paper on which a photosensitive layer is formed. As it is, it is fixed by heat or solvent vapor. Above all, fixing by using a heating roller is a contact-type fixing method, so that it has high thermal efficiency, can reliably fix an image even with a relatively low-temperature heat source, and is suitable for high-speed copying. It has the advantages of

In recent years, in addition to monochrome photographs,
The use of color electrophotography is expanding, and the need to fix images under low energy is increasing. As photocopiers have advanced into home appliances and small appliances, reduction in power consumption in the heating roller section used for fixing is required, and output terminals of high-speed appliances such as computers are required. Demands for high-speed fixing properties are also increasing. However, when an image is fixed by contacting a heating element such as a heating roller, if a conventional electrostatic toner is used,
A phenomenon in which a part of the heating element adheres and is transferred to a subsequent image portion, a so-called offset phenomenon, may occur. In particular, when the temperature of the heating roller is low, the electrostatic toner cannot be sufficiently softened by this heating, so that the fixing property of the toner to the printing paper or film is likely to decrease simultaneously with the offset phenomenon. In particular, in existing color copiers and color printers that require wax addition or the like and are difficult to prevent the occurrence of offset, for example, by impregnating the roller surface with silicone oil or supplying silicone oil to the roller surface, The offset phenomenon is eliminated. However, in this case, there are problems such as the roller itself becoming dirty, the obtained image being glaring, the equipment being unable to be miniaturized, and the need for periodic replenishment of silicone oil.

[0009] As a binder which is a main material of the electrostatic toner,
Various thermoplastic resins have been used. Among these thermoplastic resins, aromatic polyester resins using a low molecular weight styrene / (meth) acrylic acid ester copolymer, a BIS-phenol A derivative or phthalic acid are particularly preferable because of their good chargeability. Softening point (around 100 ° C)
That it has good fixability, low hygroscopicity,
It has features such as good mixing with carbon black and pigment, which are colorants, easy pulverization, and easy cleaning of the photoconductor when the resin adheres to the photoconductor, minimizing contamination. . However, even in the conventional electrostatic toner, it is required to design a resin having sharper melt and higher fluidity from the viewpoint of colorization and maintenance of image quality at that time. It is difficult to prevent the occurrence of offset in the temperature range.

In order to solve such a problem, it has been proposed to add a polyolefin wax as a release agent in the conventional electrostatic toner (Japanese Patent Publication No. 52-3304).
JP-A-52-3305, JP-A-57-52574,
58-58664 and JP-A-58-59455), and monochrome electrostatic toners have been put to practical use.
However, it has been difficult to improve high-temperature releasability and low-temperature fixability.

(Pigment dispersant) As a method for coloring a synthetic resin such as polystyrene, ABS, polycarbonate, polyester, polyamide, etc., a dry color method or a color compound method is mainly employed, and it is possible to rapidly disperse and mix. The masterbatch method was not widely adopted. In either method, a pigment dispersant is used to uniformly disperse the pigment in the synthetic resin. Conventionally, various metal salts of higher fatty acids such as stearic acid, low molecular weight polystyrene, and styrene-acrylate copolymer oligomers have been used as pigment dispersants for these synthetic resins. However,
When these are used as a pigment dispersant, there are drawbacks such as that pigments and the like bleed out from the obtained polymer, and that the dispersibility of the pigment is lowered and the transparency of the polymer is lowered. Further, when a low-molecular-weight polyolefin is used as a pigment dispersant, there is a problem that the kneading workability is reduced when a dry color is prepared in the dry color method or when the dry color is kneaded with a styrene-based polymer, for example. Further, there was a disadvantage that the obtained polymer had poor pigment dispersibility. Further, when the pigment dispersant is used, a large amount of pigment cannot be uniformly dispersed in the synthetic resin, so that it has been difficult to adopt the master batch (MB) method.

On the other hand, in a method of coloring a polyolefin resin such as polyethylene or polypropylene and a polyvinyl chloride resin, a pigment is dispersed at a high concentration in polyethylene or other resin using a dispersant such as low molecular weight polyethylene or fatty acid metal soap. Masterbatch methods that can be used are often used. However, with the conventional masterbatch method, the pigment concentration could not be made too high. In recent years, the coloring of polyolefin or other synthetic resins tends to require high dilution ratio and high-speed coloring, and it is becoming difficult to sufficiently cope with the conventional masterbatch method. In particular, in thin and large injection molded articles, the dispersion rate of the dye and pigment in the fatigue-colored resin of the master batch is insufficient, so that the problem of poor appearance such as uneven color of the molded articles has been unavoidable.

(Lubricant for polyvinyl chloride resin) Since polyvinyl chloride resin has extremely poor thermal stability and the thermal decomposition temperature of the resin itself is lower than the molding temperature, the molding of the resin is performed with thermal decomposition. . Therefore, the polyvinyl chloride resin requires a large amount of a heat stabilizer and a lubricant to suppress the deterioration of the resin. It is well known that lead, cadmium, barium and other organic compounds and inorganic compounds are excellent as heat stabilizers for polyvinyl chloride resin, but due to regulations on food hygiene or the working environment,
The use of such heavy metal compounds has been restricted, and some metal compounds have been banned. Therefore, octyltin, calcium compounds, zinc compounds and the like, which are considered to be less toxic, have begun to be used as heat stabilizers. However, these stabilizers are inferior in the stabilizing effect and the lubricating effect as compared with conventional lead-based stabilizers and the like, and therefore, it is necessary to supplement these effects with a lubricant. The lubricant is compatible with the resin and has an internal lubricant that accelerates plasticization of the resin and reduces the melt viscosity, and prevents adhesion between the resin and metal during mixing or melting in the extruder, reducing frictional resistance. Workability (melt lubricity) and plasticization (hereinafter referred to as gelling)
External lubricants that have the function of delaying (powder lubricity). As the internal lubricant, for example, butyl stearate,
Glycerin monostearate and the like can be mentioned. Examples of the external lubricant include stearic acid and calcium stearate. Among the other external lubricants, those having a function of delaying gelation, that is, those having an initial lubricity, such as paraffin wax, microcrystalline wax, and polyethylene wax are known, but are satisfactory in the effect of preventing adhesion to a metal surface. Does not show good performance. Further, as an external lubricant, rice bran wax, oxidized polyethylene wax and its ester wax, its metal chloride, stearic acid, monoglyceride and the like are known. However, these have an effect of preventing the adhesion, but have little effect of delaying the gelation.

[0014]

An object of the present invention is to produce a low molecular weight ethylene polymer having a narrow molecular weight distribution and containing a functional group at one end of a polymer chain, and having excellent toner releasability at high temperature and low temperature fixability. It is an object of the present invention to provide a pigment dispersant having improved pigment dispersibility, and an outer lubricant for vinyl chloride resin having excellent initial lubricity.

[0015]

SUMMARY OF THE INVENTION The low molecular weight ethylene-based polymer according to the present invention contains a vinyl-type or vinylidene-type unsaturated bond at one end of the polymer chain, and ethylene alone or ethylene and α-C 3-10. A low molecular weight polymer composed of an olefin and (1) 81 to 100 mol% of ethylene units and 0 to 19 mol% of α-olefin units, and (2) intrinsic viscosity measured in decalin at 135 ° C. [Η] 0.01 to 1.7, (3) the molecular weight distribution (Mw / Mn) measured by GPC is 3 or less, and (4) the number of vinyl groups per 1000 carbons measured by the infrared absorption method. M and the number N of vinylidene groups satisfy the following relational expression (I).

M + N ≧ 14000 / Mw (I) The low-molecular-weight polymer according to the present invention has a terminal at one end of the polymer chain of the low-molecular-weight ethylene-based polymer (that is, a terminal containing a vinyl-type or vinylidene-type unsaturated bond). ) Is obtained by replacing an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, a halogen-containing group or a tin-containing group with a bond (modification). .

The low molecular weight polymer according to the present invention comprises (A) a transition metal compound represented by the following general formula (II) and (B) (B)
-1) an organic metal compound, (B-2) an organic aluminum oxy compound, and (B-3) at least one compound selected from compounds which react with the transition metal compound (A) to form an ion pair. Ethylene alone or ethylene and carbon number 3
It is produced by polymerizing from 10 to 10 α-olefins.

[0018]

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The release agent for a toner according to the present invention comprises a low molecular weight ethylene polymer which may be modified at the terminal as described above. This release agent is used as a component of a toner for developing an electrostatic image together with a binder resin (a) and a colorant (b), and if necessary, a charge control agent, and the like. Contribute to the improvement of

The pigment dispersant according to the present invention comprises a low molecular weight ethylene polymer which may be terminal-modified as described above. This dispersant is mixed with the pigment,
Next, after mixing with the resin to be colored, the mixture is kneaded and granulated by an extruder and used as a dry color, a color compound or a master batch to prevent the aggregation of the pigment and further improve the dispersibility of the pigment.

The lubricant for vinyl chloride resin according to the present invention comprises a low-molecular-weight ethylene polymer which may be terminal-modified as described above. This lubricant is further compounded with a polyvinyl chloride resin and a heat-resistant stabilizer to reduce the kneading torque at the time of processing such as extrusion molding, thereby enabling stable processing for a long time.

[0022]

DETAILED DESCRIPTION OF THE INVENTION The low molecular weight ethylene polymer according to the present invention contains a vinyl-type or vinylidene-type unsaturated bond at one end of the polymer chain, and is composed of ethylene alone or ethylene having 3 to 10 carbon atoms. And low-molecular-weight (co) polymers of α-olefins. As the α-olefin having 3 to 10 carbon atoms used in the present invention, for example, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 3-pentene
Methyl-1-butene, 1-hexene, 4-methyl-1-pentene,
4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, and the like, and one or more of these are used. Of these, propylene is particularly preferred.

The low molecular weight ethylene polymer of the present invention contains 81 to 100 mol% of ethylene units, preferably 90 to 1 mol%.
0 to 19 mol%, preferably 0 to 10 mol%, more preferably 0 to 6 mol% of an α-olefin having 3 to 10 carbon atoms containing 00 mol%, particularly preferably 94 to 100 mol%.
Mol%.

The low molecular weight ethylene polymer 13 of the present invention
The intrinsic viscosity ([η]) measured in decalin at 5 ° C. is
0.01 to 1.7 dl / g, preferably 0.01 to 1.7 dl / g.
-0.6 dl / g, more preferably 0.01-0.4 d
1 / g.

The weight average molecular weight (Mw) and number average molecular weight (Mw) of the low molecular weight ethylene polymer of the present invention measured by gel permeation chromatography (GPC).
The ratio (Mw / Mn) of n) is 1.1 to 3.0, preferably in the range of 1.2 to 2.5.

The number M of vinyl groups and number N of vinylidene groups per 1000 carbons of the low molecular weight ethylene polymer of the present invention measured by an infrared absorption method satisfy the following relational expression (I). M + N ≧ 14000 / Mw (I) <Infrared absorption method (infrared absorption spectrum method)> Using a commercially available infrared spectrophotometer (DS-702G, manufactured by JASCO Corporation), using a standard sample, a hot rolling method 0.15c thickness
A solid thin film of about 0.25 cm from m.
Infrared absorption spectrum between cm ^-1 than 850 cm ^-1 is measured.

<Method of measuring the number of vinyl groups> Using 1-aicosene (carbon number: 20) as a model substance, it is confirmed that the out-of-plane bending vibration of this substance is at 910 cm ^-1 . Using this absorption band, using 1-aicosene and polyethylene containing no unsaturated bond, measure the absorbance of a sample whose vinyl group number is known in advance and measure the film thickness of the sample,
Determine the absorbance per unit thickness. When the relationship between the number of vinyl groups and the absorbance per unit film thickness is illustrated, a substantially linear calibration curve is obtained. Therefore, the absorbance per unit film thickness of various samples is measured using this calibration curve, and the corresponding vinyl group number is obtained by using this calibration curve.

<Method for measuring the number of vinylidene groups> A calibration curve similar to the above-mentioned calibration curve for the number of vinyl groups is prepared. In this case, 2,5-dimethyl-1,5-hexadiene is used as the model substance. The absorption band used is 890 cm ⁻¹ that is observed.

The low molecular weight ethylene polymer according to the present invention is characterized in that one end of the polymer chain has an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, It is preferable to modify with a halogen-containing group or a tin-containing group. These modifications are based on Die Makromolecular Chemie Makromolekular from terminal vinyl or vinylidene groups on the polymer chains of low molecular weight polymers.
Symposia 48/49, 317-332, 1991 can be used for denaturation.

For example, oligomers having an oxygen-containing group modified with maleic anhydride at the end and oligomers containing an amide group and an amine group are suitable as paint additives and pigment dispersants for imparting thixotropy.
The oligomer having a silicon-containing group or a tin-containing group is suitable for use as a polyvinyl chloride lubricant, a lubricant for engineering plastics, a paper treating agent, and the like.

The low molecular weight ethylene polymer according to the present invention comprises (A) a transition metal compound represented by the following general formula (II), (B) an organometallic compound (B-1), and (B-2) ) An olefin polymerization catalyst comprising: an organoaluminum oxy compound; and (B-3) at least one compound selected from compounds which form an ion pair by reacting with the transition metal compound (A). It is preferable to produce it by polymerizing ethylene alone or ethylene and an α-olefin having 3 to 10 carbon atoms.

Each of the catalyst components forming the olefin polymerization catalyst used in producing the polymer of the present invention will be described. (A) Transition metal compound

[0033]

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(Note that N ... M generally indicates coordination, but in the present invention, it may or may not be coordinated.) In the general formula (II), M represents a transition metal atom of Groups 3 to 11 of the periodic table (Group 3 also includes lanthanoids), preferably a metal atom of Groups 3 to 9 (Group 3 also includes lanthanoids), more preferably Is a metal atom of groups 3 to 5 and 9 and particularly preferably a metal atom of group 4 or 5. Specifically, scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum,
Cobalt, rhodium, yttrium, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium and the like, preferably scandium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, cobalt, rhodium, and more preferably,
Titanium, zirconium, hafnium, cobalt, rhodium, vanadium, niobium, tantalum and the like are particularly preferable, and titanium, zirconium and hafnium are particularly preferable.

M represents an integer of 1 to 6, preferably 1 to 4. R ^{1 to} R ⁶ may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group,
A sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group;
More than one may be connected to each other to form a ring.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, and n-hexyl having 1 to 30 carbon atoms, preferably A linear or branched alkyl group having 1 to 20 carbon atoms, such as vinyl, allyl, and isopropenyl;
30, preferably 2 to 20 linear or branched alkenyl groups; ethynyl, propargyl and the like having 2 carbon atoms
A linear or branched alkynyl group having a carbon number of 3 to 30, preferably 2 to 20; a cyclic saturated hydrocarbon group having a carbon number of 3 to 30, preferably 3 to 20, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and adamantyl. A cyclic unsaturated hydrocarbon group having 5 to 30 carbon atoms such as cyclopentadienyl, indenyl and fluorenyl; phenyl, benzyl, naphthyl, biphenyl, terphenyl,
6 carbon atoms such as phenanthryl and anthracenyl
To 30, preferably 6 to 20 aryl groups; tolyl, is
Examples include alkyl-substituted aryl groups such as o-propylphenyl, t-butylphenyl, dimethylphenyl, di-t-butylphenyl, and the like.

In the above hydrocarbon group, a hydrogen atom may be substituted with a halogen. For example, a halogenated carbon atom having 1 to 30, preferably 1 to 20 carbon atoms such as trifluoromethyl, pentafluorophenyl and chlorophenyl. And a hydrogen group.

The hydrocarbon group may be substituted with another hydrocarbon group, for example, an aryl-substituted alkyl group such as benzyl and cumyl. Furthermore, the hydrocarbon group is a heterocyclic compound residue;
Oxygen-containing groups such as alkoxy groups, aryloxy groups, ester groups, ether groups, acyl groups, carboxyl groups, carbonate groups, hydroxy groups, peroxy groups, and carboxylic anhydride groups; amino groups, imino groups, amide groups, and imide groups Nitrogen-containing groups such as hydrazino group, hydrazono group, nitro group, nitroso group, cyano group, isocyano group, cyanate ester group, amidino group, diazo group, amino group having an ammonium salt; borandiyl group, borantriyl group , A boron-containing group such as a diboranyl group; a mercapto group, a thioester group, a dithioester group, an alkylthio group, an arylthio group, a thioacyl group, a thioether group,
Sulfur-containing groups such as thiocyanate group, isothiocyanate group, sulfone ester group, sulfonamide group, thiocarboxyl group, dithiocarboxyl group, sulfo group, sulfonyl group, sulfinyl group, and sulfphenyl group; phosphide group, phosphoryl group, Thiophosphoryl group,
It may have a phosphorus-containing group such as a phosphato group, a silicon-containing group, a germanium-containing group, or a tin-containing group.

Of these, methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, sec-
Butyl, t-butyl, neopentyl, n-hexyl and other linear or branched alkyl groups having 1 to 30, preferably 1 to 20 carbon atoms; phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl and the like. Aryl groups having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms; halogen atoms, alkyl or alkoxy groups having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms, 6 to 30 carbon atoms, Preferably 6 to 20 substituents such as an aryl group or an aryloxy group are 1 to
Preferred is a 5-substituted substituted aryl group.

Oxygen-containing groups, nitrogen-containing groups, boron-containing groups,
Examples of the sulfur-containing group and the phosphorus-containing group include the same as those exemplified above. Heterocyclic compound residues include pyrrole, pyridine, pyrimidine, quinoline, nitrogen-containing compounds such as triazines, furans, oxygen-containing compounds such as pyran, residues such as sulfur-containing compounds such as thiophene, and heterocyclic compounds thereof. Examples include groups in which the compound residue is further substituted with a substituent such as an alkyl group or an alkoxy group having 1 to 30, preferably 1 to 20 carbon atoms.

Examples of the silicon-containing group include a silyl group, a siloxy group, a hydrocarbon-substituted silyl group, and a hydrocarbon-substituted siloxy group. Specific examples include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, and diphenylmethyl. Silyl, triphenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like. Among them, methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, dimethylphenylsilyl, triphenylsilyl and the like are preferable. Particularly, trimethylsilyl, triethylsilyl, triphenylsilyl and dimethylphenylsilyl are preferred. Specific examples of the hydrocarbon-substituted siloxy group include trimethylsiloxy.

Examples of the germanium-containing group and the tin-containing group include those in which silicon of the silicon-containing group is replaced with germanium and tin. Next, the examples of R ^{1 to} R ⁶ described above will be described more specifically.

Among the oxygen-containing groups, alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy and the like, and aryloxy groups include phenoxy, 2,
6-dimethylphenoxy, 2,4,6-trimethylphenoxy and the like, and the acyl group includes a formyl group, an acetyl group, a benzoyl group, a p-chlorobenzoyl group, a p-methoxybenzoyl group, and the like. Groups include acetyloxy, benzoyloxy, methoxycarbonyl, phenoxycarbonyl, p-chlorophenoxycarbonyl, and the like.

Among the nitrogen-containing groups, the amide group includes acetamido, N-methylacetamido, N-methylbenzamide, and the like, and the amino group includes dimethylamino, ethylmethylamino, diphenylamino, and the like. Examples of the group include acetimide and benzimide, and examples of the imino group include methylimino, ethylimino, propylimino, butylimino, and phenylimino.

Among the sulfur-containing groups, examples of the alkylthio group include methylthio and ethylthio, and examples of the arylthio group include phenylthio, methylphenylthio, and the like.
And thioester groups.
Acetylthio, benzoylthio, methylthiocarbonyl, phenylthiocarbonyl and the like are mentioned, examples of the sulfone ester group include methyl sulfonate, ethyl sulfonate and phenyl sulfonate, and examples of the sulfonamide group include phenylsulfonamide and N- Methyl sulfonamide, N-methyl-p-toluene sulfonamide and the like can be mentioned.

Preferably, R ⁶ is a substituent other than hydrogen. That is, R ⁶ is preferably a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a boron-containing group, a sulfur-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group. In particular, R ⁶
Halogen atom, hydrocarbon group, heterocyclic compound residue, hydrocarbon-substituted silyl group, hydrocarbon-substituted siloxy group, alkoxy group, alkylthio group, aryloxy group, arylthio group, acyl group, ester group, thioester group, amide group , An amino group, an imide group, an imino group, a sulfone ester group, a sulfonamide group, a cyano group, a nitro group or a hydroxy group, and more preferably a halogen atom, a hydrocarbon group, or a hydrocarbon-substituted silyl group. .

Preferred hydrocarbon groups for R ⁶ include:
1 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, neopentyl, tert-amyl, n-hexyl
A linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 20; a cyclic saturated hydrocarbon group having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. An aryl group having 6 to 30, preferably 6 to 20 carbon atoms, such as phenyl, benzyl, naphthyl, biphenylyl, and triphenylyl; and an alkyl group having 1 to 30, preferably 1 to 20 carbon atoms in these groups. Group or alkoxy group, having 1 to 30 carbon atoms, preferably 1 to
20 halogenated alkyl groups having 6 to 30 carbon atoms,
Preferable examples include groups further substituted with 6 to 20 substituents such as an aryl group or an aryloxy group, a halogen, a cyano group, a nitro group, and a hydroxy group.

Preferred hydrocarbon-substituted silyl groups for R ⁶ include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, diphenylmethylsilyl, triphenylsilyl,
Dimethylphenylsilyl, dimethyl-t-butylsilyl,
Dimethyl (pentafluorophenyl) silyl and the like. Particularly preferred are trimethylsilyl, triethylphenyl, diphenylmethylsilyl, isophenylsilyl, dimethylphenylsilyl, dimethyl-t-butylsilyl, dimethyl (pentafluorophenyl) silyl and the like.

In the present invention, R ⁶ is particularly a branched alkyl group having 3 to 30, preferably 3 to 20 carbon atoms, such as isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl and tert-amyl. And the hydrogen atoms of these groups have 6 to 30 carbon atoms, preferably 6 to 30 carbon atoms.
A group selected from a cyclic saturated hydrocarbon group having 3 to 30, preferably 3 to 20 carbon atoms such as a group substituted with an aryl group of 20 (such as a cumyl group), adamantyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Preferably, or phenyl, naphthyl,
An aryl group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, such as fluorenyl, anthranyl, and phenanthryl;
Alternatively, it is also preferably a hydrocarbon-substituted silyl group.

R ^{1 to} R ⁶ are two or more of these groups, preferably, adjacent groups are linked to each other to form an aliphatic ring, an aromatic ring, or a hydrocarbon ring containing a hetero atom such as a nitrogen atom. And these rings may further have a substituent.

[0051] When m is 2 or more, belong to R ¹ to R ⁶ and the other ligands belonging to one of the ligands R ¹ to R ⁶
And may be connected. Furthermore, R ¹ each other when m is 2 or more, R ² together, R ³ together, R ⁴ together, R ⁵ each other, R ⁶ to each other may be the same or different from each other.

N is a number that satisfies the valence of M, and is specifically 0 to 5, preferably 1 to 4, and more preferably 1 to 3.
Is an integer. X represents a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, or a silicon-containing residue. Group, germanium-containing group, or tin-containing group. When n is 2 or more, they may be the same or different.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine. As the hydrocarbon group, the aforementioned R
^{The same} ones as exemplified for ^{1 to} R ⁶ can be mentioned. Specifically, alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, and eicosyl; cycloalkyl groups having 3 to 30 carbon atoms such as cyclopentyl, cyclohexyl, norbornyl, and adamantyl; vinyl, Alkenyl groups such as propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl, propylphenyl, biphenyl, naphthyl,
Examples include, but are not limited to, aryl groups such as methylnaphthyl, anthryl, and phenanthryl. These hydrocarbon groups also include halogenated hydrocarbons, specifically, groups in which at least one hydrogen of a hydrocarbon group having 1 to 20 carbon atoms has been replaced with halogen.

Of these, those having 1 to 20 carbon atoms are preferred. As the heterocyclic compound residue, the aforementioned R
^{The same} ones as exemplified for ^{1 to} R ⁶ can be mentioned.

Examples of the oxygen-containing group include the same groups as those exemplified for R ^{1 to} R ⁶ above. Specific examples include a hydroxy group; an alkoxy group such as methoxy, ethoxy, propoxy and butoxy; a phenoxy group and a methyl group. Aryloxy groups such as phenoxy, dimethylphenoxy, and naphthoxy; arylalkoxy groups such as phenylmethoxy and phenylethoxy; acetoxy groups; and carbonyl groups, but are not limited thereto.

Examples of the sulfur-containing group include the same ones as those exemplified in the above R ^{1 to} R ⁶ , and specifically, methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, Sulfonate groups such as trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate and pentafluorobenzenesulfonate; methylsulfinate, phenylsulfinate, benzylsulfinate, p-toluenesulfinate, trimethylbenzenesulfinate Nate,
Examples include, but are not limited to, sulfinate groups such as pentafluorobenzenesulfinate; alkylthio groups; arylthio groups.

Specific examples of the nitrogen-containing group include the aforementioned R ¹ to
The same ones as those exemplified for R ⁶ can be mentioned, and specifically, an amino group; an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino; phenylamino, diphenylamino , Ditolylamino, dinaphthylamino, an arylamino group such as methylphenylamino or an alkylarylamino group.
It is not limited to these.

Specific examples of the boron-containing group include BR
₄ (R represents hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like). Specific examples of the phosphorus-containing group include trialkylphosphine groups such as trimethylphosphine, tributylphosphine, and tricyclohexylphosphine; triphenylphosphine;
Triarylphosphine groups such as tolylphosphine; phosphite groups (phosphide groups) such as methyl phosphite, ethyl phosphite and phenyl phosphite; phosphonic acid groups; phosphinic acid groups, and the like, but are not limited thereto. is not.

Specific examples of the silicon-containing group include the aforementioned R ¹
To R ⁶ , and specifically include phenylsilyl, diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, methyldiphenylsilyl, and tolylsilyl. A hydrocarbon-substituted silyl group such as trinaphthylsilyl; a hydrocarbon-substituted silyl ether group such as trimethylsilyl ether; a silicon-substituted alkyl group such as trimethylsilylmethyl; a silicon-substituted aryl group such as trimethylsilylphenyl.

Specific examples of the germanium-containing group include the same ones as those exemplified above in R ^{1 to} R ⁶ , and specific examples include a group in which silicon of the silicon-containing group is replaced with germanium. .

Specific examples of the tin-containing group include the aforementioned R ¹ to
The same groups as those exemplified for R ⁶ can be mentioned, and more specifically, a group in which silicon of the silicon-containing group is substituted with tin is mentioned.

Specific examples of the halogen-containing group include P
F₆, BF_FourFluorine-containing groups such as ClO _Four, SbCl₆What
Which chlorine-containing groups, IO_FourAnd iodine-containing groups such as
However, the present invention is not limited to these.

Specific examples of the aluminum-containing group include A
lR ₄ (R represents a hydrogen, an alkyl group, an aryl group which may have a substituent, a halogen atom, or the like), but is not limited thereto.

When n is 2 or more, a plurality of groups represented by X may be the same or different from each other.
May be bonded to each other to form a ring. Hereinafter, specific examples of the transition metal compound represented by the general formula (II) are shown, but the invention is not limited thereto.

In the following specific examples, M is a transition metal element, and is individually Sc (III), Ti (III), Ti (I
V), Zr (III), Zr (IV), Hf (IV), V (IV), Nb
(V), Ta (V), Co (II), Co (III), Rh (II), R
h (III) and Rh (IV) are shown, but not limited thereto. Among these, Ti (IV), Zr (IV), H
f (IV) is preferable, and Zr (IV) and Hf (IV) are particularly preferable.

X represents a halogen such as Cl or Br, or an alkyl group such as methyl, but is not limited thereto. When there are a plurality of Xs, they may be the same or different.

N is determined by the valence of the metal M. For example, if two monoanion species are bound to a metal,
N = 0 for a divalent metal, n = 1 for a trivalent metal, n = 2 for a tetravalent metal, and n = 3 for a pentavalent metal. For example, when the metal is Ti (IV), n = 2, when Zr (IV), n = 2, and when Hf (IV), n = 2.

[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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In the above examples, Me is a methyl group, Et is an ethyl group, iPr is an i-propyl group, tBu is a tert-butyl group, Ph is
Represents a phenyl group. Further, as the transition metal compound (B) represented by the general formula (II), there is a transition metal compound represented by the following general formula (II-a).

[0077]

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(Wherein M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, and R ^{1 to} R ¹⁰ may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group, a hetero atom, A cyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group; two or more of these May be linked to form a ring, n is a number satisfying the valence of M, X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, Represents a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and is represented by X when n is 2 or more. Multiple groups may be the same or different It may have I, and a plurality of groups represented by X may be bonded to each other to form a ring, Y
Is oxygen, sulfur, carbon, nitrogen, phosphorus, silicon, selenium,
It represents a divalent bonding group containing at least one element selected from the group consisting of tin and boron. In the case of a hydrocarbon group, it is a group having three or more carbon atoms.

In the general formula (II-a), R ⁶ or R ¹⁰
At least one, especially both, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, Alternatively, it is preferably a tin-containing group.

In the general formula (II-a), M, R ^{1 to} R ¹⁰
As X and X, the same groups as those of M, R ^{1 to} R ⁶ and X described for the compound of the general formula (II) can be used. X is, in particular, a halogen atom, having 1 carbon atom.
Up to 20 hydrocarbon or sulfonate groups are preferred.
When n is 2 or more, the ring formed by linking two or more Xs to each other may be an aromatic ring or an aliphatic ring.

Y is oxygen, sulfur, carbon,
A divalent linking group containing at least one element selected from the group consisting of nitrogen, phosphorus, silicon, selenium, tin, and boron, and, in the case of a hydrocarbon, a linking group having 3 or more carbon atoms. is there.

These bonding groups Y preferably have a structure in which the main chain is composed of 3 or more atoms, more preferably 4 or more and 20 or less, particularly preferably 4 or more and 10 or less. In addition, these bonding groups may have a substituent.

As the divalent linking group (Y), specifically,-
A chalcogen atom such as O-, -S-, -Se-; -NH
-, -N (CH ₃ )-, -PH-, -P (CH ₃ )-and other nitrogen or phosphorus atom-containing groups; -SiH _2- , -Si (C
A silicon atom-containing group such as H ₃ ) _2- ; -SnH _2- , -Sn
(CH _{3) 2} - tin atom-containing groups such as; -BH -, - B
And a boron atom-containing group such as (CH ₃ ) — and —BF—. The hydrocarbon group _{- (CH 2) 4 -,} - (C
A saturated hydrocarbon group having 3 to 20 carbon atoms such as H ₂ ) ₅ — and — (CH ₂ ) ₆ —; a cyclic saturated hydrocarbon group such as a cyclohexylidene group and a cyclohexylene group; A part of 1 to 10 hydrocarbon groups, fluorine, chlorine,
Groups substituted by heteroatoms such as halogen such as bromine, oxygen, sulfur, nitrogen, phosphorus, silicon, selenium, tin and boron; cyclic hydrocarbons having 6 to 20 carbon atoms such as benzene, naphthalene and anthracene; Group; a residue of a cyclic compound having 3 to 20 carbon atoms including a hetero atom such as pyridine, quinoline, thiophene, and furan.

Hereinafter, specific examples of the transition metal compound represented by the general formula (II-b) will be shown, but the invention is not limited thereto.

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[0086]

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In the above examples, Me represents a methyl group,
Ph represents a phenyl group. In the present invention, a transition metal compound in which titanium metal is replaced with a metal other than titanium, such as zirconium or hafnium, in the compounds described above can also be used.

(B-1) Organometallic Compounds The (b-1) organometallic compounds used in the present invention are, specifically, those of Groups 1 and 2 and Groups 12 and 1 of the periodic table shown below.
A group 3 organometallic compound is used.

[0089] (b-1a) formula _{^{R a m Al (OR b)}} n H p
X _q (wherein, R ^a and R ^b may be the same or different from each other and have 1 to 15 carbon atoms, preferably 1 to
4 represents a hydrocarbon group, X represents a halogen atom, m is 0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0
≤q <3, and m + n + p + q = 3. The organoaluminum compound represented by).

[0090] (b-1b) In the general formula M ² AlR ^a ₄ (wherein, M ² represents a Li, Na or K, R ^a is the number of carbon atoms 1 to 15, preferably 1 to 4 hydrocarbon groups A complex alkylated product of a metal belonging to Group 1 of the periodic table and aluminum.

(B-1c) Formula R ^a R ^b M ³ (wherein R ^a and R ^b may be the same or different and each have 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms) A dialkyl compound of a metal of Group 2 or 12 of the periodic table represented by a hydrocarbon group, wherein M ³ is Mg, Zn or Cd.

As the organoaluminum compound belonging to (b-1a), the following compounds can be exemplified. In the general formula _{^{R a m Al (OR b)}} 3-m ( wherein, R ^a and R ^b may be the same or different, 1 to 15, preferably 1 to 4 hydrocarbon group having carbon atoms are shown, m is preferably a number 1.5 ≦ m ≦ 3) an organoaluminum compound represented by;. in the formula R ^a _m AlX _3-m (wherein, R ^a is 1 to carbon atoms 15, preferably 1
4 represents a hydrocarbon group, X represents a halogen atom, and m is preferably 0 <m <3. An organoaluminum compound represented by); the general formula R ^a _m AlH _3-m (wherein, R ^a is the number of carbon atoms 1 to 15, preferably 1 to
4 represents a hydrocarbon group, and m is preferably 2 ≦ m <3. An organoaluminum compound represented by); In the formula _{^{R a m Al (OR b)}} n X q ( wherein, R ^a and R ^b may be the same or different from each other, the number of carbon atoms 1 to 15, It preferably represents 1 to 4 hydrocarbon groups, X represents a halogen atom, and m represents 0 <
m ≦ 3, n is a number of 0 ≦ n <3, q is a number of 0 ≦ q <3,
And m + n + q = 3. The organoaluminum compound represented by).

More specifically, the organoaluminum compounds belonging to (b-1a) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum. Tri-n-alkyl aluminum such as triisopropyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-
Butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3-methylpentylaluminum, tri4-methylpentylaluminum, tri2-methylhexylaluminum, tri3-methylhexyl Aluminum, tribranched alkyl aluminum such as tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum; triaryl aluminum such as triphenyl aluminum and tritolyl aluminum; dialkyl aluminum such as diisobutyl aluminum hydride Hydride; (i-C ₄ H ₉ ) _x
Trialkenyl aluminum such as triisoprenyl aluminum represented by Al _y (C ₅ H ₁₀ ) _z (where x, y and z are positive numbers and z ≧ 2x); isobutylaluminum methoxy Aluminum alkoxides such as dimethyl, isobutylaluminum ethoxide and isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; alkyls such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide Aluminum sesquialkoxide; ^Ra
_2.5 Al (OR ^b ) _0.5 partially alkylated alkyl aluminum having an average composition represented by _0.5 ; diethyl aluminum phenoxide, diethyl aluminum (2,6-di-t-butyl-4-methylphenoxide), ethyl Aluminum bis (2,6-di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-)
Dialkylaluminum aryl oxides such as methylphenoxide) and isobutylaluminum bis (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, etc. Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride and ethyl aluminum sesquibromide; partially halogen such as alkyl aluminum dihalides such as ethyl aluminum dichloride, propyl aluminum dichloride and butyl aluminum dibromide Alkylaluminide; diethylaluminum hydride Dialkylaluminum hydrides such as dibutylaluminum hydride; other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride; ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide, ethyl Partially alkoxylated and halogenated alkyl aluminum such as aluminum ethoxy bromide can be mentioned.

Further, a compound similar to (b-1a) can also be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, as such a compound,
(C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

Compounds belonging to the above (b-1b) include Li
Al (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ can be exemplified. In addition, (b-1) organometallic compounds include methyllithium, ethyllithium, propyllithium, butyllithium, methylmagnesium bromide, methylmagnesium chloride, ethylmagnesium bromide, ethylmagnesium chloride, propylmagnesium bromide, propylmagnesium Chloride, butylmagnesium bromide, butylmagnesium chloride, dimethylmagnesium, diethylmagnesium, dibutylmagnesium, butylethylmagnesium and the like can also be used.

Further, a compound which forms the above-mentioned organoaluminum compound in the polymerization system, for example, a combination of aluminum halide and alkyl lithium, or a combination of aluminum halide and alkyl magnesium can also be used.

(B-1) Among the organometallic compounds, an organoaluminum compound is preferred. The (b-1) organometallic compound as described above is used alone or in combination of two or more.

(B-2) Organoaluminum oxy compound The (b-2) organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, and is exemplified in JP-A-2-78687. May be a benzene-insoluble organic aluminum oxy compound.

The conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent. (1) Compounds containing water of adsorption or salts containing water of crystallization such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerium chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of the above, and reacting the water of adsorption or water of crystallization with the organoaluminum compound. (2) A method in which water, ice or steam is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organic metal component. The solvent or unreacted organoaluminum compound may be removed from the recovered solution of the aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for the aluminoxane.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include the compounds (b-1a)
And the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferred, and trimethylaluminum is particularly preferred. The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane. Alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; petroleum fractions such as gasoline, kerosene and light oil; and halogens of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons Hydrocarbon solvents such as chlorides, bromides and the like. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons and aliphatic hydrocarbons are particularly preferred.

In the benzene-insoluble organic aluminum oxy compound used in the present invention, the Al component soluble in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom. Certain, ie, those that are insoluble or poorly soluble in benzene, are preferred.

As the organic aluminum oxy compound used in the present invention, an organic aluminum oxy compound containing boron represented by the following general formula (III) can also be mentioned.

[0106]

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In the formula, R ¹⁷ represents a hydrocarbon group having 1 to 10 carbon atoms. R ¹⁸ may be the same or different, and each has a hydrogen atom, a halogen atom, and 1 to 10 carbon atoms.
Represents a hydrocarbon group.

The organoaluminum oxy compound containing boron represented by the general formula (III) is represented by the following general formula (I)
The alkylboronic acid represented by V) and R ¹⁷ -B- (OH) ₂ ... (IV) (in the formula, R ¹⁷ represents the same group as described above). It can be produced by reacting in an inert solvent at a temperature of -80C to room temperature for 1 minute to 24 hours.

Specific examples of the alkylboronic acid represented by the general formula (IV) include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, and n -Hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3,5-difluoroboronic acid, pentafluorophenylboronic acid, 3,5-bis (trifluoromethyl) phenylboronic acid and the like. Among these, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3,5-difluorophenylboronic acid, and pentafluorophenylboronic acid are preferred. These are used alone or in combination of two or more.

Specific examples of such an organoaluminum compound to be reacted with an alkylboronic acid include those described in (b-1a) above.
And the same organoaluminum compounds as those exemplified as the organoaluminum compounds belonging to the above.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable. These are used alone or in combination of two or more.

The above-mentioned (b-2) organoaluminum oxy compounds are used alone or in combination of two or more. (b-3) Compound forming an ion pair by reacting with a transition metal compound Compound (b-3) forming an ion pair by reacting with a transition metal compound (A) used in the present invention (hereinafter referred to as “ionized ion ) Is described in JP-A-1-5019.
No. 50, Japanese Unexamined Patent Publication No.
-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207
And Lewis acids, ionic compounds, borane compounds and carborane compounds described in US Pat. No. 704, US Pat. No. 5,321,106. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

Specifically, as the Lewis acid, BR ₃
(R is a phenyl group or a fluorine which may have a substituent such as fluorine, a methyl group and a trifluoromethyl group.), For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) ) Boron, tris (3,5-dimethylphenyl) boron and the like.

Examples of the ionic compound include a compound represented by the following general formula (V).

[0115]

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In the formula, R ¹⁹ includes H ⁺ , carbonium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.

R ^{20 to} R ²³ may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group. Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation, tri (methylphenyl) carbonium cation, and tri (dimethylphenyl) carbonium cation.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation; N, N-dimethylanilyl; Nium cation, N,
N, N-dialkylanilinium cations such as N-diethylanilinium cation and N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation No.

Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.

As R ¹⁹ , a carbonium cation, an ammonium cation and the like are preferable, and a triphenylcarbonium cation, an N, N-dimethylanilinium cation and an N, N-diethylanilinium cation are particularly preferable.

The ionic compounds include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts,
Dialkylammonium salts, triarylphosphonium salts and the like can also be mentioned.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p -Tolyl) boron, trimethylammoniumtetra (o-tolyl) boron, tri (n-butyl) ammoniumtetra (pentafluorophenyl) boron, tripropylammoniumtetra (o, p-dimethylphenyl) boron,
Tri (n-butyl) ammonium tetra (m, m-dimethylphenyl) boron, tri (n-butyl) ammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (3,5-ditri Fluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron and the like.

Specific examples of the N, N-dialkylanilinium salt include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N-2, 4,6-pentamethylanilinium tetra (phenyl) boron and the like.

Specific examples of the dialkyl ammonium salt include, for example, di (1-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (phenyl) boron.

Further, as an ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl)
Borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex,
An N, N-diethylanilinium pentaphenylcyclopentadienyl complex, a boron compound represented by the following formula (VI) or (VII), and the like can also be mentioned.

[0126]

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(In the formula, Et represents an ethyl group.)

[0128]

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Specific examples of the borane compound include decaborane (14); bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, and bis [tri (n-butyl) ammonium ] Undecaborate, bis [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-
Salts of anions such as butyl) ammonium] dodecachlorododecaborate; tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydride dodecaborate) Borate) salts of metal borane anions such as nickelate (III).

Specific examples of the carborane compound include, for example, 4-carbanonaborane (14), 1,3-dicarbanonaborane (13), 6,9-dicarbadecaborane (14), dodecahydride-1-phenyl- 1,3-dicarbanonaborane,
Dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarboundecaborane (13), 2,
7-dicarboundecaborane (13), undecahydride-7,8-dimethyl-7,8-dicarboundecaborane, dodecahydride-11-methyl-2,7-dicarboundecaborane, tri (n-butyl ) Ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carboundecaborate, tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadeca Borate, tri (n-butyl) ammonium bromo-1-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate (14), tri (n-butyl) ammonium 6-carbadecaborate (1
2), tri (n-butyl) ammonium 7-carboundecaborate (13), tri (n-butyl) ammonium 7,8-
Dicarboundecaborate (12), tri (n-butyl)
Ammonium 2,9-dicarboundecaborate (12),
Tri (n-butyl) ammonium dodecahydride-8-
Methyl-7,9-dicarboundecaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-
Dicarbaune decaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaune Decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carboundecaborate Salts of anions such as tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydride-7,8 -Dicarboundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) co Belt salt (III), tri (n- butyl) ammonium bis (undecapeptide 7,8-dicarbaundecaborate deca borate)
Nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7) , 8-Dicarboundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III) (N-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarboundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-7,8 -Dicarboundecaborate) cobaltate (II
I), tris [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) chromate (III), bis [tri (n-butyl) ammonium]
Bis (undecahydride-7-carboundecaborate) manganate (IV), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carboundecaborate) cobaltate (III), Bis [tri (n-butyl) ammonium] bis (undecahydride-7-
Metal carborane anions such as (carboundecaborate) nickelate (IV).

The heteropoly compound consists of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphorus vanadic acid, germanovanadate, arsenic vanadate, phosphorus niobate, germanoniobate, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphorus molybdate, phosphorus Tungstic acid, germanotungstic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorus tungstovanadic acid, germanotangostvanadate acid, phosphomolybdodovanstovanadate,
Germanomolybdo tungstovanadate, phosphomolybdotungstate, phosphomolybdniobate, and salts of these acids, such as metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, A salt with rubidium, cesium, beryllium, magnesium, calcium, strontium, barium and the like, and an organic salt with triphenylethyl salt and the like can be used, but not limited thereto.

The (b-3) ionized ionic compound as described above is used alone or in combination of two or more. At the time of polymerization, the method of use and the order of addition of each component are arbitrarily selected, and the following methods are exemplified.

(1) Component (A), (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound and (B-3)
A method in which at least one component (B) selected from ionized ionic compounds (hereinafter, simply referred to as “component (B)”) is added to a polymerization vessel in an arbitrary order.

(2) A method in which the component (A), the catalyst component in which the component (B-1) is brought into contact in advance, and the component (B-3) are added to the polymerization reactor in any order. (3) A method in which the catalyst component in which the component (A) and the component (B-1) are brought into contact in advance, and the component (B-1) and the component (B-3) are added to the polymerization reactor in an arbitrary order. In this case, the components (B-1) may be the same or different.

(4) A method in which component (A), component (B-1) and component (B-3) are brought into contact in advance with the catalyst component and component (B-1) are added to the polymerization reactor in any order. . In this case, the components (B-1) may be the same or different.

(5) A method in which the catalyst in which the component (A) and the component (B-2) are brought into contact in advance is added to a polymerization reactor. (6) a catalyst component in which the component (A) and the component (B-2) are brought into contact in advance,
And adding the component (B-1) or (B-2) to the polymerization reactor in any order. In this case, the components (B-2) may be the same or different.

In the present invention, the polymerization can be carried out by any of liquid phase polymerization such as solution polymerization and suspension polymerization or gas phase polymerization. Specific examples of the inert hydrocarbon medium used in the liquid phase polymerization method include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane Alicyclic hydrocarbons such as benzene, toluene, xylene, etc .; halogenated hydrocarbons such as ethylene chloride, chlorobenzene, dichloromethane and the like, and mixtures thereof, and the olefin itself is used as a solvent. You can also.

When olefin polymerization is carried out using the olefin polymerization catalyst as described above, the amount of the component (A) is usually 10 ^-12 to 10 ^-2 mol, preferably 10 ^-10 to 10 ^-3 mol. Used in appropriate amounts.

Component (b-1) is composed of component (b-1) and component (A)
Molar ratio [(b-1) / M] with the transition metal atom (M) in the solution is usually 0.01 to 100,000, preferably 0.05 to 500.
It is used in such an amount as to give 00. Component (b-2) is a component
The molar ratio [(b-2) / M] between the aluminum atom in (b-2) and the transition metal atom (M) in the component (A) is usually 10 to 50.
0000, preferably 20 to 100,000. The component (b-3) is obtained by a molar ratio [(b-3) / M] between the component (b-3) and the transition metal atom (M) in the component (A).
Is usually used in an amount of 1 to 20, preferably 1 to 10.

The polymerization temperature of olefin using such an olefin polymerization catalyst is usually -50 to +200.
° C, preferably in the range of 0 to 170 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to
Under a condition of 50 kg / cm ² , the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages having different reaction conditions.

The release agent for toner according to the present invention comprises the low-molecular-weight ethylene-based polymer according to the present invention, which may be terminal-modified. This release agent is used together with the binder resin (a) and the colorant (b), and if necessary, as a component of a toner for developing an electrostatic image, together with a charge control agent and the like. The number average molecular weight of this release agent is in the range of 300 to 2000, preferably 400 to 1000.
Range.

The binder resin (a) is not particularly limited as long as it is made of a thermoplastic resin generally blended in a developer for an electrostatic image. For example, styrene resin, styrene-acrylic ester copolymer,
Acrylic resin, styrene-butadiene resin, ketone resin, maleic acid resin, polyester resin, polyvinyl acetate resin, coumarone resin, phenol resin, silicone resin, polyurethane, epoxy resin, terpene resin, polyvinyl butyral, polybutyl methacrylate, polyvinyl chloride , Polyethylene, polypropylene, polybutadiene, ethylene-vinyl acetate copolymer, rosin resin and the like. Among these, a styrene-acrylate copolymer, a polyester aromatic resin, and an epoxy resin having an appropriate softening point (90 ° C. to 120 ° C.) and good fixability are particularly preferable.

The colorant (b) may be any colorant which is generally compounded in a developer for an electrostatic image, and is not particularly limited. For example, carbon black, phthalocyanine blue, aniline blue, alcohol oil blue,
Pigments or dyes such as chrome yellow, ultramarine blue, quinoline yellow, lamp black, rose bengal, diazo yellow, rhodamine B lake, carmine 6B, and quinacridone derivatives, and these may be used alone or in combination of two or more. Used.

The mixing ratio of the toner release agent of the present invention is usually such that the ratio of binder resin / colorant / charge control agent / release agent of the present invention is 100/1 to 10/0 by weight. 5 / 0.5-4
0, preferably 100/1 to 6 / 0.5 to 2
/ 10-20.

The pigment dispersant according to the present invention comprises the low-molecular-weight ethylene polymer which may be terminal-modified according to the present invention. This dispersant is mixed with a pigment and then with a resin to be colored, then kneaded and granulated by an extruder, and used as a dry color, a color compound or a master batch.

The mixing ratio of the pigment dispersant is 100
It is usually in the range of 25 to 200 parts by weight, preferably 50 to 150 parts by weight based on parts by weight. The number average molecular weight is in the range of 1000 to 5000, preferably in the range of 1500 to 3000.

Examples of the coloring resin which can be used include polyethylene, polypropylene, polybutene-1, polybutene-1, and the like.
Polyolefin resins such as poly-4-methylpentene-1, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, styrene resins such as polystyrene and ABS, polycarbonate resins obtained from bisphenol-A and phosgene, polyethylene terephthalate And thermoplastic resins such as polyester resins such as polybutylene terephthalate, polyamide resins, polyphenylene oxide resins and polyvinyl chloride, and thermosetting resins such as phenol resins and epoxy resins.

In particular, the pigment dispersant of the present invention is a thermoplastic resin.
It can be suitably used for fats. Pigments that can be used
Are all pigments conventionally known for coloring synthetic resins.
Can be used for Specific examples of pigments
And metals such as aluminum, silver, and gold; calcium carbonate
Carbonates such as calcium and barium carbonate; ZnO, TiO_TwoSuch as oxidation
Object; Al_TwoO_Three・ NH_TwoO, Fe_TwoO_Three・ NH_TwoHydroxides such as O; CaSO_Four, B
aSO_FourSuch as sulfates; Bi (OH) _TwoNO_ThreeNitrates such as; PbCl_TwoWhat
Which chloride; CaCrO_Four, BaCrO_FourChromate such as CoCrO_Four
Chromite, manganate and permanganate such as
Salt; Cu (BO)_TwoBorate such as; Na_TwoU_TwoO₇・ 6H_TwoU and other uranium
Acid salt; K_ThreeCo (NO_Two)₆・ 3H_TwoNitrite such as O; SiO_TwoSuch as silicon
Acid salt: CuAsO_Three・ Cu (OH)_TwoArsenates and arsenites such as; Cu
(C_TwoH_ThreeO_Two)_Two・ Cu (OH)_TwoAcetate such as; (NH_Four)_TwoMnO_Two(P_TwoO₇)_TwoWhat
Which phosphates; aluminates, molybdates, zincates,
Antimonate, tungstate selenide, titanium
Acid, iron cyanide, phthalate, CaS, ZnS, CdS, etc.
Inorganic pigments, cochineal lake, madder lake, etc.
Natural organic pigments, naphthol green Y, naphthol
・ Nitroso pigments such as green B; naphthol yellow
S, nitro pigments such as pigment chlorin 2G;
Moment Red 4R; Hansa Yellow, Brilliant
Azo pigments such as Carmine 68 and Scarlet 2R;
Basic dyes such as Cain Green and Rhodamine B
Ki, acid, green lake, eosin lake, etc.
Acid dye lake, alizarin lake, purpurin
Lakes, such as mordant dye lakes, thio-indigo red
Vat dyes, vat dyes such as intrene / orange,
Such as phthalocyanine blue and phthalocyanine green
Organic pigments such as phthalocyanine pigments are exemplified.

The pigment dispersant of the present invention can be used for coloring by a dry color method, coloring by a color compound method, or coloring by a master batch method, and is particularly preferably used for the master batch method. can do.

The lubricant for a polyvinyl chloride resin according to the present invention comprises the low-molecular-weight ethylene-based polymer according to the present invention, which may be terminal-modified. In the polyvinyl chloride composition using the lubricant of the present invention, the blending ratio of the lubricant is in the range of 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, per 100 parts by weight of polyvinyl chloride. Parts by weight. Further, the polymer used as a lubricant has a number average molecular weight in the range of 400 to 4000 parts by weight, preferably in the range of 500 to 1000 parts by weight. The acid value of this modified product is in the range of 2 to 70, preferably in the range of 10 to 50. When the acid value of the modified product is 70 or more, the initial lubricity of the lubricant decreases, and
Below, the effect of preventing tackiness decreases. When the number average molecular weight of the lubricant is 400 or less, the effect of preventing adhesion to metal is poor, and when the number is 4000 or more, the lubricity is reduced in the initial stage and the entire late stage. In addition, the blending ratio of the lubricant was 0.1%.
If the amount is less than 05 parts by weight, the lubricating effect is insufficient, and if it is more than 5 parts by weight, the lubrication becomes excessive, and it becomes difficult to plasticize the composition.

In order to use the above modified product as a lubricant, an unsaturated carboxylic acid or an unsaturated carboxylic acid or a monomer which modifies the vinyl group-containing or vinylidene group-containing oligomer at one end of the polymer chain of the low molecular weight ethylene polymer according to the present invention is used. Examples thereof include anhydrides, specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, citraconic acid,
Examples thereof include citraconic anhydride, fumaric acid, itaconic acid, itaconic anhydride, 3-cyclohexenecarboxylic acid, 4-cyclohexenecarboxylic acid, and 5-norbornene-2,3-dicarboxylic acid.

The polyvinyl chloride resin containing the polyvinyl chloride resin additive of the present invention may be polyvinyl chloride, or polyvinyl chloride, polyethylene, polypropylene, ABS resin, MBS resin, ethylene-vinyl acetate copolymer, polymethyl meta- Even a mixture of acrylate and the like cannot be used. These compositions may further contain a heat stabilizer.

The heat stabilizer which can be used may be any as long as it has a stabilizing effect on the polyvinyl chloride resin. Examples thereof include a lead compound, a cadmium compound, a barium compound, a calcium compound, a zinc compound, and an organotin compound. , Epoxy compounds, chelators and the like, and mixtures thereof.

The polyvinyl chloride composition containing the lubricant of the present invention may further contain other lubricants, fillers, pigments, dyes, plasticizers, antistatic agents and weather stabilizers. Since the composition containing the lubricant according to the present invention has excellent initial lubricity, the adhesiveness to metal is reduced, the composition can be formed stably, and continuous operation can be performed for a long time.

The low-molecular-weight ethylene polymer according to the present invention can be widely used in applications where known low-molecular-weight polyethylene such as wax is used. In this case,
If necessary, various additives can be added and used. For example, when the low molecular weight ethylene polymer according to the present invention is used as a paint modifier, it is possible to modify the surface of the coating film, for example, it is possible to improve the matting effect and improve the abrasion resistance of the coating film. In addition, the woodwork paint can be given a luxurious feeling and the durability can be improved.

When the low molecular weight ethylene polymer according to the present invention is used as a polishing agent for car wax, floor polish, etc., excellent gloss can be obtained and coating film properties can be improved.

The low molecular weight ethylene polymer according to the present invention is suitable as a mold release agent for resin molding, and can impart mold release properties to a thermoplastic resin or a thermosetting resin to improve a molding cycle.

The low-molecular-weight ethylene polymer according to the present invention has excellent compatibility with rubber, imparts releasability to rubber,
It is suitable as a rubber processing aid for adjusting the viscosity, and when used as a rubber processing aid, improves the dispersibility of fillers and pigments, and gives mold release and fluidity to rubber, so that a molding cycle during rubber molding, Extrusion characteristics can be improved.

The low molecular weight ethylene polymer according to the present invention is suitable as a paper quality improver for improving the lubricity and surface modification of paper. When used as a paper quality improver, it has a moisture-proof property, gloss, surface hardness, and resistance to paper. The blocking property and the abrasion resistance can be improved, and the paper can be given a high quality feeling and the durability can be improved.

The low molecular weight ethylene polymer according to the present invention is suitable as an abrasion resistance improver for ink. When used as an abrasion resistance improver, it can improve the abrasion resistance and heat resistance of the ink surface. it can. The low molecular weight ethylene polymer according to the present invention is suitable as a fiber processing aid, and when used as a fiber processing aid in processing a fiber into a resin, it can impart flexibility and lubricity to the fiber.

The low molecular weight ethylene polymer according to the present invention is suitable as a hot melt additive, and can impart heat resistance and fluidity to a hot melt adhesive. It is possible to improve the quality of hot melt adhesives in fields requiring heat resistance such as automobiles and building materials. The low molecular weight ethylene polymer according to the present invention is suitable as an electrical insulating agent, and can improve, for example, the electrical insulation and heat resistance of a film capacitor. The low molecular weight ethylene polymer according to the present invention is suitable as a compounding agent for natural waxes such as crayons and candles, and can improve surface hardness and softening point.

[0162]

According to the present invention, the low molecular weight ethylene polymer is
Since the polymer chain has a reactive vinyl-type or vinylidene-type unsaturated bond at one end of the polymer chain, an arbitrary functional group can be provided by various modification techniques.

Such a polymer and a modified product thereof can provide a toner release agent having excellent high-temperature release properties and excellent low-temperature fixability. Further, the polymer and the modified product thereof can provide a pigment dispersant having excellent pigment dispersibility.

Furthermore, the above-mentioned polymer and its modified product are
A lubricant for polyvinyl chloride resin having excellent initial lubricity can be provided.

[0165]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.

In this example, the intrinsic viscosity ([η]) was measured at 135 ° C. in decalin. The molecular weight distribution (Mw / Mn) was measured as follows using GPC-150 manufactured by Millipore.

As the separation column, the column size was 2
The column temperature was 140 ° C. using TSK GNH HT having a length of 7 mm and a length of 600 nm, and o-dichlorobenzene (Wako Pure Chemical) was used as a mobile phase and BHT was used as an antioxidant.
(Takeda Pharmaceutical Co., Ltd.) The development was performed at 1.0 ml / min using 0.025% by weight, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. Standard polystyrene manufactured by Tosoh Corporation was used.

The terminal carbonyl was determined by substituting the acid value. The acid value is determined using the potassium hydroxide neutralization method.
According to JIS K-5902.

[0169]

[Synthesis Example 1] 1 L of hexane was charged into a 2 L-volume SUS autoclave sufficiently purged with nitrogen. Then, the temperature in the system was raised to 120 ° C., and then 1.25 mmol of methylaluminoxane and 0.001 m of compound (A-1) were obtained.
The polymerization was started by injecting mol with ethylene. Thereafter, by continuously supplying ethylene, the total pressure was kept at 30 kg / cm ^2, and polymerization was carried out at 120 ° C. for 15 minutes. After terminating the polymerization by adding a small amount of methanol to the system, unreacted ethylene was purged. The obtained polymer solution was poured into a large excess of methanol to precipitate a polymer. The polymer was collected by filtration and dried under reduced pressure at 80 ° C. for 10 hours. As a result, a polyethylene oligomer 55.2 having an intrinsic viscosity [η] of 0.11 dl / g, Mn of 900, Mw / Mn of 1.9, and 14.6 vinyl groups per 1000 carbons.
g was obtained.

[0170]

Embedded image

[0171]

[Synthesis Example 2] A SUS 2L autoclave sufficiently purged with nitrogen was charged with 850 ml of heptane at room temperature.
The temperature was raised to 50 ° C. Subsequently, propylene was charged while maintaining the temperature at 50 ° C. until the pressure reached 5.5 kg / cm ² G,
Further, it was pressurized with ethylene until the total pressure reached 8 kg / cm ² G. Then, methylaluminoxane 1.25mmo
1, 0.001 mmol of the compound (A-2) was injected to initiate polymerization. 50 ° C while continuously supplying ethylene
For 15 minutes. After adding a small amount of methanol to terminate the polymerization, unreacted monomers were purged. The obtained polymer solution was poured into a large excess of methanol to precipitate a polymer. The obtained polymer was recovered by filtration and dried under reduced pressure at 130 ° C. for 10 hours. As a result, the intrinsic viscosity [η] was 0.40 dl / g, the propylene content was 4.5 mol%, Mn was 1600, and Mw / Mn was 1.
3, 6.5 g of an oligomer having 7.2 vinyl groups and 7.2 vinylidene groups per 1000 carbon atoms were obtained.

[0172]

Embedded image

[0173]

[Synthesis Example 3] [Modification of terminal unsaturated bond] 25 g of the oligomer obtained in Synthesis Example 2 and 0.41 g of SnCl ₂ · 2H ₂ O were charged into a 100 ml SUS autoclave sufficiently purged with nitrogen, and heated at 230 ° C. For 5 hours. Thereafter, 5.9 g of dissolved maleic anhydride and 3 mg of tetramethylpiperidine nitroxide were charged, and the mixture was reacted for 20 minutes by applying a pressure of 5 kg / cm ² G with nitrogen. With the sample dissolved, small portions were taken out and poured into a large excess of cyclohexane, and insolubles were removed by filtration. After cyclohexane in the filtrate was distilled off under reduced pressure, the obtained residue was concentrated at 100 ° C.
For 10 hours under reduced pressure. As a result, 25.5 g of a modified product whose terminal was modified with maleic anhydride was obtained.

[0174]

[Synthesis Example 4] A SUS 2L autoclave sufficiently purged with nitrogen was charged with 850 ml of heptane at room temperature.
The temperature was raised to 50 ° C. Subsequently, propylene was charged while maintaining the temperature at 50 ° C. until the pressure reached 5.5 kg / cm ² G,
Further, it was pressurized with ethylene until the total pressure reached 8 kg / cm ² G. Then, methylaluminoxane 1.25mmo
1, 0.001 mmol of the compound (A-3) was injected to initiate polymerization. 50 ° C while continuously supplying ethylene
For 15 minutes. After adding a small amount of methanol to terminate the polymerization, unreacted monomers were purged. The obtained polymer solution was poured into a large excess of methanol to precipitate a polymer. The obtained polymer was recovered by filtration and dried under reduced pressure at 130 ° C. for 10 hours. As a result, the intrinsic viscosity [η] was 0.20 dl / g, the propylene content was 3.8 mol%, Mn was 2,300, and Mw / Mn was 2.
28.7 g of an oligomer having 5.5 vinyl groups and vinylidene groups per 0 and 1000 carbons was obtained.

[0175]

Embedded image

[0176]

[Synthesis example 5] [Modification of terminal unsaturated bond] As a result of treating the oligomer obtained in Synthesis example 4 in the same manner as in Synthesis example 3,
23.1 g of a modified adult whose terminal was modified with maleic anhydride was obtained.

[0177]

[Table 1]

[0178]

[Example 1] Resin for binder (manufactured by Mitsui Chemicals, Inc., C
PR-100) 87 parts and carbon black (MA10
0; Mitsubishi Chemical) 8.0 parts, charge control agent (BONTRON S-3)
4; manufactured by Orient Chemical Co., Ltd.), and 1.0 part of the polyethylene oligomer synthesized in Synthesis Example 1 was preliminarily mixed with a Henschel mixer, and then 120 ° C. using a twin-screw kneader.
, And then cooled, coarsely pulverized and finely pulverized, and further classified with a classifier to obtain a toner having a size of 6.0 to 18.0 μm. Next, a hydrophobic silica (R-
972, manufactured by Aerosil Co.) was added from the outside in a ratio of 0.4% by weight, and the mixture was mixed with a Henschel mixer to obtain a toner. As a result of evaluating the toner obtained as described above, the minimum fixing temperature (A) was 135 ° C., and the offset occurrence temperature (B) was 240 ° C. or higher.

These evaluation methods were performed as follows. Minimum fixing temperature (A) An unfixed image is formed by a copying machine in which a commercially available electrophotographic copying machine is appropriately changed, and the unfixed image is formed by using a heat roller fixing device in which a fixing unit of a commercially available copying machine is appropriately changed. And settled. The fixing speed of the heat roller was set to 210 mm / sec, and the temperature of the heat roller was changed by 5 ° C. to fix the toner. The resulting fixed image was rubbed 10 times with a sand eraser (manufactured by Dragonfly Pencil) under a load of 0.5 kg, and a friction test was performed. The image density before and after the friction test was measured by a Macbeth reflection densitometer. The lowest fixing temperature at which the rate of change in image density at each temperature became 70% or more was defined as the lowest fixing temperature. The heat roller fixing device used here does not have a silicone oil supply mechanism. The environmental conditions are normal temperature and normal pressure (temperature 22 ° C,
(Relative humidity 55%).

Offset occurrence temperature (B) The anti-offset property was evaluated according to the measurement of the minimum fixing temperature. That is, after an unfixed image was created by the copying machine, the toner image was transferred, and a fixing process was performed by the above-described heat roller fixing device. Next, under the same conditions, the blank transfer paper was sent to the heat roller fixing device, and an operation of visually observing whether or not toner stains occurred on the transfer paper was performed. This operation was repeated plural times while sequentially increasing the set temperature of the heat roller of the heat roller fixing device. The minimum set temperature at which toner contamination occurred was taken as the offset occurrence temperature. The environmental conditions were normal temperature and normal pressure (temperature 22 ° C., relative humidity 55%).

[0181]

Example 2 The oligomer obtained in Synthesis Example 3 was finely pulverized (50% particle size: 80 μm) with a desktop pulverizer, dissolved at 180 ° C., and 100 parts by weight of phthalocyanine blue was gradually added thereto while kneading. As a result, a spherical kneaded material having a radius of about 2.5 cm was obtained. The kneaded solid was supplied to a three-roll mixer at 130 ° C., and the discharge speed was calculated from the passage time and the discharge amount. Further, the kneading composition and polystyrene (referred to as GPPS, manufactured by Nippon Polystyrene Co., Ltd., trade name: Toporex) or ABS (Sumitomo Chemical Co., Ltd.)
Manufactured by Clastic Co., Ltd.) at a ratio such that the pigment concentration in the kneaded molded product is 1 wt%.
The mixture was fed to a 20 mmφ extruder rotating at 50 ° C. at 0 ° C. and ABS at 230 ° C. and kneaded to obtain a master batch. The extrudability was evaluated by visually judging the surface condition of the strand and the uniformity of the strand diameter at this time.

Regarding the transparency of the pigment dispersant and the masterbatch film, a masterbatch based on GPPS was pressed at a temperature of 190 ° C. to form a 0.1 mm masterbatch film. Obtained. The pigment dispersant in this master batch film was measured with an image processor (Luzex450, manufactured by Toyo Ink Co., Ltd.). The turbidity of the obtained film was measured as a film haze. The smaller the value, the better the transparency.

The evaluation results were as follows. Film performance Pigment dispersibility: 1.00 × 103 particles having a particle size of 50 μm or less
Pieces / cm ² or less Haze: 25% Workability Three-roll discharge speed: 0.085 g / min. Extrusion workability: Good when using either GPPS or ABS

[0184]

Example 3 100 parts by weight of polyvinyl chloride (manufactured by Taiyo PVC Co., Ltd., trade name: TH-1000, degree of polymerization = 1000)
2.5 parts by weight of dioctyltin dimercaptide (trade name: OT-4, manufactured by Tokyo Fine Chemical Co., Ltd.) and 1 part by weight of the oligomer obtained in Synthesis Example 5 were mixed with a Henschel mixer for 9 parts.
Mix at 0 ° C. for 3 minutes. The obtained mixture was kneaded with two rolls, and the lubricity was evaluated. The gelation time was evaluated by charging a sample between the rolls and measuring the time until the charged sample was melted, turned into a sheet, and wound around the roll. Regarding the effect of preventing adhesion to the roll, the sample was put into the roll, mixed for 2 minutes, stopped the roll, and observed the ease of peeling of the sheet 5, 10, 15, 20, and 30 minutes after the roll was stopped. Was evaluated. The results are shown in Table 2 as ○ for good peelability, Δ for hardly peelable, and × for non-peelable. The roll operation was performed under the following conditions. Roll diameter: 8 inches Surface temperature: 190 to 195 ° C. Roll interval: 0.4 mm Roll rotation speed: 18 rpm / 20 rpm (front roll / rear roll) Sample amount: 150 g / time The results are shown in Table 2.

[0185]

[Table 2]

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Makoto Mitani, 1-2-1, Waki, Waki-cho, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Chemicals, Inc. (72) Inventor Terunori Fujita Waka-machi, Kuga-gun, Yamaguchi Prefecture 6-1-2 Ki Wood Inside Mitsui Chemicals, Inc.

Claims (6)

[Claims] 1. A polymer chain containing a vinyl- or vinylidene-type unsaturated bond at one end of a polymer chain, ethylene alone or ethylene and α having 3 to 10 carbon atoms.
(1) 81 to 100 mol% of ethylene units and 0 to 19 mol% of α-olefin units, and (2) measured in decalin at 135 ° C. Intrinsic viscosity [η] is 0.01 to 1.7 dl / g, (3) molecular weight distribution (Mw / Mn) measured by GPC is 3 or less, and (4) 1000 measured by infrared absorption method. A low molecular weight ethylene polymer, wherein the number of vinyl groups M and the number of vinylidene groups N per carbon satisfy the following relational expression (I). M + N ≧ 14000 / Mw (I) 2. An oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, and a silicon-containing group at one end of the polymer chain of the low molecular weight ethylene-based polymer according to claim 1. , A low molecular weight ethylene polymer to which a germanium-containing group, a halogen-containing group or a tin-containing group is bonded. (A) a transition metal compound represented by the following general formula (II), (B) (B-1) an organometallic compound, (B-2) an organoaluminum oxy compound, and (B-3) ) An olefin polymerization catalyst comprising at least one compound selected from the compounds forming an ion pair by reacting with the transition metal compound (A), ethylene alone, or ethylene and ethylene having 3 to 10 carbon atoms. The low molecular weight ethylene polymer according to claim 1, which is obtained by polymerizing an α-olefin of the formula (1). Embedded image (Wherein, M represents a transition metal atom belonging to Groups 3 to 11 of the periodic table, m represents an integer of ^{1 to 6} , R ^{1 to} R ⁶ may be the same or different, and each represents a hydrogen atom, Halogen atom,
A hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group, or a tin-containing group, of which Two or more may be connected to each other to form a ring, and when m is 2 or more, R ¹ to
Two of the groups represented by R ⁶ may be linked, n is a number that satisfies the valence of M, and X is a hydrogen atom, a halogen atom, a hydrocarbon group, an oxygen-containing group, A sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group, or a tin-containing group, and n is 2 or more In the case of, a plurality of groups represented by X may be the same or different, and a plurality of groups represented by X may be bonded to each other to form a ring. ) 4. A release agent for toner containing the low molecular weight ethylene polymer according to claim 1. 5. A pigment dispersant comprising the low molecular weight ethylene polymer according to claim 1. 6. A lubricant for a vinyl chloride resin containing the low molecular weight ethylene polymer according to claim 1 or 2.