JPH1090940A - Thermal fixing type electrophotographic developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermal fixing type electrophotographic developer having an excellent mold releasing property, especially during low energy fixing, a high resistance to blocking and an excellent fixing property and suitable used as a main component for electrostatic toner by preventing offset developing and without contaminating a carrier, a photosensitive body or a heating roller. SOLUTION: In a thermal fixing type electrophotographic developer containing a binding resin A, a colorant B and a lubricant C, the lubricant C is a copolymer containing ethylene of 95 to 99mol% and α-olefin of 1 to 5mol%, which is an ethylene.α-olefin copolymer obtained by copolymerizing ethylene and α-olefin under the existence of a metallocene catalyst D or an ethylene.α-olefin copolymer obtained by heat-reducing a copolymer between ethylene and α-olefin obtained by polymerization under the existence of the metallocene catalyst D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat fixing type electrophotographic developer which is suitably used as a main component of an electrostatic toner, and more particularly, it is excellent in releasing property, blocking resistance and fixing property at the time of heat fixing. In addition, the present invention relates to a heat-fixing type electrophotographic developer capable of obtaining a toner having no offset phenomenon and not contaminating a carrier, a photoreceptor, a heating roller and the like.

[0002]

2. Description of the Related Art An electrophotographic developing material is also called an electrostatic toner, and is a developing material used for developing a latent image formed by charging and exposure in electrostatic electrophotography to form a visible image. This electrostatic toner is a chargeable fine powder obtained by dispersing a colorant such as carbon black or another pigment in a resin. Electrostatic toners include dry two-component toners used with carriers such as iron powder and glass particles, wet toners dispersed using organic solvents such as isoparaffin, and dry one-component toners in which magnetic fine powder is dispersed. Are roughly divided into

By the way, an image obtained by developing on a photoreceptor with electrostatic toner is transferred to paper, and an image obtained by direct development on paper on which a photosensitive layer is formed is directly heated, Fixed by solvent vapor. Among them, fixing by 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. have.

[0004] In particular, in recent years, the use range of electrophotography has expanded,
There is an increasing need to fix electrostatic toner with lower energy than before. For example, as the advance of electrophotography into home appliances progresses, reduction in power consumption of the heating roller unit is required. Further, as a toner used for an output terminal of a high-speed device such as a computer, improvement in high-speed fixing property is also required.

[0005] However, when an image is fixed by contacting a heating member such as a heating roller, if the conventional electrostatic toner is used, an offset phenomenon, that is, a part of the electrostatic toner adheres to the heating member and a subsequent image portion is formed. Transfer phenomenon may occur. In particular, when the temperature of the heating roller is low, the electrostatic toner does not sufficiently soften, so that the fixing property to printing paper or a film is lowered, and at the same time, an offset phenomenon is likely to occur. Further, in the case of high-speed copying, if the heating element is heated to a high temperature in order to improve the fixing effect and the fixing speed, it tends to cause an offset phenomenon. For this reason, for example, the surface of the heating roller is impregnated with silicone oil, or the method of supplying the silicone oil to the surface of the heating roller is used to eliminate the offset phenomenon. Etc. may occur.

Further, various thermoplastic resins are used as a binder resin as a component of the electrostatic toner. In particular, a low molecular weight styrene / (meth) acrylate copolymer has good chargeability, It has an appropriate softening point around ℃, so it is easy to fix, it is easy to wash the photoreceptor, it is less polluted, it has low moisture absorption, it has good mixing with carbon black as a colorant, and it is pulverized. It is widely used because it has advantages such as easy operation. However, conventional electrostatic toners using this low-molecular-weight styrene / (meth) acrylate copolymer as a binder resin also require fixing with a low-temperature heating roller or high-speed copying.
There has been a problem that the offset phenomenon easily occurs.

In order to solve such a problem, it has been proposed to blend a polyolefin wax as a release agent in the electrostatic toner (Japanese Patent Publication Nos. 52-3304, 52-3305, 57-57). JP-A-52574, JP-A-58-58664, and JP-A-58-59455.

[0008]

However, even in the electrostatic toner to which the above-mentioned polyolefin wax is added as a release agent, good fixability is not exhibited under recent low energy fixing conditions, and therefore, the offset phenomenon occurs. Has not yet been prevented. In addition, for example, a toner to which a polyolefin wax is added may have another problem that the blocking resistance is reduced, the toner is blocked in the toner cartridge, and the toner is not supplied from the toner cartridge onto the photoconductor. is there.

Further, a filming phenomenon, that is, a phenomenon in which a low-crystalline substance contained in the polyolefin wax adheres to the surface of a carrier, a photoreceptor, a heating roller, or the like occurs, thereby forming an electrostatic latent image on the photoreceptor or the like. This may adversely affect the charging of the toner and cause a problem that the obtained image is significantly disturbed.

It is an object of the present invention to provide a releasability, particularly excellent releasability at the time of low energy fixing, excellent blocking resistance and fixing property, no offset phenomenon, and a carrier, a photoreceptor, a heating roller and the like. Accordingly, an object of the present invention is to provide a heat fixing type electrophotographic developer which can be suitably used as a main component of the electrostatic toner without contaminating the toner.

[0011]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and as a result, as a wax to be added to an electrostatic toner, a specific ethylene / α-olefin polymerized using a metallocene catalyst. The inventors have found that the above problems can be solved by using a copolymer, and have reached the present invention.

That is, the present invention relates to the following heat fixing type electrophotographic developer. (1) In a heat fixing type electrophotographic developer containing a binder resin (A), a colorant (B) and a lubricant (C), the lubricant (C) is a structural unit 95 to 99 derived from ethylene. An ethylene / α-olefin copolymer containing 1% to 5% by mole of a structural unit derived from an α-olefin, wherein ethylene and an α-olefin are copolymerized in the presence of a metallocene catalyst (D). Ethylene-α-olefin copolymer obtained by polymerization or ethylene-α-olefin copolymer obtained by polymerization in the presence of a metallocene catalyst (D). A heat-fixable electrophotographic developer, characterized by being an α-olefin copolymer. (2) The heat-fixable electrophotographic developer according to the above (1), wherein the α-olefin is one or two selected from the group consisting of propylene, 4-methylpentene-1, hexene-1 and octene-1. . (3) The ethylene / α-olefin copolymer used as the lubricant (C) has a weight average molecular weight (Mw) of 500 to 180.
The heat fixing type electrophotographic developer according to the above (1) or (2), which is 00.

As a binder resin which is a component (A) of the heat-fixable electrophotographic developer of the present invention (hereinafter sometimes simply referred to as a developer), a colorant (B) is fixed to paper or a film. And a resin which can maintain the formed image for a long period of time, has good chargeability, fixability and miscibility with the colorant (B), and has a suitable softening point (around 100 ° C.). Any one can be used as long as it is not particularly limited. As such a resin, a thermoplastic resin conventionally used in this type of heat-fixing type electrophotographic developing material, or a resin having substantially the same characteristics as these can be used.

Specific examples of the binder resin (A) include:
For example, styrene polymer, ketone resin, maleic acid resin, aliphatic polyester resin, aromatic polyester resin, coumarone resin, phenol resin, epoxy resin, terpene resin, polyvinyl butyral, polybutyl methacrylate, polyvinyl chloride, polyethylene, polypropylene, Examples thereof include those made of polybutadiene, ethylene / vinyl acetate copolymer, and the like. These binder resins (A)
Can be used alone or in combination of two or more. Among the binder resins (A), a styrene-based polymer is preferable because it has an appropriate softening point of about 100 ° C. and shows good fixability.

Examples of the styrene-based polymer include a homopolymer or a copolymer composed of only a styrene-based monomer, and a copolymer of a styrene-based monomer and another vinyl-based monomer. Can be Examples of the styrene monomer include styrene, p-chlorostyrene, and vinyl naphthalene. Other vinyl monomers include, for example, ethylenically unsaturated monoolefins such as ethylene, propylene, 1-butene and isobutene; vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; vinyl acetate , Vinyl esters such as vinyl propionate, vinyl benzoate and vinyl acetate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate,
2-chloro-ethyl acrylate, phenyl acrylate,
esters of α-methylene aliphatic monocarboxylic acids such as α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate; nitriles or amides such as acrylonitrile, methacrylonitrile, acrylamide; vinyl methyl ether; Vinyl ethers such as vinyl ethyl ether, vinyl propyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N- And N-vinyl compounds such as vinylpyrrolidone. Among these vinyl monomers, esters of α-methylene aliphatic monocarboxylic acid are preferred.

The styrene polymer preferably has a weight average molecular weight (Mw) of 2,000 or more, and particularly preferably has a weight average molecular weight (Mw) of 3,000 to 30,000. The styrene polymer preferably has a styrene content of 25% by weight or more.

The colorant as the component (B) of the developer of the present invention is not particularly limited as long as it is a colorant which is fixed on paper or a film to form a visible image and does not fade for a long time.
Any of these can be used, and coloring agents conventionally used in this type of heat-fixing type electrophotographic developer or coloring agents similar thereto can be used.

Specific examples of the colorant (B) include, for example, carbon black, phthalocyanine blue, aniline blue, alcohol oil blue, chrome yellow, ultramarine blue, quinoline yellow, lamp black, rose bengal, diazo yellow, rhodamine Pigments or dyes such as B lake, carmine 6B, and quinacridone derivatives. These can be used alone or in combination of two or more.

The coloring agent (B) includes oils such as azine-based nigrosine, indulin, azo-based dyes, anthraquinone-based dyes, triphenylmethane-based dyes, xanthene-based dyes, and phthalocyanine-based dyes for the purpose of complementary colors and charge control. You may mix | blend a soluble dye.

The ethylene / α-olefin copolymer (C) used in the present invention has a structural unit 9 derived from ethylene.
An ethylene / α-olefin copolymer containing 5 to 99 mol%, preferably 97 to 98 mol%, 1 to 5 mol%, preferably 2 to 3 mol% of structural units derived from α-olefin, An ethylene / α-olefin copolymer obtained using a metallocene catalyst (D).

As the α-olefin having 3 to 10 carbon atoms, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, 3-methylbutene-1 are used. , 4-methylpentene
1 and the like. One of these α-olefins may be copolymerized with ethylene alone, or two or more thereof may be copolymerized with ethylene. As the α-olefin, one or two selected from the group consisting of propylene, 4-methylpentene-1, hexene-1 and octene-1 are preferably copolymerized with ethylene.

Ethylene / α-olefin copolymer (C)
Has a weight average molecular weight (Mw) of 500 to 18,000, preferably 1,000 to 6,000. The molecular weight distribution (Mw / Mn) of the ethylene / α-olefin copolymer (C) is usually 1.0 to 6.0, preferably 1.0 to 2.2, and more preferably 1.0 to 1. 5 is desirable. In the present invention, the weight average molecular weight (M
w) or molecular weight distribution (Mw / Mn) was determined by gel permeation chromatography (GPC) using a calibration curve previously prepared using monodisperse polystyrene.
This is a value calculated in terms of monodisperse polystyrene.

The melting point of the ethylene / α-olefin copolymer (C) is usually about 80 to 115 ° C., preferably 100 to 110 ° C. In the present invention, the melting point is a value measured by a differential scanning calorimeter (DSC).

The density of the ethylene / α-olefin copolymer (C) is usually 0.91 to 0.95 g / cm.
^It is desirably about ³ and preferably 0.915 to 0.930 g / cm ³ . In the present invention, the density is JIS K
It is a value measured according to 6760.

In the present invention, the ethylene / α-olefin copolymer (C) is a graft-modified ethylene / α-olefin copolymer obtained by graft-modifying the above-mentioned ethylene / α-olefin copolymer with a styrene monomer or an unsaturated carboxylic acid monomer. Things can also be used. It is desirable that the graft amount of the graft monomer in the graft-modified product is 3 to 60% by weight, preferably 5 to 40% by weight.

The styrene monomer for graft modification includes styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene,
2,5-dimethylstyrene, 3,4-dimethylstyrene, 2,4,6-trimethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-butylstyrene, 4-
sec-butylstyrene, 4-t-butylstyrene,
-Hexylstyrene, 4-nonylstyrene, 4-octylstyrene, 4-phenylstyrene, 4-decylstyrene, 4-dodecylstyrene, 2-chlorostyrene, 3-
Chlorostyrene, 4-chlorostyrene, 2,4-dichlorostyrene, 3,4-dichlorostyrene, 2-methoxystyrene, 4-methoxystyrene, 4-ethoxystyrene and the like can be mentioned.

The unsaturated carboxylic monomers for graft modification include methyl acrylate, ethyl acrylate, butyl acrylate, sec-butyl acrylate, isobutyl acrylate, propyl acrylate, isopropyl acrylate, and acrylic acid. 2-octyl, dodecyl acrylate, stearyl acrylate, hexyl acrylate, isohexyl acrylate, phenyl acrylate,
Acrylic esters such as 2-chlorophenyl acrylate, diethylaminoethyl acrylate, 3-methoxybutyl acrylate, diethylene glycol ethoxylate acrylate, 2,2,2-trifluoroethyl acrylate; methyl methacrylate, ethyl methacrylate; Butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, propyl methacrylate, isopropyl methacrylate, 2-octyl methacrylate, dodecyl methacrylate, stearyl methacrylate, hexyl methacrylate, decyl methacrylate, phenyl methacrylate, methacrylic acid Methacrylic esters such as 2-chlorophenyl, diethylaminoethyl methacrylate, 2-ethylhexyl methacrylate, and 2,2,2-trifluoroethyl methacrylate Ethyl maleic acid, maleic acid propyl, butyl maleate, diethyl maleate,
Maleic esters such as dipropyl maleate and dibutyl maleate; fumaric esters such as ethyl fumarate, butyl fumarate and dibutyl fumarate; itaconic esters such as ethyl itaconate, diethyl itaconate and butyl itaconate Can be given.

Ethylene / α-olefin copolymer (C)
Various known methods can be employed as a method for denaturing. For example, a method may be used in which the ethylene / α-olefin copolymer (C) and a styrene-based monomer or an unsaturated carboxylic acid-based monomer are heated and melt-mixed in the presence of a radical initiator to cause a reaction. The reaction temperature at that time is preferably in the range of 125 to 325 ° C., and the radical initiator used is benzoyl peroxide,
Lauroyl peroxide, dicumyl peroxide, di-
Examples include peroxides such as t-butyl peroxide and azo compounds such as azobisisobutyronitrile.

The ethylene / α-olefin copolymer (C) obtained by using the metallocene catalyst (D) includes an ethylene / α-olefin obtained by copolymerizing ethylene and α-olefin in the presence of the metallocene catalyst (D). An α-olefin copolymer or an ethylene / α-olefin copolymer obtained by heating and degrading a copolymer of ethylene and an α-olefin obtained by polymerization in the presence of a metallocene catalyst (D) And so on. The metallocene catalyst (D) and a method for copolymerizing ethylene and an α-olefin in the presence of the metallocene catalyst (D) will be described later in detail.

As a method for heating and degrading the ethylene / α-olefin copolymer obtained by polymerization in the presence of the metallocene catalyst (D), for example, a high molecular weight ethylene / α-olefin copolymer A method of extruding while melt-kneading by feeding to an extruder having two or more shafts, a tubular reactor,
A method in which a high-molecular-weight ethylene / α-olefin copolymer is directly supplied to a tank reactor or the like to be heated and degraded, or a high-molecular-weight ethylene / α-olefin copolymer is supplied to an extruder and melt-kneaded. While extruding continuously, and supplying to a tubular reactor for heat degradation. The heating temperature in the extruder or reactor is from 350 to 450C, preferably from 380 to 430C. Among these methods,
A method of supplying a high-molecular-weight ethylene / α-olefin copolymer to an extruder, continuously extruding the mixture while melting and kneading the mixture, and supplying the resulting mixture to a tubular reactor to perform heat degradation is preferable. Further, it is preferable to perform the heat degradation under an inert atmosphere such as nitrogen.

In the developing material of the present invention, ethylene-α-
The olefin copolymer (C) can be used alone or in combination of two or more.

In the developing material of the present invention, ethylene-α-
In addition to using the olefin copolymer (C) as a release agent as it is, it is mixed and stirred with an organic solvent (SOL) such as boiling acetone or boiling hexane in advance to remove low molecular weight components, and then used as a release agent. You can use it.
As the organic solvent (SOL), boiling acetone, boiling hexane, boiling methanol, boiling ethanol, boiling tetrahydrofuran, boiling methyl acetate, boiling ethyl acetate, and the like can be used.

Next, the metallocene catalyst (D) will be described. The metallocene catalyst (D) used in the present invention includes:
Metallocene-based catalysts conventionally used as single-site catalysts, and metallocene-based catalysts similar thereto are used without limitation. Particularly, metallocene compounds of transition metals (transition metal compounds) (E) and organic aluminum oxy compounds ( A catalyst comprising F) and / or an ionized ionic compound (G) is preferably used.

As the metallocene compound (E), a metallocene compound of a transition metal selected from Group IVB of the periodic table,
Specific examples include metallocene compounds represented by the following general formula (1). MLx (1) In the formula (1), M is a transition metal selected from Group IVB of the periodic table, specifically, zirconium, titanium or hafnium, and x is the valence of the transition metal.

L is a ligand coordinating to the transition metal, and at least one of these ligands L is a ligand having a cyclopentadienyl skeleton and having this cyclopentadienyl skeleton. The ligand may have a substituent.

The ligand having a cyclopentadienyl skeleton includes, for example, cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n- or i-propylcyclopentadienyl group, n-,
i-, sec-, t-, butylcyclopentadienyl group, hexylcyclopentadienyl group, octylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl Group, pentamethylcyclopentadienyl group, methylethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylhexylcyclopentadienyl group, methylbenzylcyclopentadienyl group, Alkyl or cycloalkyl-substituted cyclopentadienyl groups such as ethylbutylcyclopentadienyl group, ethylhexylcyclopentadienyl group, methylcyclohexylcyclopentadienyl group, and further indenyl group, 4,5,6,7-tetrahydroindenyl Group, fluore And a nyl group.

These groups may be substituted with a halogen atom, a trialkylsilyl group or the like. Among these, an alkyl-substituted cyclopentadienyl group is particularly preferred.

When the metallocene compound (E) represented by the formula (1) has two or more groups having a cyclopentadienyl skeleton as the ligand L, a group having two cyclopentadienyl skeletons among them The two are linked via an alkylene group such as ethylene and propylene, a substituted alkylene group such as isopropylidene and diphenylmethylene, a silylene group or a dimethylsilylene group, a diphenylsilylene group, and a substituted silylene group such as a methylphenylsilylene group. Is also good.

L other than the ligand having a cyclopentadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a sulfonic acid-containing group (-SO
₃ R ¹ ), a halogen atom or a hydrogen atom (here, R ¹ is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, or an aryl group substituted with a halogen atom or an alkyl group). Can be

Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and the like. More specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group Groups, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group, decyl group, alkyl group such as dodecyl group, cyclopentyl group, cycloalkyl group such as cyclohexyl group, Examples include an aryl group such as a phenyl group and a tolyl group, and an aralkyl group such as a benzyl group and a neophyl group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group,
n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, pentoxy group, hexoxy group, octoxy group and the like. Examples of the aryloxy group include a phenoxy group.

Examples of the sulfonic acid-containing group (—SO ₃ R ¹ ) include a methanesulfonato group, a p-toluenesulfonato group, a trifluoromethanesulfonato group, and a p-chlorobenzenesulfonato group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

The metallocene compound (E) represented by the above formula (1) is more specifically represented by the following general formula (2) when the valence of the transition metal is 4, for example. R ² _k R ³ _l R
⁴ _m R ⁵ _n M ... (2)

In the formula (2), M is a transition metal similar to the transition metal of the formula (1), preferably zirconium or titanium, and R ² is a group (ligand) having a cyclopentadienyl skeleton. , R ³ , R ⁴ and R ⁵ are each independently the same as L except for a group having a cyclopentadienyl skeleton or a ligand having a cyclopentadienyl skeleton in the general formula (1). k is an integer of 1 or more, and k + 1
+ M + n = 4.

In the following, a ligand in which M is zirconium and having a cyclopentadienyl skeleton is at least 2
The metallocene compound (E) containing the same is exemplified. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) zirconium phenoxymonochloride, bis (methyl) (Cyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (n-
(Propylcyclopentadienyl) zirconium dichloride, bis (isopropylcyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium bis (methanesulfonate), bis (cyclopentadienyl) zirconium bis (p-toluenesulfonate ),Screw
(1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-ethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-propylcyclopentadienyl) zirconium dichloride and the like can do.

In the present invention, a metallocene compound (E) in which the 1,3-substituted cyclopentadienyl group is replaced by a 1,2-substituted cyclopentadienyl group can also be used. In the above formula (2), R ² , R ³ , R
^At least two of ⁴ and R ⁵ , that is, R ² and R ³ are groups having a cyclopentadienyl skeleton (ligand);
A bridge type metallocene compound (E) in which at least two groups are bonded via an alkylene group, a substituted alkylene group, a silylene group or a substituted silylene group, etc.
Can also be exemplified. At this time, R ⁴ and R ⁵ are independently the same as L except for the ligand having a cyclopentadienyl skeleton described in the formula (1).

Examples of such bridge-type metallocene compounds (E) include ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconiumbis (trifluoromethanesulfonate) and the like. .

In the present invention, a metallocene compound represented by the following general formula (3) can be used as the metallocene compound (E).

Embedded image

In the equation (3), M ¹ is the periodic table IVB, V
B, VIB represents a transition metal atom, specifically, titanium,
Zirconium, hafnium and the like. R ⁶ and R
⁷ is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, and a nitrogen-containing group. Or a phosphorus-containing group, specifically,
Halogen atoms such as fluorine, chlorine, bromine and iodine; alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and cyclohexyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; and arylalkyl groups such as benzyl, phenylethyl and phenylpropyl A hydrocarbon group having 1 to 20 carbon atoms, such as an aryl group such as a group, phenyl, tolyl, dimethylphenyl, naphthyl, and methylnaphthyl; a halogenated hydrocarbon group in which a halogen atom is substituted for the hydrocarbon group;

Monohydrocarbon-substituted silyls such as methylsilyl and phenylsilyl, dihydrocarbon-substituted silyls such as dimethylsilyl and diphenylsilyl, trihydrocarbon-substituted silyls such as trimethylsilyl and triethylsilyl, and silyls of hydrocarbon-substituted silyl such as trimethylsilyl ether Silicon-containing groups such as ethers, silicon-substituted alkyl groups such as trimethylsilylmethyl, and silicon-substituted aryl groups such as trimethylsilylphenyl; alkoxy groups such as hydroxy, methoxy and ethoxy; alloxy groups such as phenoxy and methylphenoxy; phenylmethoxy and phenyl An oxygen-containing group such as an arylalkoxy group such as ethoxy; a sulfur-containing group such as a substituent in which the oxygen of the oxygen-containing group is substituted by sulfur; A phosphorus-containing group such as a phosphino group such as dimethyl phosphinothricin; alkylamino group, phenylamino, nitrogen-containing groups such as an arylamino group or an alkyl aryl amino group such as methylphenylamino.

Among them, R ⁶ is preferably a hydrocarbon group, particularly preferably a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl and propyl. Also R ⁷
Is preferably a hydrogen atom or a hydrocarbon group, particularly a hydrogen atom, or methyl, ethyl or propyl having 1 to 1 carbon atoms.
It is preferably a hydrocarbon group of No. 3.

R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms; Among these, a hydrogen atom, a hydrocarbon group or a halogenated hydrocarbon group is preferred. R ⁸ and R ⁹ , R ⁹
At least one pair of R ^10, R ¹⁰ and R ¹¹ together with the carbon atoms to which they are attached, may form a monocyclic aromatic ring.

When there are two or more hydrocarbon groups or halogenated hydrocarbon groups other than the group forming an aromatic ring, these groups may be bonded to each other to form a ring. When R ¹¹ is a substituent other than an aromatic group, it is preferably a hydrogen atom.

Specific examples of the halogen atom, the hydrocarbon group having 1 to 20 carbon atoms, and the halogenated hydrocarbon group having 1 to 20 carbon atoms are the same as those described above for R ⁶ and R ⁷ .

X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group. Show. A halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
Specific examples of the oxygen-containing group include R ⁶ and R ⁷
The same can be exemplified.

The sulfur-containing groups include the above-mentioned R ⁶ and R ⁷
And the same groups as above, and methylsulfonate, trifluoromethanesulfonate, phenylsulfonate, benzylsulfonate, p-toluenesulfonate, trimethylbenzenesulfonate, triisobutylbenzenesulfonate, p-chlorobenzenesulfonate Phonate,
Sulfonate groups such as pentafluorobenzenesulfonate, and sulfinate groups such as methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzenesulfinate, and pentafluorobenzenesulfinate. Can be illustrated.

Y ¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, 2
Divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, -O-, -CO-, -S-, -SO-,-
^{_{SO 2 -, - NR 12 -}} , - P (R 12) -, - P (O) (R 12)
—, —BR ¹² — or —AlR ¹² — (where R ¹² is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group having 1 to 20 carbon atoms).

Specific examples of Y ¹ include methylene,
Alkylene groups such as dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene, diphenylmethylene Divalent hydrocarbon groups having 1 to 20 carbon atoms, such as arylalkylene groups such as diphenyl-1,2-ethylene, etc .;
A halogenated hydrocarbon group obtained by halogenating a divalent hydrocarbon group from 20 to 20; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, Methylphenylsilylene, diphenylsilylene, di (p-tolyl)
Alkylsilylenes such as silylene, di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, tetramethyl-1,2-disilylene, alkyldisilylene such as tetraphenyl-1,2-disilylene, alkylaryldisilylene, 2 such as an aryldisilylene group
A divalent silicon-containing group; a divalent germanium-containing group obtained by substituting silicon in the divalent silicon-containing group with germanium; a divalent tin-containing group substituent obtained by substituting silicon in the divalent silicon-containing group with tin And R ¹² is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms similar to those of R ⁶ and R ⁷ .

Of these, a divalent silicon-containing group, a divalent germanium-containing group, and a divalent tin-containing group are preferable, and a divalent silicon-containing group is more preferable. Preferred are silylene, alkylarylsilylene, and arylsilylene.

Specific examples of the metallocene compound (E) represented by the above formula (3) are shown below. rac-ethylene (2-methyl-1-indenyl) 2-zirconium-dichloride, rac
-Dimethylsilylene (2-methyl-1-indenyl) -2-zirconium-dichloride, rac-dimethylsilylene (2-methyl-1-indenyl) 2-zirconium-dimethyl, rac-dimethylsilylene-bis (4,7-dimethyl- 1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,
7-trimethyl-1-indenyl) zirconium dichloride,
rac-dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl -4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-
Bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (1-anthracenyl) -1-indenyl) zirconium dichloride and the like.

In the present invention, the metallocene compound (E)
As the metallocene compound represented by the following general formula (4). _{^{LaM 2 Z 2 ··· (4)}} (M 2 is a metal of the periodic table Group IV or the lanthanide series, La is a derivative of a delocalized π bond group, to the metal M ² active site The constraint geometry is given, Z
Is independently a hydrogen atom, a halogen atom or 20
The following carbon, silicon or germanium containing hydrocarbon groups, silyl groups or germyl groups. )

Among the metallocene compounds (E) represented by the formula (4), the metallocene compounds represented by the following general formula (4-1) are preferable.

Embedded image

In the formula (4-1), M ³ is titanium, zirconium or hafnium, and Z is the same as described above.
Cp is a substituted cyclopentadienyl group having a π bond to M ³ and having a substituent W or a derivative thereof.

W is oxygen, sulfur, boron or an element of group IVA of the periodic table, V is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and forms a condensed ring with W and V Is also good.

Specific examples of the metallocene compound (E) represented by the formula (4-1) include [dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] titanium dichloride, (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-ethanediyl)
Titanium dichloride, [dibenzyl (t-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) silane] titanium dichloride, [dimethyl (t-butylamido) (tetramethyl-eta ⁵ - cyclopentadienyl) silane] dibenzyl Titanium, [dimethyl (t-butylamide) (tetramethyl-η ⁵ -cyclopentadienyl) silane] dimethyltitanium and the like.

Other examples include metallocene compounds in which titanium of the above metallocene compound (E) is replaced with zirconium or hafnium. Equation (4)
Alternatively, the metallocene compound (E) represented by (4-1) is preferably a zirconocene compound in which the central metal atom is zirconium and has a ligand having at least two cyclopentadienyl skeletons.

In the present invention, the metallocene compound (E)
The following metallocene compounds can also be used.
Ethylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride, ethylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (2,7-
Dimethyl-9-fluorenyl) zirconium dichloride, ethylene {2-methyl-4 (9-phenanthryl) -1-indenyl}
(2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5-benzo-1-indenyl) (9
-Fluorenyl) zirconium dichloride, ethylene (2-
Methyl-4,5-benzo-1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-4,5-benzo-1-indenyl) (2,7-di-t -Butyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl
-α-acenaphth-1-indenyl) (9-fluorenyl) zirconium dichloride, ethylene (2-methyl-α-acenaphth-
1-indenyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, ethylene (2-methyl-α-acenaphth-1-
Indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, dimethylsilylene {2-methyl-4 (9-phenanthryl) -1-indenyl} (9-fluorenyl) zirconium dichloride and the like.

Other examples of the zirconium compound include compounds in which zirconium is replaced with titanium or hafnium.

The metallocene compound (E) used in the present invention
The metallocene compound (E) described above may be used alone or in combination of two or more. The metallocene compound (E) used in the present invention may be used after being diluted with a hydrocarbon or a halogenated hydrocarbon.

Next, the organoaluminum oxy compound (F) and the ionized ionic compound (G) used for forming the metallocene catalyst (D) will be described.

The organoaluminum oxy compound (F) used in the present invention may be a conventionally known aluminoxane (F)
Or a benzene-insoluble organic aluminum oxy compound (F) as exemplified in JP-A-2-78687.

Such a conventionally known aluminoxane (F) is specifically represented by the following general formula (5) or (6).

Embedded image [In the above general formula (5) or (6), R ¹³ is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, and a butyl group, preferably a methyl group, an ethyl group, particularly preferably a methyl group. , M is 2 or more, preferably 5 to 4
It is an integer of 0. ]

The aluminoxane (F) has an alkyloxyaluminum unit represented by the formula (OAl (R ¹⁴ )) and an alkyloxyaluminum unit represented by the formula (OAl (R ¹⁵ )) (where R ¹⁴ and R ¹⁵ can be exemplified by the same hydrocarbon groups as R ^13, and R ¹⁴ and R ¹⁵ represent different groups).

Solvents used in the preparation of aluminoxane (F) include, for example, aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, pentane, hexane, heptane, octane, decane, dodecane, hexadecane , Aliphatic hydrocarbons such as octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane; ethers such as ethyl ether and tetrahydrofuran; petroleum fractions such as gasoline, kerosene and gas oil; and Examples thereof include hydrocarbon solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbon halides, especially chlorinated compounds and brominated compounds. Among these solvents, aromatic hydrocarbons are particularly preferred.

As the ionized ionic compound (G),
Lewis acids, ionic compounds, borane compounds, and carborane compounds can be exemplified. These ionized ionic compounds (G) are described in JP-A-1-501950, JP-A-1-502036, and JP-A-3-17.
No. 9005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, and USP-5321106.

As the Lewis acid used as the ionized ionic compound (G), BR ₃ (where R is the same or different and may have a substituent such as fluorine, methyl, trifluoromethyl, etc.) A phenyl group or fluorine), for example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl)
Boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron and the like.

The ionic compound used as the ionized ionic compound (G) is a salt comprising a cationic compound and an anionic compound. The anion functions to cationize the metallocene compound (E) by reacting with the metallocene compound (E), thereby stabilizing the transition metal cation species by forming an ion pair. Examples of such anions include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion, and those which are relatively bulky and stabilize transition metal cation species are preferable. Examples of the cation include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. More specifically, triphenylcarbenium cation, tributylammonium cation,
N, N-dimethylammonium cation, ferrocenium cation and the like.

Of these, ionic compounds containing a boron compound as an anion are preferable. Specific examples of the ionic compound include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and trialkylammonium salts. Reel phosphonium salts and the like can be mentioned.

Examples of the above trialkyl-substituted ammonium salts include, for example, triethylammonium tetra (phenyl)
Boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium tetra (p-tolyl) boron and the like.

The N, N-dialkylanilinium salt includes, for example, N, N-dimethylanilinium tetra (phenyl)
Boron.

The dialkylammonium salts include:
For example, di (n-propyl) ammonium tetra (pentafluorophenyl) boron, dicyclohexylammonium tetra (phenyl) boron and the like can be mentioned.

Examples of the triarylphosphonium salt include triphenylphosphonium tetra (phenyl) boron, tri (methylphenyl) phosphoniumtetra (phenyl) boron, and tri (dimethylphenyl) phosphoniumtetra (phenyl) ) Boron and the like.

Further, as the ionic compound, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis
(Pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) borate and the like can also be mentioned.

Examples of the borane compound used as the ionized ionic compound (G) include the following compounds. Decaborane (14); salts of anions such as bis [tri (n-butyl) ammonium] nonaborate and bis [tri (n-butyl) ammonium] decaborate;
And tri (n-butyl) ammonium bis (dodecahydride dodecaborate) cobaltate (III), bis (tri
(n-butyl) ammonium] salts of metal borane anions such as bis (dodecahydride dodecaborate) nickelate (III).

As the carborane compound used as the ionized ionic compound (G), 4-carbanonaborane (1
4) salts of anions such as 1,3-dicarbanonaborane (13); and tri (n-butyl) ammonium bis (nonahydride-1,3-dicarbanonaborate) cobaltate (II
I) and salts of metal carborane anions such as tri (n-butyl) ammonium bis (undecahydride-7,8-dicarboundecaborate) ferrate (III). The ionized ionic compound (G) as described above may be used in combination of two or more.

The metallocene catalyst (D) used in the present invention comprises:
If necessary, the composition may further contain the following organoaluminum compound (H) in addition to the above components. As the organoaluminum compound (H) optionally used in the present invention, for example, an organoaluminum compound represented by the following general formula (7) can be mentioned.

(R ¹⁶ ) _n AlX _3-n (7) In the formula (7), R ¹⁶ has 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.
Wherein X is a halogen atom or a hydrogen atom, and n is 1-3.

Examples of such a hydrocarbon group having 1 to 15 carbon atoms include an alkyl group, a cycloalkyl group and an aryl group. Specifically, a methyl group, an ethyl group, an n-propyl group, Examples thereof include an isopropyl group and an isobutyl group.

Specific examples of such organoaluminum compounds include the following compounds. Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, tri n-butyl aluminum,
Triisobutylaluminum, in trialkylaluminum, formula _{(i-C 4 H 9)} xAly (C 5 H 10) z ( wherein such tri sec- butyl aluminum, x, y, z are each a positive number, z ≧ 2x) represented by alkenyl aluminum such as isoprenyl aluminum, dialkyl aluminum halide such as dimethyl aluminum chloride and diisobutyl aluminum chloride, dialkyl aluminum hydride such as diisobutyl aluminum hydride, dialkyl aluminum alkoxide such as dimethyl aluminum methoxide, and diethyl And dialkylaluminum aryloxides such as aluminum phenoxide.

As the organoaluminum compound (H), a compound represented by the following formula (8) can also be used. (R ¹⁸ ) _n Al (R ¹⁷ ) _3-n (8) (wherein, R ¹⁸ is the same as R ¹⁶ , and R ¹⁷ is —OR ¹⁹
Group, -OSi (R ²⁰⁾ ₃ group, -OAl (R ²¹⁾ ₂ group, -N (R
²² ) ₂ groups, -Si (R ²³ ) ₃ groups or -N (R ²⁴ ) Al (R ²⁵ ) ₂
A group, n is ^{1~2, R 19, R 20,} R 21 and R ²⁵ and the like methyl, ethyl, isopropyl, isobutyl, cyclohexyl, phenyl, R ²²
Is hydrogen, methyl, ethyl, isopropyl, phenyl, trimethylsilyl, etc., and R ²³ and R ²⁴
Represents a methyl group, an ethyl group or the like. )

Such an organoaluminum compound (H)
Specific examples thereof include the following compounds. (C ₂ H ₅ ) ₂ Al (OSi (CH ₃ ) ₃ ), (iso-C ₄ H ₉ ) ₂ A
l (OSi (CH ₃ ) ₃ ), (C ₂ H ₅ ) ₂ Al (OAl (C
_{2 H 5) 2), (} CH 3) 2 Al (N (C 2 H 5) 2), (C 2 H 5) 2 Al
(NH (CH ₃ )), (iso-C ₄ H ₉ ) ₂ Al [N (Si (C
Such as H _{3) 3) 2].}

Metallocene catalyst (D) used in the present invention
May be a solid catalyst in which at least one of the above-mentioned components (E), (F), (G) and (H) is supported on a particulate carrier.

The metallocene catalyst (D) comprises a fine particle carrier, a component (E), a component (F) (or a component (G)) and a polymer or copolymer produced by prepolymerization, and if necessary, a component. (H) may be used.

The particulate carrier used for the solid catalyst and the prepolymerized catalyst is an inorganic or organic compound having a particle size of 10 to 300 μm, preferably 20 to 200 μm.
It is a granular or particulate solid of μm.

Among them, a porous oxide is used as the inorganic carrier.
Preferably, specifically, SiO 2_Two, Al_TwoO_Three, MgO, Z
rO_Two, TiO_Two, B_TwoO_Three, CaO, ZnO, BaO, T
hO _TwoOr mixtures thereof, for example SiO 2_Two-M
gO, SiO_Two-Al_TwoO_Three, SiO_Two-TiO_Two, SiO_Two-
V_TwoO_Five, SiO_Two-Cr_TwoO_Three, SiO_Two-TiO_Two-MgO
And the like. Of these, SiO_TwoAnd
And Al_TwoO_ThreeAt least one member selected from the group consisting of
It is preferable that the main component is a component.

The inorganic oxide contains a small amount of Na ₂ C
O ₃ , K ₂ CO ₃ , CaCO ₃ , MgCO ₃ , Na ₂ SO ₄ ,
Al ₂ (SO ₄ ) ₃ , BaSO ₄ , KNO ₃ , Mg (NO ₃ ) ₂ ,
It may contain carbonate, sulfate, nitrate and oxide components such as Al (NO ₃ ) ₃ , Na ₂ O, K ₂ O and Li ₂ O.

The properties of such a fine particle carrier differ depending on the kind and the production method, but the specific surface area is 50 to 1000.
m ² / g, preferably 100~700m ² / g, it is desirable that the pore volume is 0.3~2.5cm ³ / g. The finely divided carrier may be 100 to 1000 as needed.
C., preferably at a temperature of 150 to 700 C.

Further, as the fine particle carrier, a particle size of 10
Granular or fine-grained solids of organic compounds having a size of up to 300 μm can be mentioned. Such organic compounds include ethylene, propylene, 1-butene, 4-methyl-1
A (co) polymer formed mainly of an α-olefin having 2 to 14 carbon atoms such as pentene, or a polymer or copolymer formed mainly of vinylcyclohexane or styrene.

To produce the ethylene / α-olefin copolymer (C) used in the present invention using a metallocene catalyst (D), ethylene and α-olefin are added in the presence of the metallocene catalyst (D). Usually, copolymerization is performed by solution polymerization or slurry polymerization in the liquid phase. In this case, a hydrocarbon solvent is generally used, but an α-olefin such as propylene may be used as the solvent.

Examples of such hydrocarbon solvents include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane and kerosene and halogen derivatives thereof, and alicyclic hydrocarbons such as cyclohexane, methylcyclopentane and methylcyclohexane. Hydrogen and halogen derivatives thereof, aromatic hydrocarbons such as benzene, toluene and xylene, and halogen derivatives such as chlorobenzene are used. These solvents may be used in combination.

Ethylene and α-olefin may be copolymerized by either a batch method or a continuous method. When carrying out the copolymerization by a continuous method, the metallocene catalyst (D) is used in the following concentrations.

That is, the concentration of the metallocene compound (E) in the polymerization system is usually 0.00005 to 0.1 mmol / liter (polymerization volume), preferably 0.0001 to 0.1.
05 mmol / liter. The organoaluminum oxy compound (F) is supplied in an amount of 1 to 10000, preferably 10 to 5000 in terms of the ratio of aluminum atom (Al / transition metal) to the metallocene compound (E) in the polymerization system.

The molar ratio of the ionized ionic compound (G) to the metallocene compound (E) in the polymerization system (the ionized ionic compound (G)
/ Metallocene compound (E)) in an amount of 0.5 to 20, preferably 1 to 10.

When the organoaluminum compound (H) is used, it is used in an amount of usually about 0 to 5 mmol / liter (polymerization volume), preferably about 0 to 2 mmol / liter.

Ethylene / α-olefin copolymer (C)
Is usually at a temperature of −20 to +2.
50 ° C, preferably 0 to 200 ° C, pressure exceeding 0 ~
80 kg / cm ² (gauge pressure), preferably more than 0 to 5
It is performed under the condition of 0 kg / cm ² (gauge pressure).

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 10 minutes. One hour.

Ethylene / α-olefin copolymer (C)
When producing ethylene and α-olefin,
The copolymer is supplied to the polymerization system in such an amount that a copolymer having the above specific composition can be obtained. Further, upon copolymerization, a molecular weight regulator such as hydrogen may be used.

When ethylene and α-olefin are copolymerized as described above, the ethylene / α-olefin copolymer (C) is usually obtained as a polymerization solution containing the same.
This polymerization liquid is treated by a conventional method to obtain an ethylene / α-olefin copolymer (C).

The ethylene / α-olefin copolymer (C) thus obtained is used as it is, or as needed, a mixture of two or more kinds. Further, in order to make the range of the ethylene / α-olefin copolymer (C) used in the present invention, the ethylene / α-olefin copolymer obtained by using the above metallocene catalyst (D) and the above metallocene catalyst ( It is also possible to appropriately blend the ethylene homopolymer obtained using D). Further, an ethylene / α-olefin copolymer obtained by subjecting the ethylene / α-olefin copolymer obtained by using the above metallocene catalyst (D) to heat degradation may be used.

In the present invention, by blending such an ethylene / α-olefin copolymer (C), the releasability, particularly the releasability at the time of low energy fixing, is excellent, and the blocking resistance and the fixing property are improved. And a heat-fixing type electrophotographic developer which does not have an offset phenomenon and does not contaminate a carrier, a photoreceptor, a heating roller and the like.

In the developing material of the present invention, the mixing ratio of the binder resin (A), the colorant (B) and the ethylene / α-olefin copolymer (C) is usually the binder resin (A) / colorant (B) / Ethylene / α-olefin copolymer (C)
Is about 100 / (1-20) / (1-20) by weight, preferably about 100 / (1-10) / (1-10).

The developing material of the present invention contains, in addition to the essential components of the binder resin (A), the colorant (B) and the ethylene / α-olefin copolymer (C), a range that does not impair the effects of the present invention. And other components may be blended. For example, other components such as a charge control material, a plasticizer, and a release agent such as another wax may be appropriately compounded.

The developer of the present invention comprises a two-component electrostatic toner,
It is used as a main component of any electrostatic toner such as a one-component electrostatic toner.

When the developer of the present invention is used as a main component of a two-component electrostatic toner, the binder resin (A), the colorant (B), Melt and knead the ethylene / α-olefin copolymer (C) and other components to be blended if necessary using a Banbury mixer or the like, or mix them by a known method using a ball mill, an attritor or the like, and then heat. The mixture is kneaded using a twin roll, a heating kneader, an extruder or the like, and then cooled and solidified. Next, the obtained solidified product is crushed using a hammer mill, crusher, or the like, or without crushing, finely crushed by a jet mill, a vibration mill, or by adding water and a ball mill, an attritor, or the like. Average particle size 5
A method of preparing a two-component system by adding a carrier to a material having a size of 35 μm can be adopted. As the carrier, known carriers can be used without any particular limitation, and examples thereof include silica sand, glass beads, iron balls having a particle size of 200 to 700 μm, and powders of magnetic materials such as iron, nickel, and cobalt.

The amount of the ethylene / α-olefin copolymer (C) in this two-component electrostatic toner is 1 to 100 parts by weight of the thermoplastic resin including the binder resin (A).
20 parts by weight, preferably 2 to 10 parts by weight.

When the developing material of the present invention is used as a one-component electrostatic toner, the one-component electrostatic toner comprises a binder resin (A), a colorant (B), an ethylene / α-olefin copolymer. Coalescing (C), other components to be blended as required,
The other thermoplastic resin and magnetic material powder can be treated according to the same method as in the preparation of the two-component electrostatic toner to prepare a one-component system without adding a carrier.

The amount of the ethylene / α-olefin copolymer (C) in this one-component electrostatic toner is 1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the binder resin (A). It is an amount in parts by weight.

As the magnetic material powder to be compounded in the one-component electrostatic toner, a fine powder of magnetite having a particle size of 1 μm or less is usually used. However, metals such as cobalt, iron, nickel and the like, alloys thereof, and oxides , Ferrite and powders of mixtures thereof can be used. The compounding amount of the magnetic material powder in this one-component electrostatic toner is:
The obtained electrostatic toner does not lower its electrical resistance, has good charge retention of the electrostatic toner, does not cause image bleeding, and has a softening point in an appropriate range, so that fixing can be suitably performed. In addition, the required charge value is obtained, and scattering is difficult, so that the magnetic material powder is usually about 40 to 100 parts by weight relative to the total 100 parts by weight of the binder resin (A) and the magnetic material powder. If necessary, a known charge control agent may be added to the two-component electrostatic toner or the one-component electrostatic toner.

Further, the ethylene / α used in the present invention
-The olefin copolymer (C) can be easily used as a component of a so-called polymerized toner because the olefin copolymer (C) can be easily made into an aqueous dispersion of fine particles alone or by adding an emulsifier such as a surfactant. Can be.

[0120]

The heat-fixing type electrophotographic developer of the present invention comprises:
Binder resin (A), colorant (B) and specific ethylene α-
Since it contains a lubricant (C) composed of an olefin copolymer, it has excellent releasability, particularly excellent releasability during low energy fixing, and has excellent blocking resistance and fixing properties,
Furthermore, there is no offset phenomenon, and carriers, photoconductors,
There is no contamination of the heating roller. Therefore, the heat fixing type electrophotographic developer of the present invention can be suitably used as a main component of the electrostatic toner.

[0121]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described specifically with reference to examples and comparative examples of the present invention, but these examples do not limit the scope of the present invention. In Examples and Comparative Examples, the weight average molecular weight (Mw) and molecular weight distribution (Mw /
Mn), the melting point, and the evaluation of the fixing property, blocking resistance, offset phenomenon, image disturbance, and contamination of the photoreceptor / heating roller of the two-component electrostatic toner in the evaluation of the toner properties are described below. Was performed according to

<< Weight Average Molecular Weight (Mw) and Molecular Weight Distribution (Mw / Mn) >> A solution sample of an ethylene / α-olefin copolymer having a concentration of 0.1% by weight was prepared using o-dichlorobenzene as a solvent. This sample was used as a column as GMH-HT (60 cm) manufactured by Tosoh Corporation and GMH-HT.
It was measured at a temperature of 140 ° C. and a measured flow rate of 1.0 ml / min using a gel permeation chromatography apparatus (GPC150C, manufactured by Waters) using a HTL (60 cm) connected. The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were determined in terms of polystyrene by a calibration curve prepared in advance using a monodisperse polystyrene standard sample. << Melting Point >> The melting point was measured at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC).

<< Fixing Property of Fixed Image >> Using a two-component electrostatic developing material, a test image was copied and developed on a selenium photosensitive member by electrophotography. The obtained image is transferred to transfer paper, and a fixing roller having a surface formed of polytetrafluoroethylene (manufactured by DuPont) and a pressure roller having a surface formed of silicon rubber (KE-1300RTV, manufactured by Shin-Etsu Chemical Co., Ltd.) And the temperature of the fixing roller is set to 20.
The temperature was adjusted to 0 ° C. to fix the image. Next, the surface of the obtained fixed image was adjusted to a height of 15 m under a load of 500 g.
After rubbing 5 times with an mx 7.5 mm sand eraser, before and after that, the optical reflection density of the surface was measured with a Macbeth reflection densitometer, and the image remaining rate defined by the following equation was obtained. did. Image remaining rate (%) = (image density after rubbing) / (image density before rubbing) × 100

<< Blocking Resistance of Toner >> 100 g of a two-component electrostatic developing material was placed in a 500 ml polyethylene container, shaken for 30 minutes, and allowed to stand at 60 ° C. for 50 hours. Thereafter, the temperature was returned to room temperature, and the state of blocking was examined. The state of blocking was visually determined according to the following evaluation criteria, and the blocking resistance was evaluated. A: No blocking at all. ：: A small amount of blocking that could be easily unraveled by hand occurred. Δ: There are quite many blockings that can be easily unraveled. ×: There are many lumps that cannot be completely loosened by hand.

<< Offset Phenomenon, Image Disturbance, and Contamination of Photoconductor and Fixing Roller >> A test image was copied and developed on a selenium photoconductor by electrophotography using a two-component electrostatic developing material. The obtained image was transferred to a transfer paper, and the surface was formed with a 200 ° C. fixing roller formed of polytetrafluoroethylene (manufactured by DuPont) and the surface formed of silicon rubber (KE-1300RTV manufactured by Shin-Etsu Chemical Co., Ltd.). The copying process for fixing the image was repeatedly performed using the pressure-bonded roller. After repeating the copying process 5000 times, the presence or absence of an offset phenomenon, the presence or absence of image disorder, and the contamination of the surface of the photoreceptor / fixing roller were visually inspected and evaluated according to the following criteria.

[Offset Phenomenon and Image Disturbance] A: There was no offset phenomenon and no image disturbance. Δ: Very slight offset phenomenon and image disturbance occurred. ×: Offset phenomenon or image disorder is quite severe.

[Stainability of Photoconductor and Fixing Roller Surfaces] A: The surfaces of the photoconductor and fixing roller are not stained at all. ：: Very little dirt is seen on the surface of the photoconductor or the fixing roller. Δ: Stain was slightly observed on the surface of the photoconductor or the fixing roller. X: The surface of the photoreceptor or the fixing roller is considerably dirty.

Production Example 1 << Production of Ethylene / α-Olefin Copolymer >> Using a metallocene catalyst, an ethylene / α-olefin copolymer was produced as follows. Internal volume 2 fully purged with nitrogen
Hexane 800 in liter stainless steel autoclave
ml and 200 ml of 4-methylpentene-1 were introduced, and hydrogen was introduced until the pressure reached 8 kg / cm ² (gauge pressure). Next, after raising the temperature in the system to 130 ° C., 0.5 mmol of triisobutylaluminum, triphenylcarbenium tetrakis (pentafluorophenyl)
The polymerization was initiated by injecting 0.002 mmol of borate and 0.001 mmol of ethylene bis (indenyl) zirconium dichloride with ethylene. Thereafter, the total pressure was maintained at 30 kg / cm ² (gauge pressure) by continuously supplying only ethylene,
Polymerization was performed for minutes.

After terminating the polymerization by adding a small amount of ethanol into the system, unreacted ethylene was purged. The polymer was precipitated by throwing the obtained polymer solution into a large excess of methanol. The polymer was collected by filtration and dried at 80 ° C. under reduced pressure overnight. As a result, Mw was 5400 and Mw / Mn was 2.15.
Having a melting point of 108 ° C. and 4-methylpentene
As a result, 54.8 g of an ethylene-4-methylpentene-1 copolymer having a content of 4.5 mol% was obtained.

Example 1 << Preparation of Toner >> Styrene / n-butyl acrylate copolymer (manufactured by Sanyo Chemical Industries, Ltd., Hymer SEM-73)
F, 100 parts by weight), 4 parts by weight of the ethylene / α-olefin copolymer wax obtained in Production Example 1, 9 parts by weight of carbon black (Diablack SH, trade name, manufactured by Mitsubishi Kasei Kogyo Co., Ltd.), 2 parts by weight of BASF Co., Ltd., Pomelo Fast Black B (trademark) and 2 parts by weight of a charge controlling agent (P-51, trade name, manufactured by Orient Chemical Industries)
The mixture was melt-kneaded with a Banbury mixer, cooled, finely pulverized by a jet mill, and classified by a classifier to obtain toner particles having an average particle diameter of 10 to 15 μm.

<< Carrier >> A ferrite carrier having an average particle size of 50 to 80 μm was used. << Preparation of Developer >> A two-component electrostatic developer was prepared by mixing 120 parts by weight of the toner particles and 100 parts by weight of a ferrite carrier. About this two-component electrostatic developing material,
The fixing method of the fixed image, the blocking resistance of the toner, the offset phenomenon, the disorder of the image, and the
The fouling of the fixing roller was evaluated. Table 1 shows the results.

Examples 2 and 3 In the same manner as in Example 1 except that the ethylene / α-olefin copolymer wax shown in Table 1 was used instead of the ethylene / α-olefin copolymer wax of Example 1, To prepare a developing material, and evaluated. Table 1 shows the results.

Example 4 High-Molecular-Weight Ethylene-Hexene-1 Copolymer (Ethylene / hexene-1 copolymer obtained by using ethylene and hexene-1 as monomers and reducing only the hydrogen supply amount in the same manner as in Example 1)
Hexene-1 copolymer. A melt index of 4 and a density of 0.920 g / cm ³ ) were supplied to a twin screw extruder (screw diameter 30 mmφ), and extruded at a screw rotation speed of 25 rpm to be heated and degraded at 400 ° C.
Hexene-1 copolymer wax was prepared. A developer was prepared and evaluated in the same manner as in Example 1 except that the ethylene / hexene-1 copolymer wax was used instead of the ethylene / α-olefin copolymer wax in Example 1. Table 1 shows the results.

[0134]

[Table 1]

────────────────────────────────────────────────── ─── front page continued (51) Int.Cl. ⁶ identifications FI C08L 23:08)

Claims (3)

[Claims] 1. A heat fixing type electrophotographic developer comprising a binder resin (A), a colorant (B) and a lubricant (C), wherein the lubricant (C) is a structural unit 95 derived from ethylene. An ethylene-α-olefin copolymer containing 1 to 5 mol% of structural units derived from α-olefin, and ethylene and α-olefin in the presence of a metallocene catalyst (D). An ethylene / α-olefin copolymer obtained by copolymerization, or a copolymer of ethylene and α-olefin obtained by polymerization in the presence of a metallocene catalyst (D), which is heated and degraded. A heat-fixable electrophotographic developer, characterized by being the ethylene / α-olefin copolymer obtained. 2. The heat fixing type electrophotographic development according to claim 1, wherein the α-olefin is one or two selected from the group consisting of propylene, 4-methylpentene-1, hexene-1 and octene-1. Wood. 3. Ethylene α-used as a lubricant (C)
The weight average molecular weight (Mw) of the olefin copolymer is 500
The heat-fixable electrophotographic developer according to claim 1, wherein the number is from 1 to 18,000.