JP3463436B2 - Toner for developing electrostatic images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to electrophotography, electrostatic recording, and the like.
Method for developing an electrostatic latent image
The present invention relates to a toner for developing an image. [0002] 2. Description of the Related Art In electrophotography, when copying,
Electrostatic latent image formed on a photoreceptor using a photoconductive material
To the toner by magnetic brush development method
Transfer the toner image on the photoreceptor to a transfer material such as paper or sheet.
After copying, fix using heat, solvent, pressure, etc.
To get an image. [0003] As a method of fixing a toner image, heating
The melting method is most often used, but this method is a contact type
And non-contact type. In particular, contact-type heating
The roller fixing method has good thermal efficiency and high-speed fixing is possible.
In recent years, widely used in commercial copiers, printers, etc.
It has been. However, this heating roll fixing method
However, it has some disadvantages. Especially with serious drawbacks
The energy, that is, the amount of power used, is
It is pointed out that the number is considerably larger than the fixing method. [0004] Of course, the intensity of the fixed image on a transfer material such as paper
Is compared with the pressure roll fusing method.
Is much better, and paper deformation due to pressure,
Also excellent in terms of generation of cracks. Therefore, heat fixing
In the schemeHowReduce power consumption or paraphrase
BaHowLower the minimum temperature required for fixing the toner image
Has been considered. [0005] As a powerful means to achieve this purpose,
Is commonly used in binder resins for toner.
Has a Tg (glass transition temperature) several tens of degrees lower than
And those with low molecular weight
You. However, many such toners are stored during storage.
Or, caking phenomenon or aggregation occurs in the copier
It has a fatal drawback of being easy to make. [0006] In contrast to the above, blocking resistance and flow
Very fine colloidal silica and aluminum for improved performance
There is a way to attach toner, titania, etc. to the toner particle surface.
You. This measure can also raise the minimum fixing temperature
No, and also improved blocking resistance and flowability
Degree is achieved. However, these microparticles
Heat treatment to fuse them to the toner particle surface
Even if the surface is treated,
Light bodies, especially those whose surfaces are coated with organic polymers, etc.
It often has a bad effect on you. That is, many times
These particles are semi-permanent on the photoreceptor surface during use
Will cause inconvenience, causing image loss.
You. Therefore, this strategy cannot be a drastic solution.
No. Further, when the above-mentioned binder resin is used,
In the case of heat roll,
Toner adheres to the heating roll and stains the next copy.
There is also a problem that the offset phenomenon occurs. Special
In order to cope with the increase in fixing speed in high-speed copying
In addition, if the heating heat per unit time is increased, the offset
The result is that the phenomenon is more likely to be triggered. A polyester resin is used as a binder resin for the toner.
There is also a method using a resin. Polyester resin is generally
Excellent low-temperature fixability compared to styrene-acrylic resin
Described in U.S. Pat. No. 3,590,000.
As described above, it can be applied to the non-contact fixing method,
There is a disadvantage that the offset phenomenon is likely to occur. In the heating roll fixing method, a fixing roll is used.
A release claw is provided in the transfer section, and the transfer material,
After passing through the roll, it is prevented from winding around the roll.
However, with the recent increase in the speed of copiers,
Due to increased stress on
Image defects at the leading edge of the transfer material due to nails
Trouble may occur. Further, the copied image is further copied as a document.
May be copied to the automatic document feeder of the copier.
When the image is loaded, the original is fed by the paper feed roller of this device.
The image is blurred or smeared due to rubbing. Also, both sides
For originals and multicolor originals, after fixing the first copy image,
The second copy is performed.
The surface is rubbed, and the image is blurred or stained. Further
And multiple documents are stored in a copier in the primary storage
One by one with a paper feed roller for the second copy
Remove the original, but also in this transfer, the back of the original and the original below
Image surface is rubbed, rubbing and smearing on both sides
And lower the image quality. In order to improve these problems, the toner
As a lubricant, low molecular weight polypropylene or polyethylene
There has been proposed a method of adding an additive (Japanese Patent Publication No. 52-33).
No. 04, Japanese Patent Publication No. 52-3305, Japanese Patent Publication No. 57
-52574, JP-B-58-58664,
JP-A-58-59455 and JP-A-60-15
No. 1650). With the toner added with the above lubricant
Is offset resistance due to poor releasability from the heating roll
For improvement of peeling nails, improvement of rubbing resistance of fixed images, etc.
Although effective to some extent, its effect is not enough.
Furthermore, the phase of these polyolefin-based lubricants and resin components
Lubricant forms large domains in toner due to poor solubility
And as a result, increase the powder fluidity and cohesion of the toner.
Worse. As a method for solving these problems,
Graft the polyolefin into the resin and make it compatible with the resin
(JP-A-60-457, JP-A-60-93)
456, JP-A-60-93457, etc.)
Using a reactive polyolefin to disperse in resin
JP-A-58-63947 and JP-A-59-17775.
No. 0, JP-A-60-3644, JP-A-62-264
No. 14508, JP-A-63-191817
Etc.) are known. However, these methods
Improves polyolefin dispersibility, powder fluidity, agglomeration
Although it is possible to suppress the deterioration of
There is a problem that the effect of improving the releasing ability to be lost is lost. On the other hand, in order to improve low-temperature fixability, polyester
When using resin, the above-mentioned problem of offset
Increase the degree of polymerization of the polymer,
Introduces a crosslinked structure or gel component to introduce toner
To the roll surface by increasing the surface cohesive force during melting
In many cases, measures are taken to prevent toner fusing. However
However, these methods have no effect on offset resistance.
Although there is, it not only raises the minimum fixing temperature,
The toner pulverizability in the manufacturing process deteriorates. In addition, a problem arises with the offset resistance.
Peeling nail scratches only with polyester resin
It is not enough to deal with
Often, wax is added to improve releasability.
Is being done. In this case, the powder characteristics and release properties may vary.
In consideration of cost, generally a polypropylene wax
Is often used, but its melting point is polyester
Temperature exceeds the minimum fixing temperature obtained by
Make full use of the effect of lowering the minimum fixing temperature of the heat roll
There is a problem that can not be. Further, a wax is used for the polyester resin.
Is added, the various methods described above may be used.
Boxes form domains and disperse. This means that
As a result, changing the dispersion of other components in the toner
The toner charging behavior, especially during long-term continuous use.
It often affects the charging behavior. [0016] SUMMARY OF THE INVENTION Therefore, the present invention
In view of the above situation in the prior art,
It was made to improve the point. You
In other words, the object of the present invention is to remove without increasing power consumption.
Lower the minimum fixing temperature, including the temperature at which nail flaws occur, to prevent off
Good settability and rubbing image strength, powder flow
Electrostatic charge image with excellent resistance and no blocking phenomenon
An object of the present invention is to provide an image toner. [0017] Means for Solving the Problems The present inventors have conducted intensive studies.
As a result, drying with binder resin, colorant and lubricant as essential components
In the formula toner, the gel content is regulated
Ter resin is used as a binder resin and meta is used as a lubricant.B
CSpecific polymer obtained by polymerization in the presence of
-By graft-modified
Finding out that the problem can be solved, and completing the present invention
Reached. That is, the toner for developing an electrostatic image of the present invention.
Contains a binder resin, a colorant and a lubricant.
And the lubricant is metaRoseFor polymerization in the presence of catalysts
Ethylene homopolymer or ethylene and carbon obtained from
Ethylene-based copolymer consisting of α-olefins of 3 to 10
Styrene monomer and / or unsaturated carboxylic acid
Polyethylene modified by graft polymerization of boric acid monomer
Len wax (hereinafter referred to as “modified polyethylene wax”
Su ". ) And the binder resin is tetrahydric
Polyethylene containing 10 to 40% by weight of insolubles in lofuran
It is characterized by containing a steal resin. In the present invention, the binder resin and the lubricant
The above polyester resin and modified polyethylene
The gel component in the toner can be
Disperse other internal components without breaking the molecular chain of
And details are unknown, but can be
Wax component with specific physical properties and ultra high molecular weight gel formation
Is present uniformly, the polyester resin
High level of offset resistance has been developed at a higher level
Will be able to In addition, the modified polyethylene wax
By controlling the components compatible with the binder resin,
Rubbing image strength and peeling of polyethylene wax itself
Powder fluidity of the toner without impairing the nail scratch suppression effect
Improves blocking and caking resistance
Can be reduced. In the present invention,
Is a small molecule that was previously unusable for the above reasons.
Amount of polyethylene wax can be used,
The effect of lowering the minimum fixing temperature of the ester resin
The melting point of the metal
Be able to conduct. [0021] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described.
This will be described in detail. Lubricants used in the present invention,
Ethylene homopolymer or ethylene having 3 to 10 carbon atoms
Grafting ethylene copolymer consisting of α-olefin
Modified ethylene homopolymer or ethylene
Tylene-based copolymers can be used in the presence of metallocene-based catalysts.
It is obtained by polymerization. Metallocene catalysts are
It can be used without being limited to that type
You. For example, (A) from group IVb, Vb, VIb of the periodic table
A compound of a transition metal selected from the group consisting of
Metal compound ". ) And (B) Combination of promoters
An example is a metallocene-based catalyst consisting of a pulp. The above transition
As the metal compound, a compound represented by the following formula (1) is used.
Examples can be given. ML_x            (1) In the above formula (1), M represents a group IVb, Vb or VIb.
Represents a transition metal atom selected from metals of zirconium
, Titanium, hafnium and the like. x is a transition metal
And the number of L is shown. L coordinates to transition metal
Wherein at least one L is
Cyclopentadiene such as clopentadienyl and indenyl
L is a ligand having a phenyl skeleton, and other L is carbon
A hydrocarbon group, an alkoxy group, an aryl
Oxy group, trialkylsilyl group, SO_ThreeR¹(However
Then R¹Represents a carbon atom 1 which may have a substituent such as halogen.
To 8 hydrocarbon groups), a halogen atom and a hydrogen atom
One group or atom selected from the group consisting of Sa
Further, the compound represented by the above general formula (1) is
When two or more ligands having a tadienyl skeleton are contained,
Having two cyclopentadienyl skeletons
Are an alkylene group such as ethylene and propylene,
Substituted alkylenes such as propylidene and diphenylmethylene
Group, silylene group, or dimethylsilylene group, diphenyl
Linked via a substituted silylene group such as a rusilylene group.
You may. Such compounds include, for example, bis
(Cyclopentadienyl) zirconium dichloride,
(Methylcyclopentadienyl) zirconium dichloride
Lido, bis (ethylcyclopentadienyl) zirconium
Mudichloride, bis (n-propylcyclopentadieni
B) zirconium dichloride, bis (n-butylcyclo)
Pentadienyl) zirconium dichloride, bis (n-
Hexylcyclopentadienyl) zirconium dichloride
Do, bis (methyl-n-propylcyclopentadienyl)
B) zirconium dichloride, bis (methyl-n-butyl)
Rucyclopentadienyl) zirconium dichloride, bi
Sus (dimethyl-n-butylcyclopentadienyl) silyl
Conium dichloride, bis (n-butylcyclopentadi
Enyl) zirconium dibromide, bis (n-butyloxy)
Clopentadienyl) zirconium methoxy chloride,
Bis (n-butylcyclopentadienyl) zirconium
Ethoxycyclolide, bis (n-butylcyclopentadie
Nyl) zirconium butoxycyclolide, bis (n-butyl)
Rucyclopentadienyl) zirconium ethoxide,
(N-butylcyclopentadienyl) zirconium
Tyl chloride, bis (n-butylcyclopentadienyl
L) dimethyl zirconium, bis (n-butylcyclope)
Antadienyl) zirconium benzyl chloride, bis
(N-butylcyclopentadienyl) dibenzylzirco
, Bis (n-butylcyclopentadienyl) silyl
Conium phenyl chloride, bis (n-butylcyclope
Antadienyl) zirconium hydride chloride, d
Tylene bis (indenyl) dimethyl zirconium, ethi
Lenbis (indenyl) diethyl zirconium, ethyl
Bis (indenyl) diphenyl zirconium, ethyl
Nbis (indenyl) methyl zirconium monochloride
, Ethylenebis (indenyl) ethyl zirconium
Nochloride, ethylenebis (indenyl) methylzirco
Monobromide, ethylenebis (indenyl) silyl
Conium dichloride, ethylenebis (indenyl) silyl
Conium dibromide, ethylene bis {1- (4,5,
6,7-tetrahydroindenyl) デ dimethylzirconi
, Ethylenebis {1- (4,5,6,7-tetrahi
Droindenyl)｝ methylzirconium monochloride,
Ethylenebis {1- (4,5,6,7-tetrahydroi)
Ndenyl) zirconium dichloride, ethylene bis
{1- (4,5,6,7-tetrahydroindenyl)}
Zirconium dibromide, ethylene bis {1- (4-
Cylindenyl) zirconium dichloride, ethylene
Bis {1- (5-methylindenyl)} zirconium di
Chloride, ethylenebis {1- (6-methylindenyl)
B) zirconium dichloride, ethylenebis
(7-methylindenyl) zirconium dichloride,
Ethylenebis {1- (5-methoxyindenyl)} zyl
Conium dichloride, ethylenebis {1- (2,3-di)
Methylindenyl) zirconium dichloride, ethyl
Bis (1- (4,7-dimethylindenyl)) zircon
Ium dichloride, ethylene bis {1- (4,7-dimethyl)
Toxinindenyl) zirconium dichloride, isop
Lopylidene (cyclopentadienyl-fluorenyl) di
Ruconium dichloride, isopropylidene (cyclopen
Tadienyl-2,7-di-t-butylfluorenyl) di
Ruconium dichloride, isopropylidene (cyclopen
Tadienyl-methylcyclopentadienyl) zirconium
Mudichloride, dimethylsilylenebis (cyclopentadi
Enyl) zirconium dichloride, dimethylsilylene bi
(Methylcyclopentadienyl) zirconium dichloride
Lido, dimethylsilylene bis (dimethylcyclopentadi
Enyl) zirconium dichloride, dimethylsilylene bi
(Trimethylcyclopentadienyl) zirconium di
Chloride, dimethylsilylenebis (indenyl) zirco
Dichloride, diphenylsilylenebis (indene
G) zirconium dichloride. In addition,
In the above examples, the cyclopentadienyl ring
Substitutes include 1,2- and 1,3-substitutes,
Transformants include 1,2,3- and 1,2,4-substituted forms.
No. In the present invention, the zirconium compound described above
And replace zirconium metal with titanium metal or hafnium
Transition metal compounds replaced with metals can be used.
You. The co-catalyst (B) may be a conventionally known co-catalyst.
It can be used without particular limitation. An example
For example, aluminoxane (B-1) or a transition metal compound
That reacts with product (A) to form an ionic complex
(B-2). The aluminoxane (B-1) includes
Physically, it is represented by the following general formula (2) or (3).
Aluminum compounds can be exemplified. Embedded image (Where R^TwoRepresents a hydrocarbon group, and m is an integer of 2 or more
Is shown. ) In the above aluminoxane, R^TwoHame
Tyl group, ethyl group, propyl group, n-butyl group, iso
-Butyl, phenyl, phenylmethyl, etc.
And preferably a methyl group, an ethyl group, an iso-butyl group
It is. m is an integer of 2 or more, preferably 3 to 50;
Particularly, it is an integer of 3 to 40. Aluminoxane can be prepared by, for example, (1) adsorption
Compounds containing water or salts containing water of crystallization, eg
For example, hydrocarbons such as magnesium hydrate and copper sulfate hydrate
Add organic alkyl such as trialkylaluminum to the medium suspension.
React minium compounds and recover as hydrocarbon solution
(2) Trial in a medium such as benzene or toluene
Directly applicable to organoaluminum compounds such as alkylaluminum
Reacts as a hydrocarbon solution by contacting water, ice, and steam.
The organic aluminum compound used
Materials include trimethyl aluminum, triethyl aluminum
Minium, tripropyl aluminum, tri-n-butyl
Aluminum, triisobutyl aluminum, tri-
sec-butylaluminum, tri-tert-butyl
Aluminum, triisopentyl aluminum, etc.
Is done. Further, it reacts with the transition metal compound (A) to form
Examples of the compound (B-2) which forms an on-complex include:
For example, a cation and an anion in which a plurality of groups are bonded to an element
And particularly preferably a coordination complex compound.
I can give it. Specific compounds include Tet
Trimethylammonium laphenylborate, tetraphenylene
Triethylammonium ruborate, tetraphenylborate
Tri (n-butyl) ammonium, tetra (pentafluoro)
Triphenylammonium borate, tetra (pe
N-fluorophenyl) triethylammonium borate,
Tetra (pentafluorophenyl) borate tri (n-butyl)
Le) ammonium, triethyl ethyl hexafluoroarsenate
Ammonium, ferrocenium tetraphenylborate, tet
Triphenyl laphenylborate, tetra (pentafluorophene)
Nyl) ferrocenium borate, tetra (pentafluoroph
Phenyl) methylferrocenium borate, tetra (pentaf
(Fluorophenyl) decamethylferrocenium borate, tet
Silver la (pentafluorophenyl) borate, tetra (penta
Fluorophenyl) trityl borate, tetrafluoroborate
Silver, silver hexafluorophosphate, hexafluoroarsenic acid
Silver, silver perchlorate, silver hexafluoroantimonate, tri
Silver fluoroacetate, silver trifluorometasulfonate, tet
La (pentafluorophenyl) borate (N-benzyl-2)
-Cyanopyridinium), tetra (pentafluorophene)
Nyl) boric acid (N-benzyl-3-cyanopyridinium)
), Tetra (pentafluorophenyl) boric acid (N-
Benzyl-4-cyanopyridinium), tetra (pentaf
Fluorophenyl) boric acid (N-methyl-2-cyanopyridi)
), Tetra (pentafluorophenyl) borate (N
-Methyl-3-cyanopyridinium), tetra (pentane
Fluorophenyl) borate (N-methyl-4-cyanopyri)
Dinium), tetra (pentafluorophenyl) borate
Limethylammonium, tetra (pentafluorophenyl
Le) trimethyl borate (m-trifluoromethylphenyi)
Le) ammonium, tetra (pentafluorophenyl)
Benzylpyridinium borate and the like. In addition to these cocatalysts (B),
If necessary, an organoaluminum compound (C) may be used.
No. Examples of such an organoaluminum compound include:
The compound represented by the general formula (4) can be exemplified.
You. R¹ _nAlX_3-n          (4) (Where R¹Represents a hydrocarbon group having 1 to 12 carbon atoms;
Represents a halogen atom or a hydrogen atom, and n represents an integer of 1 to 3.
Is a number. ) In the above general formula (4), R¹Is the carbon number
1 to 12 hydrocarbon groups such as an alkyl group,
Represents an alkyl group or an aryl group, but specifically,
Group, ethyl group, n-propyl group, iso-propyl
Group, iso-butyl group, pentyl group, hexyl group, octyl group
Tyl, cyclopentyl, cyclohexyl, phenyl
And a tolyl group. Such an organic
As the luminium compound, trimethylaluminum,
Triethyl aluminum, triisopropyl aluminum
Aluminum, triisobutyl aluminum, trioctyl aluminum
And tri-2-ethylhexyl aluminum
Lialkyl aluminums; isoprenyl aluminum
Alkenyl aluminums such as dimethyl aluminum
Chloride, diethylaluminum chloride, diisopro
Pill aluminum chloride, diisobutyl aluminum
Dialkis such as chloride and dimethylaluminum bromide
Aluminum halides; methyl aluminum sesqui
Chloride, ethyl aluminum sesquichloride, isop
Ropir aluminum sesquichloride, butyl aluminum
Musesquichloride, ethyl aluminum sesquibromide
Alkylaluminum sesquihalides such as methyla
Luminium dichloride, ethyl aluminum dichloride
, Isopropyl aluminum dichloride, ethyl alcohol
Alkyl aluminum dihalides such as minium dibromide
Compounds; diethyl aluminum hydride, diisobutyrate
Alkyl aluminum such as aluminum hydride
Compounds such as hydrides are used. In the present invention, the above transition metal compound (A)
And a co-catalyst (B), and if necessary, a compound of the above general formula
From the organoaluminum compound (C) shown in (4)
Metallocene-based catalysts are used. The polymerization reaction is charcoal
It is performed in a hydrogen hydride medium. Specific as hydrocarbon medium
Typically, butane, isobutane, pentane, hexane,
Octane, decane, dodecane, hexadecane, octadeca
Such as aliphatic hydrocarbons such as cyclopentane,
Alicyclic ring such as lopentane, cyclohexane, cyclooctane
Aromatics such as aromatic hydrocarbons, benzene, toluene and xylene
Petroleum fractions such as aromatic hydrocarbons, gasoline, kerosene, and light oil
In addition, the starting olefin is also a hydrocarbon medium. these
Among hydrocarbon media, aromatic hydrocarbons are preferred. In the present invention, the polymerization reaction is carried out by a liquid phase polymerization method.
The ratio of the transition metal compound used in the reaction is determined by the polymerization reaction.
The concentration of transition metal atoms in the system is usually 10^-8Not
10^-2Gram atoms / liter, preferably 10^-7Not
10^-3It is in the range of gram atoms / liter. Also, Al
The ratio of minoxane used depends on the amount of aluminum in the polymerization reaction system.
The concentration of atom is usually 10^-FourOr 10^-1G
Atoms / liter, preferably 10^-3Or 10^-2G
It is in the range of atoms / liter. In addition, the transition within the polymerization reaction system
The ratio of aluminum atoms to transfer metal atoms is usually 4
Chair 10⁷, Preferably 10 to 10⁶In the range
You. In the present invention, the above homopolymerization of ethylene
The molecular weight of the copolymer or ethylene copolymer is controlled by hydrogen or hydrogen.
And / or polymerization temperature. Polymerization
The reaction temperature is usually 20 ° C. or higher, particularly preferably 5 ° C.
It is in the range of 0 ° C to 230 ° C. Supplied to the polymerization reaction
The amount of hydrogen is usually expressed as the molar ratio of hydrogen to ethylene.
In the range of 0.01 to 4, preferably 0.05 to 2
It is. In the present invention, these metaRoseCatalyst
Ethylene homopolymer obtained by polymerization in the presence of
An ethylene-α-olefin having 3 to 10 carbon atoms
Tylene-based copolymers are used. The 135 ° C deca
The intrinsic viscosity [η] measured in phosphorus is preferably 0.4
dl / g or less, particularly preferably 0.005 to 0.35
dl / g. In the case of the copolymer,
The proportion of ethylene in the monomer is usually at least 80 mol%, preferably
Or more than 85 mol%. Furthermore, the ethylene thus obtained
Homopolymer or ethylene-based copolymer has a viscosity average
Range of 800-3000, density 0.95g / c
m^ThreeAbove, and penetration of 2 dmm or less, further 1 dmm
It is more preferable that: Polyethylene in this range
Is self-lubricating due to its high density and linearity of the molecule.
This reduces damage due to wear on the fixed image surface.
To prevent rubbing, smearing, etc. on the fixed image
can do. That is, after passing through the heating roll, fixing
A lubricating film is formed on the image surface, and the lubrication effect is sufficient
It is expressed in In addition, the homopolymer or ethylene of the above ethylene
Tylene copolymer (hereinafter referred to as “polyethylene wax”)
Say. ) Of gel permeation chromatography
(Hereinafter simply referred to as GPC) molecular weight distribution (Mw
/ Mn) is usually preferably 1.1 to 1.8, more preferably
More preferably, it is 1.5 or less. Molecular weight distribution Mw / M
When n is in this range, the above-mentioned range of the viscosity average molecular weight is used.
In the case of high molecular weight components in polyethylene wax,
Can reduce components and low molecular weight components
You. As a result, the molecular weight at which melting starts at low temperatures is small.
Poor blocking properties due to undesired components, poor powder flowability at room temperature
And increasing the partial melt viscosity of high molecular weight components
Can reduce the decrease in the effect of controlling peeling nail damage due to
is there. Also, this is the polyethylene wax itself.
It has a significant effect on the melting behavior. Generally polyethylene
Waxes are completely solid under normal conditions.
That is, when passing through the fixing roll,
Completely melts near the set temperature of the fixing roll in time
Is required to be expressed. The molecular weight distribution
When controlled within the range, it is more soluble than
The melting temperature range for finishing the process can be narrowed. This
As a result, the amount of wax that contributes to release (setting of the fixing roll)
The amount of wax dissolved at a constant temperature) increases,
From this point of view, efficiency is improved. The metallocene catalyst is different from the conventional catalyst system.
Thus, a polymer having a narrow molecular weight distribution can be obtained. But
The molecular weight distribution by distillation, crystallization and solvent washing.
You don't need to make it narrow, or if you need it,
Can be implemented efficiently. The polyethylene wax according to the present invention
Molecular weight distribution (Mw / Mn)
Using PC150C, temperature 140 ° C, solvent o-dichloro
Benzene, measurement flow rate 1.0 ml / min, concentration 0.1 weight
It is a value measured in% by weight. In calculating the molecular weight of the sample
Used the viscosity equation of polyethylene. As a column,
Tosoh GMH-HT (60cm) and GMH-HTL
(60 cm) connected. Also, the penetration is
JIS K2207, density according to JIS K6760
Furthermore, the melt viscosity is determined by heating the sample at 160 ° C.
And measured with a Brookfields viscometer. The polyethylene wax produced by the above method
And further degassed under vacuum at a temperature above the melting point
Dissolved in a solvent such as hexane or acetone to reduce the molecular weight.
After removing the part or dissolving the whole amount in a solvent,
By precipitating at a certain temperature, the high molecular weight
Exclusion methods may be used in combination. In addition, the polyethylene wax described above
Styrene monomer or unsaturated carboxylic acid monomer
The raft modification ratio is 5 when the total weight is 100 parts.
And preferably 30 parts by weight. Within this range,
Powder flowability, blocking properties, and resistance due to large domains
Adverse effects on caking properties, etc., and high dispersion of lubricant in toner
Excessive release effect, low rubbing image strength, etc.
Good performance can be exhibited without any lower level. In the present invention, the polymer used for graft polymerization is used.
Styrene-based monomers include styrene, α-methyl
Styrene, 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
tert-butylstyrene, 4-hexylstyrene, 4-
Nonylstyrene, 4-octylstyrene, 4-phenyl
Styrene, 4-decylstyrene, 4-dodecylstyrene
2-chlorostyrene, 3-chlorostyrene, 4-alkane
Lorostyrene, 2,4-dichlorostyrene, 3,4-di
Chlorostyrene, 2-methoxystyrene, 4-methoxy
Styrene, 4-ethoxystyrene, etc.
You. It is also used for graft polymerization.
Unsaturated carboxylic acid monomers such as methyl acrylate
, Ethyl acrylate, butyl acrylate, acrylic acid
sec-butyl, isobutyl acrylate, acrylic acrylate
Ropir, isopropyl acrylate, octyl acrylate
, Dodecyl acrylate, stearyl acrylate,
Hexyl acrylate, isohexyl acrylate, acrylic acid
Phenyl, 2-chlorophenyl acrylate, acrylic acid
Diethylaminoethyl, 3-methoxybutyrate
Diethylene glycol ethoxylate,
Acrylics such as 2,2,2-trifluoroethyl acrylate
Acrylates, methyl methacrylate, methacrylate
Chill, butyl methacrylate, sec-butyl methacrylate
, Isobutyl methacrylate, propyl methacrylate,
Isopropyl methacrylate, octyl methacrylate,
Dodecyl acrylate, stearyl methacrylate, methac
Hexyl acrylate, decyl methacrylate, methacrylic acid
Phenyl, 2-chlorophenyl methacrylate, methacrylic acid
Diethylaminoethyl acrylate, 2-ethylhexyl methacrylate
Sil, 2,2,2-trifluoroethyl methacrylate, etc.
Methacrylates, and other maleic acid esters
, Maleic propyl, maleic butyl, maleic
Diethyl acrylate, dipropyl maleate, dibutyl maleate
Maleic esters, such as toluene, ethyl fumarate, fumarate
Fumarate esters such as butyl acrylate, dibutyl fumarate,
Ethyl itaconate, diethyl itaconate, bu itaconate
And itaconic esters such as chill.
You. Graft polymerization on polyethylene wax
Styrene monomer or unsaturated carboxylic acid monomer
The above are exemplified above, but are not limited to these.
is not. Modification of polyethylene wax by the above monomers
Various known methods can be adopted as the sex method.
Wear. For example, polyethylene wax and styrenic
Radical initiation of monomer or unsaturated carboxylic acid monomer
Heating, melting and mixing in the presence of an agent
Can be used. The reaction temperature is between 125 and 32
A range of 5 ° C. is preferred and the radical initiation used
Agents include benzoyl peroxide, lauroylperoxide
Oxide, dicumyl peroxide, di-t-butylperoxide
Peroxides such as oxides, azobisisobutyronitrile, etc.
And the like azo compounds. Further, melting of the modified polyethylene wax
The viscosity is between 15 and 250 cps at 160 ° C.
Preferably. In this range, immediately after passing through the heating roll
The cohesive strength of the fixed image and the melt viscosity of the image surface are appropriate
, Image scraping by peeling nails, mold release failure,
It can suppress the occurrence of peeling nail scratches due to excessive stress during mold release.
And it is possible. In particular, polyethylene by the above method
In the wax, in the range of the viscosity average molecular weight,
Polyethylene using metallocene catalyst as described above
Due to the advantages of wax, baluns with other wax properties
Control to give the desired melt viscosity
Is easy. The modified polyethylene wax may be used as a needle.
The penetration is preferably 2 dmm or less, particularly preferably 1 dmm or less.
Good. The modified polyethylene-based wax with the penetration
The toner has a self-lubricating property, so that the
Reduces damage due to abrasion, rubs and smudges the fixed image
Can be prevented from occurring. That is,
After passing through the heat roll, a lubricating film is formed on the surface of the fixed image
As a result, the lubrication effect is sufficiently exhibited. Further, a modified polyethylene wax toner
The amount added to the toner is 1 to 20% by weight of the toner weight.
The range is appropriate, and 3 to 10% by weight is more preferable.
Good. The binder resin used in the present invention is tetra
Hydrofuran insoluble matter (hereinafter referred to as “THF insoluble matter”
U. ) Containing 10 to 40% by weight of
It is fat. This polyester resin is polyvalent hydroxylated
Compound and a polycarboxylic acid or a lower alkyl ester thereof.
Reactive acid derivatives such as steles, acid anhydrides and acid halides
Consists of The THF-insoluble matter controls the degree of crosslinking.
More can be obtained. Examples of the polyhydroxy compound include ethyl.
Len glycol, propylene glycol, 1,4-buta
Diol, 2,3-butanediol, 1,5-pentane
Diol, 1,6-hexanediol, neopentile
Glycol, 1,4-cyclohexanedimethanol,
Dipropylene glycol, tripropylene glycol, etc.
Polypropylene glycols, bisphenol A and
And its derivatives, its alkylene oxide adducts, hydrogen
Other than divalent hydroxy compounds such as added bisphenol A
Glycerin, sorbitol, 1,4-sorbitan,
Trivalent or higher hydroxyl compound such as trimethylolpropane
Things can be used. As the polycarboxylic acid, malonic acid,
Succinic acid, 1,2,5-hexanetricarboxylic acid, 1,
2,7,8-octanetetracarboxylic acid, n-octyl
Succinic acid, 1,3-dicarboxy-2-methyl-2-ca
Ruboxymethylpropane, tetra (carboxydimethy
G) Methane, maleic acid, fumaric acid, dodecenyl succinate
Acid, 1,2,4-cyclohexanetricarboxylic acid, lid
Luic acid, isophthalic acid, terephthalic acid, trimellitic acid,
Pyromellitic acid, 1,2,4-naphthalene tricarboxylic
An acid or the like can be used. Weight of polyester resin used in the present invention
Average child mass Mw is in the range of 7000 to 50,000, number average
The molecular weight Mn is in the range of 2,000 to 10,000, and the glass transition
The temperature Tg is preferably in the range of 50 to 70C. The binder resin for toner used in the present invention is T
HF insolubles must be in the range of 10-40% by weight
And preferably set in the range of 15 to 25% by weight.
You. If the THF-insoluble content is less than 10% by weight,
Even when used in combination with polyethylene wax,
Fsettability cannot be fully exhibited, and on the other hand, 40 weight
%, The grindability decreases. In the present invention, THF-insoluble matter refers to a sample
Is dissolved in tetrahydrofuran (THF) and its insolubles
Is separated by a centrifuge, and the dry weight is
Represents the percentages by weight expressed in weight percent,
Can be obtained as follows. (1) 200-300 mg of sample is put in 25 ml
Weigh directly into Lasco, add 20 ml of THF overnight
put. (2) The sample of (1) is made of polytetrafluoroethylene
Into a centrifuge tube. (3) In the Erlenmeyer flask described in (1) above, once again add 20 ml
After washing with THF, put in the tube of (2) for a total of 40 m
and seal with film. (4) The above (3) is performed at a rotation speed of 18000 rpm and -10 ° C.
And centrifugation for 20 minutes. (5) Take out the sample of (4) above and release until it returns to room temperature.
Place. (6) Take 5 ml of the supernatant of (5) above and weigh it.
Take it out on a fixed aluminum plate, then add THF
Is evaporated on a hot plate. (7) Put the sample of (6) in a vacuum dryer at 50 ° C.
Allow to dry overnight and dry the THF insolubles in 5 ml.
And weigh it together with the weight of the aluminum dish. (8) The THF insoluble content is calculated by the following equation. THF-insoluble matter (%) = [(sample amount) − [((7)
Weight of weighed sample)-(weight of aluminum pan)
× (40/5)]] ÷ (sample amount) × 100 Further, the toner for developing an electrostatic image of the present invention comprises:
Contains a colorant as one of the main constituents
Agents include dyes and pigments such as carbon black.
K, nigrosine dye, aniline blue, calcoyl bull
ー, Chrome Yellow, Ultramarine Blue, Dupont
Oil red, quinoline yellow, methylene blue black
Lido, phthalocyanine blue, malachite green oki
Salate, Lamp Black, Rose Bengal, C.I. I.
Pigment Red 48: 1, C.I. I. Pigment Red
122, C.I. I. Pigment Red 57: 1, C.I. I.
Pigment Yellow 97, C.I. I. Pigment Yellow
12, C.I. I. Pigment Blue 15: 1, C.I. I. Pi
15: 3 etc., and magnetite,
Examples of magnetic materials such as ferrite
be able to. These colorants are added 2 to 50 times in the toner.
The colorant may be contained in the range of
It is not limited to what has been done. Also, if necessary, a charge control agent substance or the like may be used.
Known additives may be added, and
Other inorganic compounds such as fluidity improvers such as fine particles
Fine particles may be added externally. The toner for developing an electrostatic image according to the present invention comprises:
Two-component toner, one-component toner containing magnetic material or
May be a capsule toner. [0057] The present invention will be described below with reference to Examples and Comparative Examples.
As will be described more specifically, the present invention is not limited to these examples.
Therefore, it is not limited at all. The following explanation
In the formula, "parts" means "parts by weight". (Production of polyethylene wax using metallocene catalyst
Build) Production example a 200 liters of purified hexane using a continuous polymerization reactor
/ Hr, methylaluminoxane (Tosoh Akzo)
0.4 mol / hr in terms of aluminum atom,
0.2 mol / hr of methyl aluminum and bis (n
-Butylcyclopentadienyl) zirconium dichloride
At a rate of 2 mmol / hr in terms of zirconium atoms.
Feed continuously and react with hydrogen in the gas phase in the polymerization reactor.
Ethylene ratio (H_Two/ C_TwoH_Four) Is 0.40, total pressure is 30
kg / cm^TwoContinuous ethylene and hydrogen to reach G
, Polymerization temperature 140 ° C, normal pressure, residence time 0.5
Time, under the condition that the polymer concentration becomes 90 g / liter.
Was performed. For 1 liter of the obtained polymer solution,
The polymer was precipitated by adding 5 liters of methanol.
Then, the polymer is recovered by filtration, dried, and
A polymer having properties was obtained. [Η]: 0.08 dl / g,
Molecular weight distribution Mw / Mn: 1.3, viscosity average molecular weight: 11
30, density: 0.96 g / cm^Three, Melt viscosity at 160 ° C
Degree: 12.0 cps. Production Example b In the polymerization reaction of Production Example a, in the gas phase in the polymerization reactor
Hydrogen to ethylene ratio (H_Two/ C_TwoH_Four) To 0.50
A polymerization reaction was carried out in the same manner as in Production Example a, except for the above. Obtained
The physical properties of the polymer were as follows. [Η]: 0.06 dl / g, molecular weight distribution M
w / Mn: 1.2, viscosity average molecular weight: 890, density:
0.96 g / cm^ThreeMelt viscosity at 160 ° C .: 7.7 c
ps. (Various graft-modified polyethylene waxes
Example of manufacturing) Production Example 1 MetaRoseOf Polyethylene Wax Production Using Carbon Catalyst
Polyethylene wax ([η]: 0.08 dl / g,
Molecular weight distribution Mw / Mn: 1.3, viscosity average molecular weight: 11
30, density: 0.96 g / cm^Three, Melt viscosity at 160 ° C
(Degree: 12.0 cps) 1000 g melted at 160 ° C
And styrene 250 g, di-tert-butyl peroxy
21 g of Sid was added dropwise from a separate conduit over 4 hours. drop
After completion of the reaction, the reaction was further continued at 160 ° C. for 1 hour.
Remove for 1 hour under a vacuum of 30 mmHg to remove the emission
Note, modified polyethylene wax (penetration: 1dmm or less)
Under the following conditions, a melt viscosity at 160 ° C .: 23.7 cps) was obtained. Production Example 2 MetaRoseExample of polyethylene wax production using a benzene catalyst
Polyethylene wax ([η]: 0.06 dl / g,
Molecular weight distribution Mw / Mn: 1.2, viscosity average molecular weight: 89
0, density: 0.96 g / cm^Three, Melt viscosity at 160 ° C
(Degree: 7.7 cps) Production example except that 1000 g was used.
In the same manner as in Example 1, modified polyethylene wax (penetration:
Melt viscosity at 160 ° C. of 1 dmm or less: 17.0 cp
s) was obtained. Production Example 3 Instead of 250 g of styrene, 125 g of styrene and
Production example except that a mixture of 125 g of dibutyl luate was used.
In the same manner as in Example 1, modified polyethylene wax (penetration:
Melt viscosity at 160 ° C. of 1 dmm or less: 18.0 cp
s) was obtained. Production Example 4 Instead of 250 g of styrene, methyl acrylate 250
Except for using g, the modified polyether
Tylene wax (penetration: 1dmm or less, at 160 ° C
(Melt viscosity: 24.8 cps). Production Example 5 Polyethylene wax (viscosity average molecular weight: 1070, min.
Molecular weight distribution: Mw / Mn: 2.61, density: 0.97 g /
cm^ThreeMelt viscosity at 160 ° C .: 85.0 cps) 10
The same procedure as in Production Example 1 was carried out except that 00 g was used.
Polyethylene wax (Penetration: 1dmm or less, 160 ° C
(Melt viscosity at 210.0 cps). Production Example 6 Instead of 250 g of styrene, 20 g of styrene, di-t
Except that 1.7 g of tert-butyl peroxide was used,
In the same manner as in Production Example 1, modified polyethylene wax (needle
Penetration: 1 dmm or less, melt viscosity at 160 ° C .: 12.0
cps). Production Example 7 Instead of 250 g of styrene, 125 g of styrene,
Same as Production Example 1 except that 540 g of dibutyl luate was used
And modified polyethylene wax (penetration: 2 dm
m, melt viscosity at 160 ° C .: 130.0 cps)
Was. Production Example 8 Polypropylene wax (viscosity average molecular weight: 3000,
Molecular weight distribution: Mw / Mn: 2.75, density: 0.89 g
/ Cm^ThreeMelt viscosity at 160 ° C .: 70.0 cps) 1
In the same manner as in Production Example 1 except that 000 g was used, modification was performed.
Polypropylene wax (Penetration: 1dmm, 180 ° C
(Melt viscosity at 250.0 cps). (Example of producing polyester resin for binder resin) Production Example A   Bisphenol A ethylene oxide 2 adduct 21 mol   Bisphenol A propylene oxide 2 adduct 21 mol   7 mol of succinic acid derivative   Terephthalic acid 4 mol   Trimellitic acid 25 mol The above substances were mixed with a stainless steel stirrer and glass nitrogen
4-neck round with gas inlet pipe and falling condenser
Charge the bottom flask and introduce nitrogen gas into the mantle.
Raise the temperature with a heater and keep the temperature of the reactants at 200 ° C.
Then, the generated water was distilled off, and the reaction was carried out for 8 hours. Got
The polyester resin A has a weight average molecular weight Mw of about 160
00, number average molecular weight Mn is about 3000, Tg is 65 ° C,
The THF insoluble content was 20%. Production Example B   Bisphenol A ethylene oxide 2 adduct 10 mol   Bisphenol A propylene oxide 2 adduct 15 mol   Neopentyl glycol 24mol   Terephthalic acid 22 mol   20 moles of isophthalic acid Using the above substance, it was obtained in the same manner as in Production Example A.
The polyester resin B has a weight average molecular weight Mw of about 900
0, number average molecular weight Mn is about 3500, Tg is 65 ° C, T
The HF insoluble content was 0%. Embodiment 1 (Preparation of toner)   100 parts of polyester resin A shown in Production Example A   Carbon black (BP1300, manufactured by Cabot Corporation) 10 parts   5 parts of the modified polyethylene wax shown in Production Example 1 Melt and knead the above components with a Banbury mixer, cool
Finely pulverized with a wet mill and classified with a classifier
Thus, toner particles having an average particle diameter of 10 μm were obtained. This particle
Fine silica particles with an average particle size of 0.012 μm
And mixed to obtain a toner. (Preparation of carrier) For ferrite core with particle diameter of 85 μm
Obtained by coating with a styrene-acrylonitrile resin. (Preparation of developer) 3 parts of the above toner and 97 parts of carrier
Was mixed to prepare a developer composition. Embodiment 2 As a lubricant, the modified polyethylene wax shown in Production Example 2 was used.
A developer composition was obtained in the same manner as in Example 1 except that the developer composition was used.
Was. Example 3 As a lubricant, the modified polyethylene wax shown in Production Example 3 was used.
A developer composition was obtained in the same manner as in Example 1 except that the developer composition was used.
Was. Example 4 As the lubricant, the modified polyethylene wax shown in Production Example 4 was used.
A developer composition was obtained in the same manner as in Example 1 except that the developer composition was used.
Was. Comparative Example 1 The modified polyester resin shown in Production Example B was used as the binder resin.
Polyethylene wax ([η]:
0.13 dl / g, molecular weight distribution Mw / Mn: 2.61,
Viscosity average molecular weight: 2000, density: 0.97 g / c
m^Three, Melt viscosity at 160 ° C .: 55.0 cps)
Except for the above, a developer composition was obtained in the same manner as in Example 1. Comparative Example 2 Polypropylene wax (viscosity average molecular weight:
3000, molecular weight distribution Mw / Mn: 2.75, density:
0.89 g / cm^ThreeMelt viscosity at 160 ° C .: 70.0
developer in the same manner as in Comparative Example 1 except that cps) was used.
A composition was obtained. Comparative Example 3 As the lubricant, the modified polyethylene wax shown in Production Example 5 was used.
Except for using, a developer composition was obtained in the same manner as in Comparative Example 1.
Was. Comparative Example 4 The modified polyethylene wax shown in Production Example 6 was used as a lubricant.
Except for using, a developer composition was obtained in the same manner as in Comparative Example 1.
Was. Comparative Example 5 The modified polyethylene wax shown in Production Example 7 was used as a lubricant.
Except for using, a developer composition was obtained in the same manner as in Comparative Example 1.
Was. Comparative Example 6 Modified polypropylene wax shown in Production Example 8 as a lubricant
Except that the developer composition was used in the same manner as in Comparative Example 1.
Obtained. Comparative Example 7 Polypropylene wax (viscosity average molecular weight:
3000, molecular weight distribution Mw / Mn: 2.75, density:
0.89 g / cm^ThreeMelt viscosity at 160 ° C .: 70.0
developer in the same manner as in Example 1 except that cps) was used.
A composition was obtained. Comparative Example 8 As a lubricant, the modified polyethylene wax shown in Production Example 1 was used.
Except for using, a developer composition was obtained in the same manner as in Comparative Example 1.
Was. The test method and the test method in the same Examples and Comparative Examples
The evaluation criteria are as follows. (1) Offset temperature Vice 550 (remodeled) fixing device (Fuji Xerox
(Manufactured by the company). Heat roll temperature to 180 ℃
Raise the temperature to 250 ° C in 5 ° C increments to generate offset
The temperature was checked visually. (It should be noted that “not generated” means 250 ° C.
Indicates that the occurrence of offset is not confirmed. ) (2) Temperature at which exfoliated nail scratches disappear Measured using a Vibase 550 (Modified) fixing device
Was. Peeling claw generated in solid black image at image tip
Heat low that reaches a level where scratches do not cause problems in actual use
Indicates the temperature. (It should be noted that “not generated” means that the measurement lower limit temperature is 12
It shows that no peeling claw occurs even at 0 ° C. ) (3) Fixing temperature Ironing test using Vivece550 (modification) fixing device
It was evaluated by the test method. (If you have iron stress
Can also exhibit a residual image of a certain area
Indicates the temperature of the steel. ) (4) Toner crushability Crusher (PJM-200, Nippon Pneumatic Industries, Ltd.)
Pulverization at a field rate of 1.0 kg / h.
Judgment was made based on the average particle diameter D50 of the toner. (5) Rubbing image intensity Using the 550 (remodeling) automatic document feeder
It was measured. Set five originals on the machine and send them.
Visually check the back of the original for dirt,
I got this. (Note that G0-G1 is not a problem in actual use.
Level) G0: Back dirt is not generated G1: Some dirt that is difficult to confirm visually G2: Slight dirt that can be visually confirmed G3: Stain that can be visually confirmed is generated. (6) Storage stability Perform a standing test for 17 hours in an atmosphere of 50 ° C / 50% RH.
went. Then, shake with a 63μm sieve for 5 minutes.
To confirm the blocking property. G1: 63 μm sieve passage rate 80% or more G2: 63 μm sieve passage rate of 50% or more and less than 80% G3: 63 μm sieve passage rate less than 50% (7) Toner transport amount Vision 800 (remodeling) as an index of powder fluidity
Measures the amount of toner transported per hour using a toner box
did. In Examples 1 to 4 and Comparative Examples 1 to 8,
Properties of lubricant and binder resin used in the obtained developer
The conditions are shown in Tables 1 and 2.
It is shown in Table 3. [Table 1] [0074] [Table 2] [0075] [Table 3][0076] According to the present invention, the toner for developing an electrostatic image is bound.
Dry toner with essential components of resin, colorant and lubricant
And the binder resin reduces the insoluble content of tetrahydrofuran by 10 to
Polyester resin containing 40% by weight and lubricant
To metaRoseOf the polymerization obtained in the presence of
Tylene homopolymer or ethylene and α having 3 to 10 carbon atoms
-Styrene-based ethylene copolymers composed of olefins
Graft polymerization of monomer or unsaturated carboxylic acid monomer
To use polyethylene wax modified by
Lower power consumption, in other words lower temperature
Temperature, good offset resistance, and
Excellent body fluidity, no blocking phenomenon, fixing
Rub without damaging the roll
A copied image having excellent image strength can be obtained.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-191817 (JP, A) JP-A-60-106808 (JP, A) JP-A-59-189346 (JP, A) 248671 (JP, A) JP-A-6-324513 (JP, A) JP-A-6-298825 (JP, A) JP-A-6-110249 (JP, A) JP-A-6-89044 (JP, A) JP-A-6-75422 (JP, A) JP-A-6-41235 (JP, A) JP-A-5-331232 (JP, A) JP-A-3-269542 (JP, A) JP-A-3-155563 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (1)

(57) [Claim 1] In a toner for developing an electrostatic charge image containing a binder resin, a colorant and a lubricant, the lubricant is obtained by polymerization in the presence of a metallocene catalyst. The styrene monomer and / or the unsaturated carboxylic acid monomer was graft-polymerized to the obtained ethylene homopolymer or the ethylene copolymer comprising ethylene and an α-olefin having 3 to 10 carbon atoms, and then modified. The binder resin is made of polyethylene wax and has a tetrahydrofuran-insoluble content of 10 to 4
A toner for developing an electrostatic image, comprising a polyester resin containing 0% by weight.