JPH02186360A - Developer for electrostatic image - Google Patents

Abstract

PURPOSE:To improve fluidity, blocking resistance, fixability at low temperature, and offset resistance and to enhance durability by coating each carrier core with an layer for controlling triboelectrifiability containing a fluoroalkyl (meth) acrylate type polymer. CONSTITUTION:Since a toner contains as a binder resin a block- or graft- copolymer of a crystalline polyester and an amorphous vinyl polymer, it obtains low temperature fixability due to the good wettability of the crystalline polyester component at the time of melt fixing and offset resistance due to the high viscoelasticity of the amorphous vinyl polymer. Since the carrier of the electrostatic image developer has high hardness and it is coated with the fluoroalkyl (meth)acrylate type polymer, abrasion resistance is exhibited and spent toner and spent additives are scarcely produced. It is necessary to control the content of the fluoroalkyl (meth)acrylate repeating units in the triboelectrifiability controlling layer for coating the carrier core to more than 50wt.%, thus permitting the electrostatic image developer itself including the carrier to be enhanced in durability.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to an electrostatic image developer used for visualizing electrostatic latent images in electrophotography or electrostatic recording, and more particularly, to This invention relates to an electrostatic image developer that has good blocking properties, a sufficiently wide fixing area, and excellent durability.

[Prior Art] For example, in electrophotography, an electrostatic latent image is usually formed by charging and exposing an electrostatic image carrier, this electrostatic latent image is developed with toner, and the resulting toner image is transferred to a transfer paper. A visible image is formed by transferring and fixing onto a support such as.

In order to obtain a visible image as described above, it is necessary to fix the toner image, and conventionally, a heat roller fixing method that has high thermal efficiency and can perform high-speed fixing has been widely adopted. In such a heat roller fixing method, the surface temperature of the heat roller is generally set at 160 to 200°C.
Recently, efforts have been made to (a) prevent thermal deterioration of the photoreceptor, (b) shorten the warm-up time required for the heat roller to rise to a temperature capable of fixing after the fixing device is activated, and ( (c) To reduce the temperature drop in the heat roller due to heat absorption into the transfer paper, making continuous copying possible multiple times; (e) To prevent failures in the conveyance system due to the occurrence of paper curling phenomenon, etc. Due to these demands, there is a strong demand to be able to perform the fixing process at a lower temperature of the heat roller. Therefore, the toner is also required to be able to be fixed well at low temperatures.

Moreover, the toner needs to have excellent anti-blocking properties, and furthermore, in the hot roller fixing system, it is required to have anti-offset properties.

Due to these demands, much research has been conducted on toners for low-temperature fixing.
No. 32 and No. 59-3446 disclose toners using a binder resin consisting of a crystalline resin and an amorphous polymer as a technique for improving low-temperature fixing properties, but these toners still have blocking problems. This phenomenon or offset phenomenon tends to occur, and when copying is repeated many times, a filming phenomenon occurs, making it impossible to obtain a satisfactory image. Further, Japanese Patent Application Laid-open Nos. 56-154740 and 57-8549 disclose a technique for improving offset resistance by using a binder resin made of a crystalline resin and an amorphous polymer in a toner. The fluidity of the toner is poor, causing blurred images and image deterioration.

Further, in order to obtain a good visible image with a two-component developer, it is necessary that the toner has good triboelectric charging properties, which is determined mainly by the relationship with the carrier. As means for this purpose, there are known methods such as making the toner contain a charge control agent or coating the surface of the carrier with a resin. For example, JP-A No. 62-229158 discloses a method of coating the surface of a carrier with a specific fluorine-containing resin, but although a developer with relatively stable charging characteristics can be obtained, it is different from conventional toners. When used in combination, none of them sufficiently satisfied both low-temperature fixing properties and anti-offset properties.

The present inventors have previously identified a developer containing a block or graft copolymer of crystalline polyester and an amorphous vinyl polymer as a toner that has good low-temperature fixing properties and anti-blocking properties and has a sufficiently wide fixing area. Kaisho 63-2
No. 7855 and No. 63-27856, but the durability was not satisfactory not only under high temperature and high humidity conditions but also under normal temperature and normal humidity conditions.

[Problems to be Solved by the Invention] It is extremely difficult to obtain a developer that is excellent in all of such low-temperature fixing properties, anti-blocking properties, anti-offset properties, and fluidity, and has high durability. Despite numerous studies, nothing satisfactory has yet been obtained.

Therefore, the purpose of the present invention is to improve fluidity, blocking resistance,
It is an object of the present invention to provide an electrostatic image developer that has good low-temperature fixing properties, good offset resistance, and excellent durability.

[1i! Means for Solving the Problems] The object of the present invention is to provide a toner used to visualize a negatively charged electrostatic latent image with a positively charged toner, and a carrier that imparts a positive charge to the toner. An electrostatic image developer comprising: the toner containing a block copolymer or graft copolymer of a crystalline polyester and an amorphous vinyl polymer, and the carrier having a core material fluorinated. Covered with a triboelectric charge control layer containing an alkyl (meth)acrylate polymer, and the triboelectric charge control]1
1 is achieved by an electrostatic image developer characterized in that it contains more than 50% by weight of fluorinated alkyl (meth)acrylate repeating units.

The present invention will be explained in detail below.

The toner constituting the electrostatic image developer of the present invention contains a block copolymer or graft copolymer of crystalline polyester and amorphous vinyl polymer as its binder resin, so that when it is melted during fixing, In this method, low-temperature fixing properties due to the good wettability of the crystalline polyester component and offset resistance due to the high viscoelasticity of the amorphous vinyl polymer are obtained.

Therefore, the toner has good low-temperature fixing properties and anti-offset properties, and can be fixed in a wide temperature range. The crystalline polyester is not particularly limited, but in order to improve the low-temperature fixability and fluidity of the toner, it is preferably a polyalkylene polyester.

Specific examples of such polyalkylene polyesters include:
For example, polyethylene sebacate, polyethylene adipate, polyethylene adipate, polyethylene succinate, polyethylene-p-(carbophenoxy) undecaate, polyhexamethylene sebacate, polyhexamethylene sebacate, polyhexamethylene decanedioate, Octamethylene dodecanedioate, polynonamethylene azelate, polydecamethylene adipate, polydecamethylene azelate, polydecamethylene adipate
polydecamethylene sebacate, polydecamethylene succinate, polydecamethylene dodecanedioate, polydecamethylene octadecanedioate, polytetramethylene sebacate, polytrimethylene dodecanedione 1-, polytrimethylene octadecanedioate, Examples include polydecamethylene azelate, polyhexamethylene-decamethylene-sebacate, polyoxydecamethylene-2-methyl-1,3-propane-dodecanedioate, and the like.

The crystalline polyester has a melting point of 50 to 1
Preferably, the temperature is in the range of 20°C. If the melting point TI of the crystalline polyester used is less than 50°C, the resulting toner will have poor blocking resistance, and if it exceeds 120°C, the melt fluidity of the toner at low temperatures will decrease, resulting in poor fixing properties. There is a risk. Here, the melting point TI of the crystalline polyester means the melting point of the crystalline polyester in a state where it is not bonded to an amorphous vinyl polymer.

When the crystalline polyester has a weight average molecular flaw MW in the range of 5×10 3 to 5×10 4 , the offset resistance of the toner and the pulverization efficiency in toner production will be good.

In order to obtain a low minimum fixing temperature of the toner and high temperature offset resistance, the proportion of the crystalline polyester used is as follows:
In a block polymer or graft copolymer with an amorphous vinyl polymer, the amount is preferably in the range of 3 to 50 wt%.

The vinyl polymer constituting the main portion of the amorphous vinyl polymer used in the present invention is at least one selected from styrene monomers, acrylic ester monomers, and methacrylic ester monomers. Obtained using seeds.

Examples of the styrene monomer include styrene, 0-
Methylstyrene, -methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,
3-dimethylstyrene, 2゜4-dimethylstyrene, p
-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3°4-dichlorostyrene, and the like.

Examples of the acrylic ester monomers include methyl acrylate, ethyl acrylate, butyl acrylate,
Isobutyl acrylate, propyl acrylate, octyl acrylate, dodecyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-ethyl acrylate, phenyl acrylate, methyl α-chloroacrylate etc.

Examples of the above-mentioned methacrylic acid ester monomers include methyl methacrylate, ethyl methacrylate, butyl methacrylate, butyl methacrylate, isobutyl methacrylate, octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, and -2 methacrylate. -ethylhexyl, stearyl methacrylate, phenyl methacrylate,
Examples include methacrylic dimethylamine ethyl, diethylaminoethyl methacrylate, and the like.

Further, the amorphous vinyl polymer used in the present invention may contain a monomer having a carboxyl group, a water 1L amino group, or an epoxy group that participates in block or graft copolymerization with the crystalline polyester. .

Examples of monomers having a carboxyl group, hydroxyl group, amino group or epoxy group include acrylic acid, β, β-dimethylacrylic acid, α-ethyl acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, crotonic acid. ,
Hydroxyethyl methacrylate, phthalic acid monoacryloyloxyethyl ester, succinic acid monoacryloyloxyethyl ester, N-hydroxyethyl acrylamide, N-human mixyethyl methacrylamide, p-
Examples include aminostyrene and glycidyl methacrylate. A monomer having such a functional group is included in a monomer composition for obtaining an amorphous vinyl polymer at a concentration of 0.
It is used within the range of 1 to 20 mol%.

The amorphous vinyl polymer used in the present invention is preferably one in which a polyvalent metal compound reacts with the carboxyl group of a vinyl polymer having a carboxyl group to form an ionic crosslink.

As the metal element of the polyvalent metal compound, alkaline earth gold 1 or a zinc group element is preferable, and MCI and Zn are particularly preferable.

Examples of polyvalent metal compounds containing these metals include:
Fluorides, chlorides, chlorates, bromides, iodides, oxides, hydroxides, sulfides, sulfites, sulfates of the above metal elements,
Lower alkyl metal compounds such as selenides, tellurides, nitrides, nitric salts, phosphides, phosphinates, IIA salts, carbonates, orthosilicates, acetates, oxalates, methyl compounds or ethyl compounds, etc. In particular, acetates or oxides of the above metal elements are preferred.

In order to ionically crosslink a vinyl polymer, for example, the polyvalent metal compound is mixed with a solution containing a vinyl polymer having carboxyl groups obtained by polymerization using a solution polymerization method, and the mixture is heated to form a reaction system. When the temperature reaches about 150 to 180°C, it is preferable to maintain this temperature for one hour or more to complete the reaction.

In addition, from the viewpoint of further improving low-temperature fixing properties and anti-offset properties, the amorphous vinyl polymer preferably has at least two or more overlaps (large towns) in the molecular balance distribution. That is, at least a low molecular component and high molecular weight component 2
In the molecular m distribution curve, which has a molecular chain distribution divided into groups and is measured by gel permutation chromatography (GPC), at least one maximum value is within the range of 2X10'' to 2X104, and at least one It is preferable to have at least two maximum values, such that one maximum value is in the range of 1×10 5 to 1×10 B.

As a method for obtaining such an amorphous vinyl polymer, for example, a first stage polymerization is carried out to obtain either a high molecular weight component or a low molecular weight component, and one of the components thus obtained is combined with the other. By dissolving it in the monomer composition for obtaining the component and carrying out the second stage polymerization, thereby producing the other component, as a result, a polymer having at least two maximum values in the molecular weight distribution curve is obtained. You can get a combination. This two-stage polymerization can be carried out, for example, by a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or the like.

The above-mentioned high molecular weight components make the amorphous vinyl polymer even stronger, which prevents the toner particles from being destroyed by external mechanical forces such as FJ friction with the carrier or stirring in the developing device, which causes the filming phenomenon. The generation of fine powder slag is suppressed. Note that the proportion of the high molecular weight component in the amorphous vinyl polymer is preferably 15 wt% or more.

When the amorphous vinyl polymer is an ionically crosslinked amorphous vinyl polymer and is composed of one polymeric component and a low molecular weight G component as described above, the carboxyl group that reacts with the polyvalent metal compound is at least It is preferable that it is introduced into the low molecular weight G component.

In other words, the destruction of toner particles caused by external mechanical forces such as friction with the carrier or stirring within the developing device is mainly caused by relatively brittle components of low molecular weight contained in the toner particles. It is preferable to ionically crosslink such low molecular weight components to impart fracture resistance to the toughened toner particles.

In addition, in an amorphous vinyl polymer, the mold mouth average molecular ff
The value of the ratio MW/Mn of 1Mw and number average molecule llMn is 3
．． 5 or more, especially 4-40 is preferable. When the ratio MW/Mn is too small, sufficient offset resistance and durability cannot be obtained. Here, the values of the double-lipped average molecule IMW and the number average molecule ffiMn were determined by the following measurement method.

That is, by gel permutation chromatography (GPC) under the conditions described below! Weight average molecule [
Measure IMW, number average molecular llMn, and peak molecular weight. At a temperature of 40°C, the solvent (tetrahydrofuran) was flowed at a flow rate of 1.2-d/min to a concentration of 0.2 g/min.
Measurement is performed by injecting 3 mQ of 201Q tetrahydrofuran sample solution as the sample weight. When measuring the molecular weight of a sample, the molecules of the sample are composed of several types of monodisperse polystyrene al! Using the quasi-sample, measurement conditions are selected that fall within a range in which the logarithm of the molecular weight of the prepared sample 1111 and the count number form a straight line.

Further, as the GPC column to be used, specifically, for example, TSK-GEL, GMH (manufactured by Tosoh ■), etc. can be used. Note that the solvent and measurement temperature are not limited to the above conditions, and may be changed to other conditions as appropriate.

Further, from the viewpoint of low temperature fixability, offset resistance, blocking resistance, and durability, the glass transition point To of the amorphous vinyl polymer is preferably 50 to 100°C.

Here, the glass transition point Tg is the differential scanning thermal
19 standard method (DSC), specifically, for example, rDSC-204 (manufactured by Seiko Electronics Co., Ltd.)
When measuring at a heating rate of 10" C/win, Refers to temperature.

Furthermore, the softening point of the amorphous vinyl polymer is 100 to 1
50°C is preferred. This softening point was determined using a Koka Type A-Tester (manufactured by Shima R Seisakusho) and heating a 1C13 sample at a heating rate of 6°C/min while using a plunger to 20k (20k).
Apply a load of J/Cf, diameter 1mm, length 11IIID
By this, draw the plunger falling knee temperature curve (softening flow curve) of the O-tester, and when the height of the S-shaped curve is h, the temperature corresponding to h/2 is drawn. This is the softening point.

In order to obtain a copolymer formed by chemically linking the crystalline polyester and the amorphous vinyl polymer, the crystalline polyester and the amorphous vinyl polymer may be bonded to each other in a head-to-tail manner, for example, by a coupling reaction between the terminal functional groups present in each polymer. Can be combined directly.

Alternatively, it can be bonded to the terminal functional group of each polymer using a bifunctional coupling agent, and examples of the bifunctional coupling agent include diisocyanate, dicarboxylic acid, glycol, phosgene, dichlorodimethylsilane, etc. Can be done.

In the present invention, it is preferable that the copolymer is contained in an amount of at least 5 wt % in the entire toner.

Auxiliary agents and the like can be added to the toner used in the present invention for various technical and performance improvements. For example, as the auxiliary agent, a magnetic substance, a coloring agent, a fixing property improving agent, a cleaning property improving agent, a charge control agent, a fluidizing agent, etc. are used.

Examples of the magnetic material include compounds exhibiting strong wiping properties such as iron, cobalt, and nickel, including ferrite and magnetite. In the case of magnetic toner, the content is 20 to 15 parts per 100 parts by weight of binder resin.
It is 0 jutanbe.

Examples of colorants include carbon black, chrome yellow, DuPont oil red, quinoline yellow,
Phthalocyanine blue, malachite green offsalate, etc. can be used.

The coloring agent is usually used in an amount of 0.1 to 20 parts by weight per 10 parts by weight of the binder resin.

Examples of fixability improvers include polyolefins, fatty acid ester waxes, higher alcohols, paraffin waxes, polyamide waxes, etc.
is K2531) 60-150°C wax is used.

As cleaning property improvers, fatty acid gold monosalt, talc,
Stone powder, mica, molybdenum disulfide, zinc oxide, chilium, etc. can be used.

As the charge control agent, conventionally known ones can be used, such as nigrosine dyes, metal-containing dyes, and the like.

I-free fine particles are used as the fluidizing agent. For FA,
Fine silica powder, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica,
Wollastonite, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate,
Examples include silicon carbide and silicon nitride, but fine silica powder is particularly preferred.

Furthermore, in the present invention, these inorganic fine particles are amine-modified silicon compounds, such as amino-modified silane coupling agents,
Preferably, the surface is treated with amine-modified silicone oil or polysiloxane ammonium salt.

The particle size of the inorganic fine particles thus obtained is preferably such that the average particle size of the primary particles is within the range of 3ffiμ to 2μm.

The content ratio of the non-binding fine particles is 0.1 to 5 wt of the toner.
% is preferable.

Inorganic fine particles whose surfaces have been treated with an amine-modified silicon compound in this way become inorganic fine particles with excellent positive chargeability.
Furthermore, the inorganic fine particles have excellent moisture resistance and durability, and have stable positive triboelectric charging properties that are not affected by environmental conditions.

To give an example of a preferred method for manufacturing the toner according to the present invention, first, a binder resin or a binder resin to which auxiliary agents such as a colorant are added as necessary is melted and kneaded using, for example, an extruder, and after cooling, a jet A toner having a desired particle size can be obtained by pulverizing the toner using a mill or the like and classifying the powder.

The carrier of the electrostatic image developer of the present invention has high hardness and is coated with a fluorinated alkyl (meth)acrylate polymer having low surface energy, so it exhibits wear resistance and is free from toner particles and external particles. Additive spent is less likely to occur. Furthermore, since it has high positive charge imparting properties and low environmental dependence, it has good copying durability.

The core materials of the carrier of the present invention include inorganic powders such as glass peas, metal powders such as aluminum powder, iron powder J'3 and nickel powder, metal oxide powders such as iron oxide, ferrite and magnetite, and carbonium iron powder. Materials used as the core material of ordinary coated carriers, such as shaped metal powders, can be used.

The core material is usually obtained by coating a triboelectric charge control layer on the core material, and the particle size of the carrier particles is 10 to 500.
It has a particle size within the range of μm. Further, the shape of the particles of the core material is not particularly limited as long as it has a commonly used shape.

In the present invention, the triboelectric charge control layer covering the core material contains a fluorinated alkyl (meth)acrylate-1 polymer.

It is necessary that the content of fluorinated alkyl (meth)acrylate repeating units in this group be more than 50% by weight. If this content is less than 50% by weight, the charging properties of the carrier will vary, making it impossible to stably charge the toner positively.

Also, it becomes difficult to stand up. In particular, when used under high temperature and high humidity conditions, the above fluctuation range may become large. Furthermore, scattering of electrostatic image developer within the apparatus also tends to increase.

On the other hand, by increasing the content of fluorinated alkyl (meth)acrylate repeating units to more than 50% by weight, the initial charge amount of the electrostatic image developer can be reduced to usually 10 to 40 μC/
Since the electrostatic charge m can be controlled within the range of a and the decrease in the charge m is reduced even with repeated use, clear developed images without fog can be continuously obtained from the beginning of use of the electrostatic image developer. Furthermore, various properties such as the mechanical strength of chitria are improved, and the durability of the electrostatic image developer itself containing the carrier of the present invention is also improved.

The fluorinated alkyl (meth)acrylate repeating unit in the fluorinated alkyl (meth)acrylate polymer forming the rIl friction coating layer of the carrier of the static N image developer of the present invention is represented by the following formula [I] Examples include repeating units represented by:

General formula [I] 1←CH, -CRI← ■ 0=C-R2 In the formula, R1 represents a hydrogen atom or a methyl group, and R2 includes an alkyl group in which at least one of the hydrogen atoms is substituted with a fluorine atom. The hydrogen of the hydroxyl group of the alcohol compound is l
! This is the residue removed from ilI.

In the above general formula [I], examples of alcohol compounds that can form a residue represented by R2 include 1 to 1 carbon atoms;
8 perfluoroalcohol, 1,1 represented by the following formula
-dihydroperfluoroalcohol or trihydroperfluoroalcohol CFzX (CFi)CHtO)! (however,
n is 0 or an integer from 1 to 16, X is a water M atom or a fluorine atom), a tetrahydroperfluoroalcohol CFs (Crt) II (CHtGHz) (CFt) II represented by the following formula
OH (where n is O or an integer from 1 to 15,
0 or 1), other fluoroalcohols (e.g. 2, 2.3°, 3.4
．． 4-tetrafluoropropatol, 1°1, ω-trihydroperfluorohexanol, 1.1. ω-trihydroperfluorooctator, 1,1,1.3,3.
3-hexafluoro-2-propatol), acetyl alcohol (e.g., 3-perfluorononyl-2
-Acetylpropatur, 3-perfluorolauryl-
2-acetylpropatol), N-fluoroalkylsulfonyl-N-alkylamino alcohol (e.g., N-perfluorohexylsulfonyl-N-methylamine ethanol, N-perfluorooctylsulfonyl-N-methylamine ethanol, Examples include N-perfluorodecylsulfonyl-N-methylaminoethanol and N-perfluorolaurylsulfonyl-N-ethylaminoethanol.

Preferred examples of the repeating unit represented by the general formula [11] are shown below. These can be used alone or in combination.

In formulas (a) and (b), R1 each represents a hydrogen atom or a methyl group, and n and p each represent 1
represents an integer of ~8, 1 and q are each 1~19
represents an integer.

Particularly in the present invention, the following fluorinated alkyl (meth)acrylate repeating units are desirable.

However, R1 is a hydrogen atom or a methyl group.

The fluorinated alkyl(meth)acrylate, -t-based polymer is
It may be a copolymer containing only the above repeating unit, or may further contain other repeating units.

In the present invention, together with the above fluorinated alkyl (meth)acrylate repeating unit, fluorinated alkyl (meth)acrylate
Examples of other repeating units that can form acrylate-based polymers include repeating units derived from aliphatic olefins (e.g., ethylene, butene-1), halogenated aliphatic olefins (e.g., vinyl chloride,
Vinyl bromide, 1,2-dichloroethylene, allyl chloride,
(vinylidene fluoride), repeating units derived from conjugated diene-based aliphatic diolefins (e.g., 1,3-butadiene, 2,3-dimethyl-1,3-butadiene), aromatic vinyl-based Examples include repeating units derived from compounds (e.g., styrene, methylstyrene), repeating units derived from nitrogen-containing vinyl compounds (e.g., 2-vinylpyridine, 2-vinyl-6-methylpyridine), These can be used alone or in combination for 2 seconds or more.

Styrene, methylstyrene, or methyl (meth)acrylate is particularly preferred as the repeating unit.

If the molecular value of the fluorinated alkyl (meth)acrylate polymer is too high, the viscosity of the solution will increase, making pinholes more likely to occur during film formation. In the present invention, in order to ensure properties such as good film formability, the intrinsic viscosity measured in methyl ethyl ketone (35°C) is usually within the range of 0.1 to 5.0 dl /Q. Use polymers.

In the present invention, the S triboelectric coating layer may be formed of the fluorinated alkyl (meth)acrylate polymer itself, or may be formed of the fluorinated alkyl (meth)acrylate polymer and other polymers (for example, acrylic It may also be formed with a resin.

The thickness of the triboelectric charge control layer can be set as appropriate by taking into account the particle size of the core material, but usually it is (weight of fluorinated alkyl (meth)acrylate polymer 1)/(core material weight 1) weight) is adjusted appropriately so that it is 0.2 to 5.0.

a! The thickness of the triboelectrification control layer obtained by using the resin forming the triboelectrification control layer within the above range for the core material is usually 0.05 μm or more.

By keeping it within the above range, the initial band '1llfi of the SVI electrophotographic developer becomes particularly good, and furthermore, this charge amount is less likely to fluctuate over time, and the powder properties are improved especially under high temperature and high humidity conditions. tends to be good.

The above carrier can be manufactured by forming a triboelectrification control layer around a core material according to a normal method for manufacturing coated Kyrelia.

[Example 1 Examples of the present invention will be specifically described below, but the present invention is not limited to these Examples.

Production of crystalline polyester> (1) Crystalline polyester 1 Sebacine G isoog and 964 g of hexamethylene glycol were mixed using a thermometer, a stainless steel stirrer,
It is placed in a round bottom flask with a capacity of 5 cm equipped with a glass nitrogen inlet tube and a flow-down condenser, then this flask is set on a mantle heater, and nitrogen gas is introduced through the glass nitrogen inlet tube to inert the inside of the reactor. The temperature was raised while maintaining the atmosphere. Then, 13.2C+ p-toluenesulfonic acid was added and reacted at a temperature of 150°C. When the amount of distilled water reached 250 mj2, the reaction was stopped and the reaction system was cooled to air temperature to produce crystalline polyester 1 made of polyhexamethylene sebacate having a hydroxyl group at the molecular end. The melting point TI of this crystalline polyester 1 is 64
℃, and the weight average molecular weight MW is 14,000.

(2) Crystalline polyester 2 Same as crystalline polyester 1, melting point T11 is 72
°C, weight average molecule [IMw Ka12,800 (7) H'
J I tyrene sebacate J: A crystalline polyester 2 was produced.

(3) Crystalline polyester 3 Same as crystalline polyester 1, melting point TI is 92°C
,! A crystalline polyester 3 made of ethylene succinate having an average molecular weight of 1 fi 14,800 (D) was produced.

(4) Crystalline polyester 4 Same as crystalline polyester 1, melting point T1M is 77
A crystalline polyester 4 made of polydecamethylene adipate having a weight average molecular weight Mw of 8,370 was produced.

Production of amorphous vinyl polymer> (1) Amorphous vinyl polymer 1 100 parts by weight of toluene was placed in a separable flask with a capacity of 12, and 100 parts by weight of toluene was added to the polymer as a component monoalyst. parts, and 25 parts by weight of butyl acrylate.
After adding 0.2 parts by weight of benzoyl peroxide and replacing the gas phase in the flask with nitrogen gas, the temperature was raised to 80° C. and maintained at this temperature for 15 hours to carry out the first stage polymerization.

In addition, the weight average molecular IMW of the monopolymer for cough high molecular weight component is 451,000, and the glass transition point T (
+ is 61°C.

Thereafter, the inside of the flask was cooled to a temperature of 40°C, and 85 parts by weight of styrene, 10 parts by weight of butyl methacrylate, and acrylic M51 were added as monomers for low molecular weight components.
[1 part and 4 parts by weight of benzoyl peroxide were added, and stirring was continued for 2 hours at a temperature of 40°C, then the temperature was raised again to 80°C and maintained at that temperature for 8 hours to carry out the second stage polymerization. I did it.

Next, add 0 zinc oxide, which is a polyvalent metal compound, to the flask.
．． 50 was added thereto, and the reaction was carried out for 2 hours while maintaining the temperature at reflux and stirring.

Thereafter, toluene was distilled off using a subilator and a vacuum pump to produce amorphous vinyl polymer 1 in which zinc oxide reacted with the carboxyl groups of the vinyl polymer to form ionic crosslinks.

This amorphous vinyl polymer 1 has two peaks in the molecular m distribution determined by GPC, and the peak molecular weight on the high molecular weight side is 363,000. The peak molecular weight on the low molecular weight side is 7°590. Moreover, the weight average molecularization MY is IEf5.
000, the value of the ratio Mw/Mn is 25.9, the glass transition point TO is 62°C, and the softening point Tso is 130°C.

(2) Amorphous vinyl polymer 2 100ffi of toluene in a separable flask with a volume of G1t
ffi part, and add thereto 85 parts by weight of styrene, 10 parts by weight of butyl acrylate, 5 parts by weight of monoacryloyloxyethyl nisdel succinate, and 1 part by weight of benzoyl peroxide. After replacing the gas phase with nitrogen gas, the temperature was raised to 80°C and maintained at this temperature for 5 hours to carry out polymerization.

Thereafter, 4 parts by weight of benzoyl peroxide was further added and polymerization was continued at a temperature of 80° C. for 10 hours.

Next, add 0 zinc oxide, which is a polyvalent metal compound, to the flask.
．． 59 was added thereto, and the reaction was carried out for 2 hours while maintaining the temperature at reflux and stirring.

Thereafter, toluene was distilled off using an aspirator and a vacuum pump to produce amorphous vinyl polymer 2 in which zinc oxide reacted with the carboxyl groups of the vinyl polymer to form ionic crosslinks.

This amorphous vinyl polymer 2 has one peak in the molecular m distribution determined by GPC, and has a weight average molecular weight MW of 8.
3,000, the value of the ratio MW/Mn is 7.5, the glass transition point To is 67°C, and the softening point Tsp is 127°C.

(3) Amorphous vinyl polymer 3 Amorphous vinyl polymer 3 was produced in the same manner as in the production of amorphous vinyl polymer 1 above, except that zinc oxide was not added.

This amorphous vinyl polymer 3 has two peaks in the molecular weight distribution by GPC, the peak molecular weight on the high molecular weight side is 355,000, the peak molecular weight on the low molecular weight side is 6,
It is 840. Also, ill average molecular mmy is 142,0
00, the value of the ratio MW/M1m is 24.5, the glass transition point Tg is 60°C, and the softening point Tsp is 128.5°C.

<Manufacture of toner resin> (1) Toner resin A 2511 parts of crystalline polyester 1, 75 parts of amorphous vinyl polymer 1, and 0.0 p-toluenesulfonic acid.
5 parts by weight and 100 parts by weight of xylene were placed in a separable flask with a volume of Ti31 and refluxed at a temperature of 150°C for 1 hour, and then the xylene was distilled off using an aspirator and an empty pump to form a crystalline polyester. A toner tree 111A made of a graft copolymer with an ionically crosslinked amorphous vinyl polymer was produced.

(2) Toner resin B-F In the production of toner resin A above, the crystalline polyester and amorphous vinyl polymer were used in the same manner except that the crystalline polyester and amorphous vinyl polymer were changed as shown in Table 1. Each of toner resins BF consisting of a graft copolymer with a polymer was produced.

Table 1 Manufacture of carrier> (1) Coachite carrier
*A coating solution for the frictional charging control layer 611 was prepared by dissolving in fl.

Using this coating liquid, coat the surface of ferrite core material (Japanese iron powder (made by barrel: F-150, average particle size: 80 μm > 2 kg).
A triboelectric charge control layer was formed using a fluidized transfer coating device (manufactured by Kaida Seiko ■; Subira Coat) to produce a coachite carrier 1 with positive charge imparting properties.

(2) Coachit Carrier 2 In the production of Coachit Carrier 1, the following formula (a-1
A coachite carrier was prepared in the same manner except that a fluorinated alkyl methacrylate polymer consisting of repeating units represented by the following formula (b-1') was used instead of a fluorinated alkyl methacrylate polymer consisting of repeating units not shown in formula (b-1'). 2 was manufactured.

(3) Coachit Carrier 3 In manufacturing Coachit Carrier 1, If fi! Fluorinated alkyl methacrylate polymer 28a and polymethyl methacrylate 12 used in the production of Coachite Carrier 111J were used as a coating liquid for charging control tlllJij.
J was dissolved in acetone/toluene mixture ts (mixing volume ratio -9:
1) G friction charging system DI dissolved in 800d! Coachite carrier 3 was produced in the same manner except that the layer coating liquid was used.

(4) Coachite Carrier 4 In the production of Coachite Carrier 1, the fluorinated alkyl methacrylate polymer 22 (l) used in the production of Coachite Carrier 1 and 18 g of polymethyl methacrylate were used as a coating liquid for the triboelectric charge control layer. A coachite carrier 4 was produced in the same manner except that a coating solution for the yl triboelectric charge control layer dissolved in 800 i.rho.

(5) Comparative Coachite Carrier 1 Vinylidene Fluoride/Ethylene Tetrafluoride Copolymer 1'VT
-100J (copolymerization molar ratio 80:20. Intrinsic viscosity 0.95dj! 10) (manufactured by Daikin Industries, Ltd.)
6g and methyl methacrylate copolymer [Acrivet M
Dissolve 6g of FJ (Mitsubishi Rayon Co., Ltd. 11) in 500d of a mixed solvent of 7cetone and medylethyl (1:1) for frictional charging! A coating solution for the iI1 layer was prepared. Using this coating solution, a triboelectric charging layer was formed on the surface of a ferrite core material (manufactured by Nippon Steel Powder ■; 1"-150, average particle size: 80 μm 21r+) using a fluidized transfer coating system U (Kaida Seiko ■; Subira Coat). A comparative coachite carrier 1 having positive charge imparting properties was manufactured.

(6) Comparative Coachite Carrier 2 In the production of Coachite Carrier 2, the fluorinated alkyl methacrylate polymer 12Ω and polymethyl methacrylate 28Ω used in the production of Coachite Carrier 1 were mixed with acetone as a coating liquid for the triboelectric charge control layer. Comparative Coachite Carrier 2 was produced in the same manner except that a coating liquid for the triboelectric charge control layer was dissolved in 800 d of toluene mixed solvent (mixing volume ratio -9:1).

(7) Comparative Coachite Carrier 3 In the production of Coachite Carrier 2, the formula (b-1 ') and methyl methacrylate (copolymerization molar ratio 50:50) was dissolved in an acetone/toluene mixed solvent (mixed volume ratio = 9:1) 800iR [coating liquid for 1 layer] Comparative Coachite Carrier 3 was produced in the same manner except that the following was used.

Example 1 Resin A for toner (present invention) 1 ool part carbon black [Mogul LJ 101 ffi parts (manufactured by Cabot Corporation) Paraffin wax [Sasol Wax HIJ (manufactured by Sasol Marketing Company) 3 parts by weight Alkylene bis fatty acid amide "Hoechst WaXCJ" (Manufactured by Hoechst)
Three parts of 1 part or more of the substances are mixed, melted and kneaded using heated rolls, cooled, coarsely pulverized, finely pulverized using a supersonic jet mill, and classified using an air classifier to obtain an average particle size of 11. A powder of Oμ layer was obtained. This powder 10
01i [1 part contains 0.8 parts by weight of sawt particles (x is an integer) prepared by treating 5% by weight of the polysiloxane ammonium salt shown below on silica "Aerosil 200J (manufactured by Nippon Aerosil Co., Ltd.)" and 0.0 parts by weight of zinc stearate. 5 parts by weight V
Electrostatic image developer sample 1 was prepared by mixing the toner obtained by mixing with a mold mixer with coachite carrier 1 so that the content (toner concentration) was 5% by weight.

Examples 2 to 8 and Comparative Examples 1 to 4 Samples 2 to 8 and Comparative Samples $41 to 4 was prepared.

The samples thus obtained were evaluated as follows.

<Evaluation> (1) Evaluation of low temperature fixability Equipped with a latent image carrier made of an organic photoconductive semiconductor, a developing device for a two-component developer, and a heating roller qualifier.

Electrophotographic copying n r U-8ix 1550 MRJ (
By modifying the rock (manufactured by Konica #), the linear speed of the heating roller can be increased to 13
9a+m/sec, and while keeping the temperature of the pressure roller lower than the set temperature of the heating roller, and gradually changing the set temperature of the heating roller within the range of 100 to 240°C, apply each of the above developers. A real photo test was conducted to form a fixed toner image using the
After rubbing with a constant load using a rubbing tester, the residual rate of the image at the edge was measured with a microdensitometer, and the lowest set temperature that showed a residual rate of 80% (I low fixing temperature) was determined.
I asked for Note that the surface layer of the heating roller fixing device is PF.
A heating roller with a diameter of 301 m1 made of tetrafluoroethylene-barfluoroalkyl vinyl ether copolymer) and a silicone rubber RKE-1300RT VJ (manufactured by Shin-Etsu Chemical Co., Ltd.) whose surface layer is coated with PFA. It has a linear pressure of 0.8 kg/cm, a nip width of 4.3111 m, and is not equipped with a mechanism for applying a release agent such as silicone oil.

(2) Under-offset resistance (temperature at which wrapping occurs)
Evaluation: Using a so-called solid black original, a live copying test was conducted in the same manner as in the evaluation of low-temperature fixing performance while gradually decreasing the set temperature of the heating roller. Find the temperature of (winding temperature),
A case where no wrapping occurred was evaluated as "good", and a temperature unsuitable for practical use was evaluated as "poor".

(3) Evaluation of anti-offset property A fixed toner image was formed in the same manner as in the evaluation of low-temperature fixing properties above, except that the pressure roller was kept at a temperature close to the set temperature of the heating roller, and immediately after that, a blank sheet was recorded. The material is sent to the heating roller fixing device under similar conditions and visually observed to see if toner stains occur on it at each set temperature of the heating roller, and the lowest setting when toner stains occur is performed. The temperature (offset occurrence temperature) was determined.

(4) Evaluation of toner fluidity Taking advantage of the fact that powder with high fluidity has a low degree of compression,
Each of the above-mentioned toners was loosely filled from above into a container having a diameter of 28 cm and a volume of 100, and the weight was measured to determine the static bulk density of the toner. The evaluation is when the static bulk density is 0.380/112 or higher, 0.38fl/1Q 64 wor
].

(5) Evaluation of durability Using each of the above developers, the electrophotographic copying machine "U-Bix"
1550 MRJ (manufactured by Konica ■) modified machine,
The linear speed of the heating roller was set to 139+u+/sec, the set temperature of the heating roller was set to the lowest window @ temperature of each toner, and the temperature was set to the minimum window @ temperature of each toner, and the temperature was set to eo and ooo times under normal temperature and normal humidity environmental conditions (temperature 20°C, relative humidity 60%). A live photo test was conducted, and durability was evaluated by visually observing the resulting images. The image density (Dmax) and fog of the final image were also evaluated. However, [QmaxJ represents the image @ density to R,
It is expressed as the relative density of the developed image when the image density of the original image is 13.

"Fog" is evaluated as follows based on the relative density of the developed image when the temperature of the original image is set to 0.

None: less than 0.01 slightly present: 0.01 or more but less than 0.02 present:
...0.02 or more As is clear from the results in Table 2, only the samples of the present invention had good fluidity, anti-blocking properties, low-temperature fixing properties, and anti-offset properties, and had excellent durability. We were able to provide an electrostatic image developer.

Claims (1)

[Claims] An electrostatic image developer comprising a toner used to visualize a negatively charged electrostatic latent image with a positively charged toner and a carrier that imparts a positive charge to the toner, the toner comprising:
The carrier contains a block copolymer or a graft copolymer of a crystalline polyester and an amorphous vinyl polymer as a binder resin, and the carrier has a triboelectric charge whose core material contains a fluorinated alkyl (meth)acrylate polymer. An electrostatic image developer coated with a control layer, the triboelectric charge control layer containing more than 50% by weight of fluorinated alkyl (meth)acrylate repeating units.