JPH0830017A - Electrostatic charge image developing one-component toner - Google Patents

Abstract

PURPOSE:To provide an electrostatic charge image developing one-component toner having excellent durability without causing contamination of a sleeve, cleaning defects or electrification defects so that good images can be maintained. CONSTITUTION:This electrostatic charge image developing one-component toner contains a resin charge controlling agent (I) and is used for a developing device in which an electrifying member 5 is pressed to touch a developer carrier body 2 arranged to face a latent image holding body 1. The toner consists of a copolymer having 2000 to 15000 weight average mol.wt. and components of (a) 2- acrylamide-2-methylpropane sulfonic acid, (b) polymerizable monomers having carboxyl groups, (c) styrene and/or alpha-methylstyrene, and (d) polymerizable monomers having hydroxyl groups. Proportions of these components are specified that (a):(b) = 95:5 to 70:30, (a) and (b):(c) = 3:97 to 20:80, (a) and (b) and (c):(d)= 100 pts.wt.:(0.05 to 2.0 pts.wt.), and (a) and (b):(d):100 pts.wt.: (20 pts.wt. or less).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-component toner used for remarkably visualizing an electrostatic latent image in electrophotography and electrostatic recording.

[0002]

2. Description of the Related Art As a conventional electrophotographic method, U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Publication (US Pat. No. 3,666,363) and Japanese Patent Publication No. 43-24748 (US Pat. No. 4,074)
1,361) and the like, various methods are described. The developing methods applied to these electrophotographic methods are roughly classified into a dry developing method and a wet developing method, and the former is divided into a method using a one-component developer and a method using a two-component developer. .

The toner is a colorant composed of a dye, a pigment or the like, a charge control agent, a magnetic material, in a natural or synthetic binder resin,
Wax or the like is internally added, and particles finely pulverized to about 1 to 30 μm are used. Further, a fluidizing agent such as silica may be mixed. It is necessary for any of the toners to be positively or negatively charged depending on the polarity of the electrostatic latent image to be developed, and a charge control agent has been added in order to make the toner retain an electric charge.

The charge control agent promotes triboelectric charging of the toner,
It controls the triboelectric charge amount and maintains the triboelectric charge amount. Typical negatively chargeable charge control agents include carboxylic acid metal complex compounds, diazo compounds, and boron complex compounds, and positively chargeable charge control agents include quaternary ammonium salt compounds. Dyes and pigments such as imidazole compounds, nigrosine, azine dyes, and triphenylmethane dyes. These charge control agents have a poorer compatibility with the binder resin than the charge control agents of resins, so that the ones existing on the toner surface are likely to be released, and the toner charge variation and sleeve contamination are likely to occur. There is. Therefore, as charge control agents capable of improving the compatibility with the binder resin and the transparency of the toner, JP-A-63-184762 and JP-A-3-5 have been proposed.
6974 discloses a negatively chargeable resin charge control agent, and is disclosed in JP-A-63-60458 and JP-A-3-8.
Japanese Patent No. 0259 discloses a positively chargeable resin charge control agent. Since these resin charge control agents have good compatibility with the binder resin, stable charging characteristics can be obtained, and the resin charge control agent has good transparency even when mixed with the binder resin, so that the color toner can be used. . However, the charge control agent is disadvantageous in that it has a lower charge amount as compared with the charge control agents such as metal complex compounds and azo dyes, and therefore it is used in a two-component developer or the charge control agent in the toner. It is necessary to increase the amount of agent added.

When the amount of the charge control agent added is increased, the compatibility with the binder resin may decrease and the offset may occur. Therefore, the compatibility of the charge control agent with the binder resin may be further improved. desired.

By the way, as a developing method using a one-component developer consisting of toner only, US Pat. No. 4,121,
The touch-down developing method described in Japanese Patent No. 931 and the like are mentioned, and a jumping developing method is proposed in Japanese Patent Laid-Open No. 55-18656. In addition, JP-A-58-
In the one-component developing method disclosed in JP-A-116559, JP-A-60-120368, JP-A-63-271371, etc., a developer is coated on a developer carrier with a blade or the like, and the developer is a blade. Alternatively, since the toner is charged by friction with the surface of the developer bearing member, the charging ability of the toner can be improved as compared with the case of non-contact. In this method, the blade material is preferably one that is easily charged to the opposite polarity to the developer, and is disclosed in JP-A-61-250666 and JP-A-62-2.
4285, JP-A-62-203177, JP-A-63-81376, and JP-A-63-25066.
It is proposed in Japanese Patent Laid-Open No. 2 etc. to add a charge control component having a polarity opposite to that of the toner into the blade. By these means, the initial charging characteristics are remarkably improved even if the charging is low.
However, with long-term use, the toner will be damaged by the blade pressure, etc., and the additives present on the toner surface will be easily peeled off.Especially, the charge control agent that is easily charged by itself adheres to the blade or sleeve and contaminates the surface. There was a problem of doing.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a developer carrying member arranged facing a latent image holding member because of its excellent durability, without sleeve contamination, cleaning failure, and toner deterioration. An object of the present invention is to provide a one-component toner for developing an electrostatic charge image, which can maintain a good image even if a developing device in which a charging member is pressed is used.

[0008]

Means and Actions for Solving the Problems As a result of intensive studies by the present inventor, as a result of being arranged facing the latent image carrier,
It has been found that the above problems can be solved by using a toner containing a resin charge control agent in a developing device in which a charging member is pressed against a developer carrier. Recently,
It is effective to use a highly safe resin charge control agent in consideration of the environmental load of chemical substances. By taking advantage of the fact that the charge control agent has excellent compatibility with the binder resin, separation of the charge control agent due to mechanical and thermal load of the toner is suppressed,
The durability of the toner can be improved. However, although the charge stability is excellent, the toner containing the charge control agent has problems in low density and environmental stability due to insufficient charge amount.
Therefore, the present inventor has found that the amount of charge of the toner can be increased by the friction between the development carrier and the charging member that is in pressure contact with the development carrier. It was also found that charge-up can be prevented because the charge amount of the toner can be controlled depending on the type of the charge-giving member.

An example of the developing device for the non-magnetic one-component toner used in the present invention will be described, but the developing device is not limited thereto. In FIG. 1, reference numeral 1 is a latent image carrier, and the latent image is formed by electrophotographic process means or electrostatic recording means (not shown). 2 is a developer carrier,
It consists of a non-magnetic sleeve made of aluminum or stainless steel. The developer carrying member 2 may be a rough tube made of aluminum or stainless steel as it is, but preferably, its surface is uniformly roughened by spraying glass beads or the like, mirror-finished, or coated with resin or the like. Things are good.
The developer is stored in the hopper 3, and the supply roller 4
Is supplied onto the developer carrier 2. The supply roller 4 is made of a foam material such as polyurethane foam,
The developer is rotated in a forward or reverse direction at a relative speed which is not 0 with respect to the developer carrying member 2, and the developer is supplied and the developer (undeveloped developer) after development on the developer carrying member 2 is stripped off. There is. The developer supplied onto the developer carrying member 2 is uniformly and thinly applied by the elastic blade serving as the charging member 5. The contact pressure between the charging member 5 and the developer carrying member 2 is 3 to 25 as a linear pressure in the sleeve generatrix direction.
0 g / cm, preferably 10 to 120 g / cm is effective. If the contact pressure is less than 3 g / cm, it becomes difficult to apply the toner uniformly, and the charge amount distribution of the toner becomes broad, causing fog and scattering. The contact pressure is 25
If it exceeds 0 g / cm, a large pressure is applied to the developer,
Since the external additive of the developer deteriorates, aggregation of the developer occurs, which is not preferable. In addition, a large torque is required to drive the developer carrying member 2, which is not preferable. The charging member 5 is preferably made of a triboelectric material suitable for charging the developer to a desired polarity. For example, to positively charge the developer, use silicone rubber, polyurethane, fluororubber, polychlorobutadiene rubber, etc., and to negatively charge it, use styrene-butadiene rubber, nylon, etc. as a blade. The charging efficiency is higher. Further, by blending silica, resin fine particles and the like, the triboelectric charge imparting property of the charge imparting member 5 to the developer can be adjusted. Also, by blending conductive powder such as carbon and titanium oxide,
By providing the charge imparting member 5 with appropriate conductivity,
It is possible to prevent the developer from being excessively charged.

The resin charge control agent (I) that can be used in the toner of the present invention has a weight average molecular weight of 2,000 having the following respective component constitutions (a), (b), (c) and (d).
It is a copolymer of 0 to 15,000.

(A) 2-Acrylamido-2-methylpropanesulfonic acid (b) Carboxyl group-containing polymerizable monomer (c) Styrene and / or α-methylstyrene (d) Hydroxyl group-containing polymerizable monomer Component (a): Component (b) = 95: 5 to 70: 30% Component (a) and component (b): Component (c) = 3: 97 to
20: 80% Component (a), Component (b) and Component (c): Component (d) =
100 parts: 0.05-2.0 parts The weight average molecular weight of the resin charge control agent (I) is 2,000-.
It should be 15,000. Preferably 3,
It is 000 to 8,000. Weight average molecular weight is 2,000
If it is less than 0, the moisture resistance of the toner tends to decrease, and offset tends to occur. If it exceeds 15,000, the dispersion in the binder resin tends to be poor, and fog and ghost tend to be poor, such being undesirable.

Examples of the (b) carboxyl group-containing polymerizable monomer include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and crotonic acid.

Examples of the (d) hydroxyl group-containing polymerizable monomer include hydroxyethyl methacrylate,
Examples thereof include hydroxyethyl acrylate and hydroxyisopropyl acrylate.

Further, the component (a): the component (b) is 95: 5.
˜70: 30% is preferable, and 90:10 to 80: 20% is more preferable. 95% of component (a)
If the content exceeds 5% (component (b) is less than 5%), the dispersibility of the magnetic material, colorant, wax and other internal additives in the toner may be deteriorated, and component (a) is less than 70% (component (b)). Is more than 30%), the environmental stability of the toner tends to deteriorate, which is not preferable.

Component (a) and component (b): The component (c) is preferably 3:97 to 20: 80%, more preferably 5:95 to 13: 87%. When the amount of the component (a) and the component (b) exceeds 20% (the amount of the component (c) is less than 80%), the charge amount of the toner tends to decrease under high humidity,
Component (a) and component (b) are less than 3% (component (c) is 9%
If it exceeds 7%), the chargeability of the resin charge control agent tends to be low, which is not preferable.

Component (a), component (b) and component (c):
Component (d) is preferably 100 parts: 0.05 to 2.0 parts, more preferably 100 parts: 0.1 to 1.5.
Good part. Component (d) is less than 0.05 parts or 2.0
If it exceeds the amount, the effect of dispersing the toner particles in the toner tends to be lost, which is not preferable.

The resin charge control agent (II) which can be used in the toner of the present invention has a weight average molecular weight of 2,000 to each having the following repeating units (e), (f) and (g).
It is a copolymer of 20,000.

[0018]

Embedded image

Repeating unit 65 to 97% by weight of component (e), repeating unit 35 to 3% by weight of component (f), repeating unit of component (e) and component (f): repeating unit of component (g) = 100 parts by weight: 0.1 to 2.0 parts by weight The weight average molecular weight of the resin charge control agent (II) is 2,000.
It is preferably 20,000 to 20,000, and more preferably 5,000 to 16,000. When the weight average molecular weight is less than 2,000, the moisture resistance of the toner tends to be low, and offset tends to occur. When it exceeds 20,000, dispersion with the binder resin tends to be poor, and fog and ghost tend to be poor. There is not preferable.

Further, the repeating unit of the component (e) is 65 to
It is preferably 97% by weight, more preferably 77
˜97 wt%, and more preferably 80 to 95 wt%. If it is less than 65% by weight, the compatibility with the binder resin tends to deteriorate, and if it exceeds 97% by weight, the compatibility with the binder resin tends to be good, but the environmental stability of the toner tends to deteriorate, which is not preferable. .

The repeating unit of the component (f) is preferably 35 to 3% by weight, more preferably 23 to 3% by weight, still more preferably 20 to 5% by weight. 3% by weight
If it is less than 35% by weight, the chargeability as a charge control agent tends to decrease, and if it exceeds 35% by weight, the moisture resistance tends to decrease, which is not preferable.

Further, the repeating unit of the component (e) and the component (f): 100 parts by weight of the repeating unit of the component (g):
The amount is preferably 0.1 to 2.0 parts by weight, more preferably 100 parts by weight: 0.3 to 1.5 parts by weight.
If it is less than 0.1 parts by weight or exceeds 2.0 parts by weight, dispersion in the toner tends to be poor, which is not preferable.

The amount of internal addition is preferably 0.1 to 10 parts by weight, more preferably 0.5, based on 100 parts by weight of the binder resin.
~ 6 parts by weight.

In addition, the present inventors have found that the melt viscosity (S _PB ) of the binder resin measured by a flow tester and the melt viscosity η _PB and η _{PC at} the softening point (S _PC ) of the resin charge control agent are 5 × 10 5. ^{In the case of -2} ≤ η _PC / η _PB ≤ 10, the charge amount in the toner is increased. Therefore, even if the amount of the charge control agent added is increased, compatibility between the two does not decrease, and sleeve contamination and cleaning are performed. It has been found that a one-component toner excellent in durability and free from defects and charging defects can be obtained.

At this time, S_PBAnd S_PCDifference is less than 30 ℃
Preferably. Also η_PC/ Η _PBIs 5 × 10^-2From
It is preferably in the range of 1. η_PC/ Η_PBIs 5 × 10^-2
If it is less than 10 or more than 10, the charge in the binder resin and the resin charge
The compatibility of the control agent is poor, and the resin charge control agent in the toner is
Dispersed state deteriorated and it was placed facing the latent image holder
A developing device in which a charging member is pressed against a developer carrier
In the case of using
Release of the resin charge control agent may cause sleeve contamination or cracking.
Leaning failure and charging failure occur.

Next, the method of measuring the viscosity according to the present invention will be described.

The viscosity of the binder resin or toner is measured by an elevated flow tester (Shimadzu flow tester CFT shown in FIG.
-500 type), a sample of about 1.5 g, which was first molded using a pressure molding machine, was pressed by a plunger at a constant temperature.
A load of 0 kgf was applied to push out from a nozzle having a diameter of 1 mm and a length of 1 mm, and thereby the plunger drop amount (flow rate) of the flow tester was measured. This outflow rate is measured at each temperature (in the temperature range of 100 ° C. to 180 ° C. at 5 ° C. intervals), and the apparent viscosity η ′ can be obtained from the following equation from this value.

[0028]

[Equation 1]

Η ': Apparent viscosity (poise) TW': Apparent shear stress on the tube wall (dyne / cm ² ) DW ': Apparent shear rate on the tube wall (1 / sec) Q: Outflow rate (cm ³⁾ / Sec = ml / sec) P: Extrusion pressure (dyne / cm ² ) [10 Kgf = 98
0 × 10 ⁴ dyne] R: Nozzle radius (cm)

In the flow tester measurement, the softening point S _P here is an intermediate between the temperature T ₁ at which the entire sample melts and starts to flow out stably as the temperature rises, and the temperature T _{2 at} which the outflow rate is saturated. Is the temperature.

In the toner of the present invention, a resin charge control agent, a colorant, a magnetic material, a wax and the like are added to the binder resin. The amount of these compounds used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. .

Examples of the resin for forming the toner particles used in the present invention include polystyrene and poly-p-
Chlorostyrene, homopolymers of styrene such as polyvinyltoluene and its substitution products; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid ester copolymers Coal, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene- Vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-
Styrene-based copolymers such as indene copolymers; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide Resin, furan resin,
Epoxy resin, xylene resin, polyvinyl butyral,
Terpene resin, coumarone indene resin, petroleum resin, etc. can be used.

A crosslinked styrene copolymer is also a preferred binder resin. Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate,
2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate,
A monocarboxylic acid having a double bond such as acrylonitrile, methacrylonitrile, acrylamide or the like; or a dicarboxylic acid having a double bond such as maleic acid, butyl maleate, methyl maleate or dimethyl maleate. And substituted products thereof; vinyl esters such as vinyl chloride, vinyl acetate, vinyl benzoate, etc .; ethylene-based olefins such as ethylene, propylene, butylene, etc .; such as vinyl methyl ketone, vinyl hexyl ketone, etc. Vinyl monomers such as vinyl ketones; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc .; or two or more vinyl monomers are used. Derivatives having two or more polymerizable double bonds are mainly used as the cross-linking agent, and examples thereof include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate and ethylene glycol diethylene. Methacrylate, 1,3-
A carboxylic acid ester having two double bonds such as butanediol dimethacrylate; a divinyl derivative such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and a derivative having three or more vinyl groups; Used as.

When the pressure-fixing system is used, a binder resin for pressure-fixing toner can be used. Examples thereof include polyethylene, polypropylene, polymethylene, polyurethane elastomer, ethylene-ethyl acrylate copolymer, ethylene-acetic acid. Examples thereof include vinyl copolymers, ionomer resins, styrene-butadiene copolymers, styrene-isoprene copolymers, linear saturated polyesters and paraffins.

External addition of silica to the toner containing the resin charge control agent of the present invention is a preferred form.

The amount of silica used at that time is not uniquely limited, but is preferably 0.05 to 10 parts by weight, and more preferably 0.2, based on 100 parts by weight of the toner.
It is used in the range of up to 5 parts by weight.

As such a silica fine powder, silica fine powder produced by a dry method or a wet method can be used. The dry method referred to here is a method for producing fine silica powder produced by vapor phase oxidation of a silicon halogen derivative, and by using another metal halogen derivative such as aluminum chloride or titanium chloride together with the silicon halogen derivative in the production process. It is also possible to obtain a composite fine powder of silica and another metal oxide. On the other hand, as a method for producing fine silica powder by a wet method, various conventionally known methods can be applied. For example, decomposition of sodium silicate by acid,
Decomposition of sodium silicate with ammonia salts or alkali salts, a method of producing alkaline earth metal silicate from sodium silicate, and then decomposing with acid to obtain silicic acid,
There are a method of converting a sodium silicate solution into a silicic acid by an ion exchange resin, a method of utilizing a natural silicic acid or a silicate, and the like.

The silica fine powder referred to here is anhydrous silicon dioxide (silica), other than aluminum silicate, sodium silicate, potassium silicate, magnesium silicate,
Any silicate such as zinc silicate can be applied.

Among the above silica fine powders, those having a specific surface area by nitrogen adsorption of 30 m ² / g or more (particularly 50 to 400 m ² / g) measured by the BET method give good results.

The silica fine powder used in the present invention is
If necessary, it may be treated with a treating agent such as a silane coupling agent or an organic silicon compound, and a known method can be used as well, which is treated by reaction with the fine silica powder or physical adsorption.

Examples of treatment agents for obtaining positively chargeable silica include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylamino. Propyltrimethoxysilane, monobutylaminopropyltrimethoxysilane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ-propylphenylamine, Trimethoxysilyl-γ-propylbenzylamino, etc., and in the nitrogen-containing heterocyclic system, trimethoxysilyl-
γ-propylpiperidine, trimethoxysilyl-γ-propylmorpholine, trimethoxysilyl-γ-propylimidazole and the like.

Further, examples of the treating agent for obtaining negatively chargeable silica include hexamethyldisilazane, trimethylsilane,
Trimethylchlorosilane, trimethylethoxysilane,
Dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane , Triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,
There are 3-diphenyltetramethyldisiloxane, dimethylpolysiloxane having 2 to 12 siloxane units per molecule, and each of the terminally located units has a hydroxyl group bonded to Si. These are used alone or in a mixture of two or more.

As the silicone oil, methyl silicone oil, dimethyl silicone oil, phenylmethyl silicone oil, chlorophenylmethyl silicone oil, alkyl modified silicone oil, fatty acid modified silicone oil, polyoxyalkylene modified oil and the like are preferable. These are used alone or as a mixture of two or more.

In the present invention, the positive triboelectrically chargeable silica fine powder refers to one having a positive charge with respect to the iron powder carrier when measured by the blow-off method.

The applied amount of these treated fine silica powders exerts an effect when the amount of the developer is 0.01 to 20%, particularly preferably 0.03 to 5%, based on the weight of the developer. It exhibits positive triboelectricity with stability. To describe a preferable mode of addition, it is preferable that 0.01 to 3% by weight of the treated silica fine powder with respect to the weight of the developer is attached to the surface of the toner particles.

The electrostatic image developing toner of the present invention can be used as a magnetic toner by incorporating a magnetic material.
Examples of the magnetic material used include iron oxides such as magnetite, γ-iron oxide, ferrite, and iron-rich ferrite; iron,
Metals such as cobalt and nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin,
Examples thereof include alloys with metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof. These magnetic materials have an average particle size of 0.1.
The amount contained in the magnetic toner is preferably 20 to 150 parts by weight, and more preferably 30 to 120 parts by weight, based on 100 parts by weight of the binder resin component. Is.

As the magnetic toner using the charge control agent of the present invention, a toner having a weight average particle diameter of 3 to 15 μm can be used. In particular, 12 to 60% by number of magnetic toner particles having a particle size of 5 μm or less are contained, 1 to 33% by number of magnetic toner particles having a particle size of 8 to 12.7 μm are contained, and a particle size of 16 μm or more. Magnetic toner particles are 2.
The content of the magnetic toner is 0% by weight or less, and the weight average particle diameter of the magnetic toner is 4
From the standpoint of development characteristics, it is more preferably 10 μm.

The particle size distribution of the toner can be measured by various methods, but in the present invention, it is suitable to use a Coulter counter.

That is, a Coulter counter TA-II type (manufactured by Coulter) is used as a measuring device, and an interface (manufactured by Nikkaki) for outputting number distribution and volume distribution and a CX-1 personal computer (manufactured by Canon) are connected. As the electrolytic solution, an about 1% NaCl aqueous solution is prepared using first-grade sodium chloride. For example, ISOTO
N (R) -II (made by Coulter Scientific Japan) can be used. As a measuring method, a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant in 100 to 150 ml of the electrolytic aqueous solution in an amount of 0.1 to 5 m.
1 and 2 to 20 mg of the measurement sample are further added. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toners were measured with the Coulter Counter TA-II type using a 100 μm aperture as an aperture. The volume distribution and number distribution of particles of 2 to 40 μm were calculated. Then, the weight-based weight average diameter (D ₄ ) obtained from the volume distribution according to the present invention (the median value of each channel is a representative value for each channel), and the weight-based coarse powder amount obtained from the volume distribution (20.2 μm or more), and the number-based fine powder number (6.35 μm or less) determined from the number distribution was determined.

Further, the toner of the present invention may be mixed with an additive, if necessary. Examples of the additives include lubricants such as zinc stearate, abrasives such as cerium oxide and silicon carbide, fluidity-imparting agents such as aluminum oxide and titanium oxide, anti-caking agents, or carbon black, tin oxide and the like. There is a conductivity-imparting agent.

Fluorine-containing polymer fine powders such as polyvinylidene fluoride fine powders are also preferable additives from the viewpoints of fluidity, abrasivity and charge stability.

For the purpose of improving releasability at the time of heat roll fixing, a wax-like substance such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, carnauba wax, sazol wax and paraffin wax is added in an amount of 0.5-5. It is also one of the preferred embodiments of the present invention to add about wt% to the toner.

In producing the toner according to the present invention, the toner constituent materials as described above are thoroughly mixed by a ball mill or other mixing machine, and then thoroughly kneaded by using a heat kneader such as a hot roll kneader or an extruder. A method of obtaining a toner by mechanical pulverization and classification after cooling and solidification is preferable. Another method is to obtain a toner by dispersing constituent materials in a binder resin solution and then spray-drying; or in a so-called microcapsule toner comprising a core material and a shell material, a core material or a shell material, or these materials. A method of incorporating a predetermined material into both of them; and the like can be applied.

Further, if desired, desired additives can be sufficiently mixed with a mixer such as a Henschel mixer to produce the toner according to the present invention.

The toner of the present invention can be used by any conventionally known means for development for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing and the like.

[0056]

EXAMPLES Production examples of the resin charge control agent used in the present invention are shown below.

Production Example 1 of Resin Charge Control Agent (I) A 2-liter flask was equipped with a stirrer, a condenser, a thermometer, and a gas introduction tube, and 400 g of xylene and 2-acrylamido-2-methylpropanesulfone were placed in the flask. Acid 24g, Methacrylic acid 6g, Styrene 575
g, 1.2 g of hydroxypropyl methacrylate, and 1.5 g of benzoyl peroxide were added, and 9 under N ₂ gas was added.
Solution polymerization was carried out at 0 ° C. for 7 hours. After that, the solvent was removed under reduced pressure at 120 ° C., the mixture was pulverized by a jet mill, and the softening point S _PC = 12.
A resin charge control agent (I-1) having a melt viscosity η _PC = 5 × 10 ³ Pa · s at 5 ° C. was obtained.

Production Example 2 of Resin Charge Control Agent (II) A 2 liter flask was equipped with a stirrer, a condenser, a thermometer and a gas introduction tube, and xylene 2 was placed in the flask.
80 g, 540 g of styrene, 6 g of hydroxymethacrylate, 60 g of diethylaminoethyl methacrylate and 10 g of benzoyl peroxide were added, and solution polymerization was carried out at 90 ° C. for 7 hours under introduction of N ₂ gas. After that, 73 g of methyl methylsulfonate and 320 g of xylene were added and reacted at 90 ° C. for 4 hours, then the solvent was removed under reduced pressure at 120 ° C., and the mixture was pulverized by a jet mill to obtain a softening point S _PC = 115 ° C. and a melt viscosity at the softening point. A resin charge control agent (II-1) having η _PC = 6 × 10 ³ Pa · s was obtained.

Production Example 3 of Resin Charge Control Agent (II) In the same manner as in Production Example 2 of resin charge control agent (II), 300 g of xylene, 528 g of styrene, and butyl acrylate 7 were added.
2 g, 9 g of diethylaminoethyl methacrylate, and 8 g of benzoyl peroxide were added, and 9 g was introduced under introduction of N ₂ gas.
Solution polymerization was carried out at 0 ° C. for 6.5 hours, then 12 g of para-toluenesulfonic acid and 300 g of xylene were added and reacted at 90 ° C. for 4 hours, the solvent was removed under reduced pressure at 120 ° C., and jet mill pulverization was carried out to give a softening point S _PC = A resin charge control agent (II-2) having a melt viscosity η _PC = 3.7 × 10 ⁴ Pa · s at a softening point of 120 ° C. was obtained.

Example 1 Styrene-butyl acrylate copolymer 100 parts (S _PB = 115 ° C., η _PB = 3.7 × 10 ⁴ Pa · s) Magnetic iron oxide 90 parts Low molecular weight propylene 3 parts Resin control agent (I -1) 5 copies

The above mixture was kneaded by a twin-screw kneading extruder heated to 140 ° C. The cooled kneaded material is coarsely crushed with a hammer mill, the coarsely pulverized material is finely pulverized with a fine pulverizer using a jet stream, and the finely pulverized powder obtained is a multi-division classifier utilizing the Coanda effect. An ultra-fine powder and a coarse powder were strictly classified at the same time by an elbow jet classifier manufactured by Sangyo Co., Ltd. to obtain a negatively chargeable magnetic toner having a weight average particle diameter (D ₄ ) of 8.0 μm.

To 100 parts by weight of this toner, 0.6 parts by weight of hydrophobic silica (BET specific surface area 160 m ² / g) was mixed with a Henschel mixer to obtain a one-component magnetic toner.

The obtained magnetic toner was subjected to an image forming test with a commercially available laser beam printer LASER SHOT A404 (using urethane blade) (manufactured by Canon Inc.), and a density of 1.43 was obtained from the initial stage. However, the image density was 1.40 and no decrease in density was observed even after copying 5,000 sheets. The charge amount of the developer on the sleeve of the 500th sheet was -8.3 mC / kg. In addition, neither sleeve dirt nor cleaning failure occurred.

Example 2 Styrene-acrylate copolymer 100 parts (S _PB = 125 ° C., η _PB = 9.8 × 10 ³ Pa · s) Carbon black 4 parts Low molecular weight polypropylene 4 parts Resin charge control agent (II- 1) 4 copies

Using the above materials, a positively chargeable one-component toner having a weight average particle diameter of 11.3 μm was obtained in the same manner as in Example 1.

To 100 parts by weight of this toner, 0.6 parts by weight of positively charged silica was mixed with a Henschel mixer to obtain a one-component non-magnetic toner.

A commercially available copying machine NP1215 (manufactured by Canon Inc.) was modified to have the developing device shown in FIG. 1, and the elastic blade 5 was formed by molding silicone rubber into a sheet having a thickness of 1.2 mm. Then, a copy test was conducted with the above developer. A density of 1.27 was obtained from the initial stage, a density of 1.30 was obtained on the 100th sheet, and the rise of the image density was also good. Also, 10
The charge amount of the developer on the 0th sleeve is 28 mC / kg
Met. After that, when the image formation was continued up to 10,000 sheets, the density did not decrease and the sleeve was not stained.

Example 3 Styrene-butyl acrylate copolymer 100 parts (S _PB = 125 ° C., η _PB = 6.7 × 10 ⁴ Pa · s) Carbon black 4 parts Low molecular weight polypropylene 3 parts Resin charge control agent (II -1) 5 copies

Using the same materials as in Example 1, a positively chargeable one-component toner having a weight average particle diameter of 10.8 μm was obtained.

To 100 parts by weight of this toner, 0.6 parts by weight of positively chargeable silica was mixed with a Henschel mixer to obtain a one-component non-magnetic toner.

A copy test was conducted in the same manner as in Example 2. An image density of 1.23 was obtained from the initial stage, the start-up was good, and a good image with a density of 1.24 was obtained even after outputting 8,000 sheets. The charge amount at this time is 22 mC / k
g.

Example 4 100 parts of styrene-methacrylate copolymer (S _PB = 115 ° C., η _PB = 2.7 × 10 ³ Pa · s) 80 parts of magnetic iron oxide 4 parts of resin charge control agent (II-2) Low molecular weight propylene 3 parts

Using the same materials as in Example 1, a positively chargeable magnetic toner having a weight average particle diameter of 9.6 μm was obtained. Then, 100 parts by weight of this toner was mixed with 0.6 part by weight of positively chargeable silica by a Henschel mixer to finally obtain a one-component magnetic toner.

With this toner, commercially available Family Copier PC
When a copying test was conducted with a modified machine in which the blade of -10 (manufactured by Canon Inc.) was changed to a silicon rubber blade, an image density of 1.40 was obtained from the initial stage, and 1.30 was obtained even after 3,000 copies. Was stable. The charge amount of the toner on the sleeve was stable at around 9 mC / kg.

Comparative Example 1 A 8.3 μm single-component magnetic toner was obtained in the same manner as in Example 1 except that 3 parts of a salicylic acid derivative was added instead of the resin charge control agent (I-1). When an image output test was conducted using the laser beam printer used in Example 1, 5
The image density decreased from about the 00th sheet to 1.00 or less, and the fog also worsened.

Comparative Example 2 In the production of the resin charge control agent (II-1), 5 parts of styrene and 5 parts of diethylaminoethyl methacrylate were used, respectively.
Solution polymerization was performed in the same manner with 90 g and 10 g. Then, 14 g of methyl methyl sulfonate and 33 g of xylene were used.
After adding 0 g and reacting at 90 ℃ for 4 hours, 120 ℃
The solvent was removed under reduced pressure and pulverization was carried out by a jet mill, and the softening point S _PC = 120 ° C. and the solution viscosity at that softening point η _PC = 7.
A resin charge control agent (II-3) of × 10 ³ Pa · s was obtained.

In Example 2, the resin charge control agent (II-
4 parts of the resin charge control agent (II-3) was added instead of 1) to obtain a 11.6 μm single-component non-magnetic toner.

An image output test was conducted in the same manner as in Example 2. As a result, the initial density rise was 1.17 and the density was low at 1.20 even with 1,000 sheets, and the fog was also poor. . The charge amount was as low as 8 mC / kg.

Comparative Example 3 Using the same compound as in Production Example 3 of the resin charge control agent (II-2), the softening point S _PC = 125 ° C. and the melt viscosity at the softening point η _PC = 3.8 × 10 ⁵ Pa · A resin charge control agent (II-4) of s was obtained.

Polyester resin 100 parts (S _PB = 85 ° C., η _PB = 2 × 10 ⁴ Pa · s) Magnetic iron oxide 80 parts Resin charge control agent (II-4) 5 parts Low molecular weight propylene 3 parts

Using the same materials as in Example 1, a one-component magnetic toner having a weight average particle diameter of 12.1 μm was obtained. Example 2
When an image output test was conducted in the same manner as above, the initial density was as low as 1.05, and the charging amount on the sleeve was 4 due to poor charging.
There was only mC / kg. Also, around the 100th sheet,
Drum fusion also occurred.

[0082]

As described above, according to the present invention, there is no sleeve contamination, cleaning failure, charging failure, and excellent durability, and electrostatic image development capable of maintaining a good image is continued. It is possible to obtain a one-component toner for use.

[Brief description of drawings]

FIG. 1 is a diagram showing an example of a developing device used in the present invention.

FIG. 2 is a diagram showing an elevated flow tester for measuring viscosity.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03G 9/08 344

Claims (3)

[Claims] 1. An electrostatic charge image developing device for use in a developing device, comprising a binder resin and a resin charge control agent, wherein a charging member is brought into pressure contact with a developer carrying member which is arranged opposite to a latent image holding member. One-component toner for use. 2. The one-component toner for developing an electrostatic charge image according to claim 1, wherein the resin charge control agent contains the following resin charge control agent (I) or (II). Resin charge control agent (I) Copolymer having a weight average molecular weight of 2,000 to 15,000 and having the following constituents (a), (b), (c) and (d) (a) 2-acrylamide- 2-Methylpropanesulfonic acid (b) Carboxyl group-containing polymerizable monomer (c) Styrene and / or α-methylstyrene (d) Hydroxyl group-containing polymerizable monomer Component (a): Component (b) = 95: 5 to 70 : 30% Component (a) and component (b): Component (c) = 3: 97-
20: 80% Component (a), Component (b) and Component (c): Component (d) =
100 parts: 0.05 to 2.0 parts Resin charge control agent (II) Copolymer having a weight average molecular weight of 2,000 to 20,000 and having the following repeating units (e), (f) and (g). Coalescing Repeating unit 65 to 97% by weight of component (e), repeating unit 35 to 3% by weight of component (f), repeating unit of component (e) and component (f): repeating unit of component (g) = 100 parts by weight : 0.1 to 2.0 parts by weight 3. The temperature difference between the softening point (S _PB ) of the binder resin measured by a flow tester and the softening point (S _PC ) of the resin charge control agent according to claim 2 is 30 ° C. or less. A one-component toner for developing electrostatic images, in which each melt viscosity η _PB and η _{PC at the} softening point is 5 × 10 ⁻² ≦ η _PC / η _PB ≦ 10.