toner for electrostatic imaging, developer, process cartridge, and imaging apparatus

专利摘要:
TONER FOR ELECTROSTATIC IMAGING, DEVELOPER, PROCESS CARTRIDGE, AND IMAGING APPARATUS. To provide a toner, which contains a colorant, a binder resin A, and a release agent, wherein the toner satisfies the following (a) to (c): (a) the toner contains at least one polyester resin A as a resin A binder; (b) the toner has 1a Tg from 25°C to 50°C; and (c) the toner has a compressive strain ratio TMA (TMA%) of 10% or lower at 50°C under a condition that has a relative humidity of 70%, where ai Tg is the toner's glass transition temperature for first heating, as the toner is measured by a DSC system (a differential scanning calorimeter).
公开号:BR102013023982B1
申请号:R102013023982-8
申请日:2013-09-18
公开日:2021-06-22
发明作者:Daisuke Asahina；Hiroshi Yamashita；Tsuyoshi Sugimoto；Yukari Fukuda；Rintaro Takahashi；Masana Shiba
申请人:Ricoh Company, Ltd；
IPC主号:

专利说明:

FIELD OF THE INVENTION
The present invention relates to a toner for forming an electrostatic image, which is used in an electrophotographic image forming apparatus, such as a copier, a printer, and FAX, and to a developer using the toner, a process cartridge, and an imaging apparatus in which the process cartridge is mounted.
A technology to fix a toner with low energy is desired due to the abundance of environmentally friendly products. There are several ways to achieve such fixation, but among them there is a strong demand for a toner to form an electrostatic image, which can be fixed at low temperature.
As one method of lowering the setting temperature of a toner, typically performed is lowering the glass transition temperature (Tg) of a toner binder. As Tg is simply made low, however, dust aggregation (blocking) tends to occur. If toner powder is aggregated inside an imaging apparatus, the operation of a developing device is affected, and there is a case where the developing device cannot be operated. Even if the developing device can still be operated, a toner cannot be supplied as the toner is aggregated inside a toner container which leads to low toner density and defective imaging.
Since a toner is designed to have a low Tg, moreover, the toner tends to settle onto a conveyor, a photoconductor, and multiple blades, and therefore, defective images can form. Consequently, it is necessary to prevent occurrences of blocking or film formation, and to improve the anti-blocking property of a toner. Furthermore, the shelf stability of a toner present on a surface of a still image is degraded as Tg is low. If the still image is easily merged and shifted, toner may be deposited on another recording medium stacked on the recording medium supporting the still image, and therefore may not be able to store the still image for a long period.
Tg is an important factor in the design of a toner binder. According to one method, by simply reducing Tg, a toner, which can be fixed by a fixing device temperature that is set lower than the temperature used in the conventional technique, was not obtained.
However, as a method to obtain anti-blocking property, anti-film property and ability to fix a low temperature of a toner, the use of a crystalline resin A as a toner binder has been known for a long time. However, such toner has a problem that hot offset is caused due to lack of elasticity when the toner is fused.
Furthermore, as a method for obtaining anti-blocking property, anti-blocking property, anti-film-forming property and temperature-fixing ability of a toner, a core-shell type toner having a shell formed by a melt suspension method, or method, is proposed. of emulsification aggregation (see, for example, JP Patent Applications Open to the Public (JP-A) Nos. 2009-053695 and 2011-150229). However, these toners are still insufficient to obtain excellent anti-blocking properties and anti-film-forming properties while maintaining low temperature fixing capabilities.
Furthermore, to solve the above-mentioned problem, a method focusing on a crystalline resin A is proposed (see JP-A no 2011-123483). However, such crystalline resin A is easily influenced by external conditions (history of heating during production, storage and fixation, and partial phase mixing), and a crystal structure thereof is not stable, which can adversely affect various properties of a toner, anti-blocking property and image stability.
According to these conventional techniques, moreover, crystalline polyester resin A melts sharply compared to non-crystalline polyester resin A, and therefore, these toners can achieve low temperature setting ability. It is possible to obtain both the low temperature fixing ability and heat resistant storage stability of a toner according to these conventional techniques, however there are problems, particularly in the case where a toner is used in a high speed device, that toner aggregates as the voltage applied to the toner in the developing device is large, and a white missing area (lack of transfer) is formed over the output toner image due to tamper-blocking. In the case of a toner containing a crystalline polyester resin A, moreover, there is a problem that the toner forms aggregates in high temperature high humidity environment.
Consequently, it is the current situation that is needed for a toner, which has low temperature fixing capability, anti-blocking property, and anti-film formation property, and capable of preventing high transfer. SUMMARY OF THE INVENTION
The present invention aims to provide a toner for forming a latent electrostatic image, which realizes low temperature fixation capability, anti-blocking property, anti-film forming property, and white transfer failure prevention.
As a means of solving the above-mentioned problems, the toner of the present invention contains a colorant, a binder resin A, and a release agent, wherein the toner satisfies the following (a) to (c): (a) the toner contains at least one polyester resin A as binder resin A; (b) the toner has a 1st Tg of 25°C to 50°C; and (c) the toner has a TMA compressive strain ratio (TMA%) of 10% or lower at 50°C under a condition having a relative humidity of 70%, where the 1st Tg is the glass transition temperature of the toner. for the first heat, as the toner is measured by a DSC system (a differential scanning calorimeter).
The present invention can solve the various problems mentioned above in the art, and can provide a toner for forming a latent electrostatic image, which realizes low temperature fixing capability, anti-blocking property, anti-film forming property, and white transfer failure prevention. .
Specifically, the toner has the anti-blocking property just before heat is applied to the toner for fixing, and it allows for low temperature fixing as the toner shows a marked softening when heat is applied, and therefore the toner can carry out the low-temperature clamping ability, anti-blocking property, anti-film-forming property, and white transfer lack prevention, which are paradoxical characteristics. BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a schematic diagram illustrating an example of the imaging apparatus of the present invention.
Figure 2 is a schematic diagram illustrating another example of the imaging apparatus of the present invention.
Figure 3 is a schematic diagram illustrating an imaging unit of each color.
Figure 4 is a schematic diagram illustrating an example of the process cartridge of the present invention. DETAILED DESCRIPTION OF THE INVENTION (Toner)
The toner of the present invention contains at least one colorant, binder resin A, and a release agent, and may contain other components if necessary.
Furthermore, the toner contains a polyester resin A as the binder resin A. The toner preferably contains at least one non-crystalline resin A, such as polyester resin A. <Non-crystalline polyester resin A>
Non-crystalline polyether resin A contains a diol component as a constitutional component. The diol component contains C3-C10 aliphatic diol in an amount of 50% mol or greater. The non-crystalline polyether resin A, moreover, contains trivalent or higher acid, or trihydric or higher alcohol, as a crosslinking component.
Non-crystalline polyether resin A can be used alone, or in combination. Non-crystalline polyether resin A is preferably a non-crystalline polyether resin A obtained through a reaction between a hydrogen group-containing compound and a polymer that reacts with the active hydrogen group-containing compound, as such resin A has excellent adhesion to a medium such as paper. More preferably, the non-crystalline polyether resin A contains a urethane bond and/or a urea bond. In such non-crystalline polyether resin A, a urethane bond and/or urea bond act as apparent crosslinking points, and therefore the rubber characteristics of a non-crystalline polyether resin A are enhanced to thereby improve the heat-resistance storage stability and heat-shift resistance of a resulting toner.-Diol-
The diol is appropriately selected depending on the intended purpose without any limitation, with the proviso that the diol contains C3-C10 aliphatic diol in an amount of 50% mol or greater. Examples thereof include: aliphatic diol such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1 ,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol; diols containing an oxyalkylene group, such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; alicyclic diol such as 1,4-cyclohexane dimethanol, and hydrogenated bisphenol A; alkylene oxide (for example, ethylene oxide, propylene oxide, and butylene oxide) alicyclic diol adduct; bisphenol, such as bisphenol A, bisphenol F, and bisphenol S; and alkylene oxide (e.g., ethylene oxide, propylene oxide, and butylene oxide) bisphenol adduct. Among them, C3-C7 aliphatic diol is preferable. These diols can be used alone, or in combination.
Furthermore, it is preferred that the number of carbon atoms in a main chain of the diol component is an odd number, and the diol component has an alkyl group on a side chain thereof, as a resultant non-crystalline resin A can demonstrate rubber elasticity maintaining high thermal deformability over a set temperature range to thereby further improve the low temperature setting and anti-blocking property of a resulting toner.-Dicarboxylic acid-
The dicarboxylic acid is appropriately selected depending on the intended purpose without any limitation, and examples thereof include aliphatic dicarboxylic acid, and aromatic dicarboxylic acid. Furthermore, the anhydride thereof, lower alkyl ester (C1-C3) thereof, and the halogenated product thereof can be used.
The aliphatic dicarboxylic acid is appropriately selected depending on the intended purpose without any limitation, and examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid and fumaric acid.
The aromatic dicarboxylic acid is appropriately selected depending on the intended purpose without any limitation, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalene dicarboxylic acid. Among them, C4-C12 aliphatic dicarboxylic acid is preferable.
These dicarboxylic acids can be used alone, or in combination.-Trivalent or higher acid or trihydric or higher alcohol-
Higher trivalent acid or higher trihydric alcohol is appropriately selected depending on the intended purpose without any limitation. Examples thereof include trimellitic acid, pyromellitic acid, glycerin, trimethylol ethane, trimethylol propane, pentaerythritol, sorbitol, sorbitan, and dipentaerythritol. These trivalent or higher acids or trihydric or higher alcohols can be used alone, or in combination.
When trivalent or higher acid or trihydric or higher alcohol is contained, the elasticity of the rubber is demonstrated, and the anti-blocking property is further improved. The use of trivalent acid or trihydric alcohol is preferable, as the elasticity of rubber is demonstrated while maintaining the high thermal deformability of resin A over a set temperature range, and the low temperature setting ability and anti-locking property of a resulting toner are improved.-Polyester resin A containing urethane bond and/or urea bond-
Polyester resin A containing a urethane bond and/or urea bond is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a reaction product between polyester resin A containing an active hydrogen group and polyisocyanate. -Polyisocyanate-
The polyisocyanate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include diisocyanate, and trivalent or higher isocyanate.
Examples of diisocyanate include aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, aromatic aliphatic diisocyanate, isocyanurate, a phenol derivative thereof, a blocked product thereof with oxime or caprolactam.
The aliphatic diisocyanate is suitably selected depending on the intended purpose without any limitation. Examples thereof include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethine diisocyanate, dodecamethylene diisocyanate, tetradeamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate.
The alicyclic diisocyanate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include isophorone diisocyanate, and cyclohexylmethane diisocyanate.
The aromatic diisocyanate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanate-3, 3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, and diphenyl ether-4,4'-diisocyanate.
The aliphatic aromatic diisocyanate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include,,,’-tetramethylxylene diisocyanate.
The isocyanurate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include tris(isocyanatoalkyl) isocyanurate, and tris(isocyanatocycloalkyl) isocyanurate.
These polyisocyanates can be used alone, or in combination. Furthermore, the polyisocyanate is preferably used as a reaction precursor (referred to as "prepolymer" hereinafter) to be reacted with a curing agent described below.
The curing agent is suitably selected depending on the intended purpose without any limitation, with the proviso that it can react with the prepolymer. Examples of the same include m compound containing active hydrogen group.-Compound containing active hydrogen group-
An active hydrogen group contained in the active hydrogen group-containing compound is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, and a mercapto group. These can be used alone, or in combination.
The active hydrogen group-containing compound is suitably selected depending on the intended purpose without any limitation, but is preferably amine insofar as a urea bond can be formed.
The amine is appropriately selected depending on the intended purpose without any limitation, and examples thereof include diamine, trivalent or higher amine, amino alcohol, aminomercaptan, amino acid, and a blocked product thereof, wherein an amine group of any of the amines mentioned above is blocked.
The diamine is appropriately selected depending on the intended purpose without any limitation, and examples thereof include aromatic diamine, alicyclic diamine and aliphatic diamine.
The aromatic diamine is appropriately selected depending on the intended purpose without any limitation, and examples thereof include phenylene diamine, diethyltoluene diamine, and 4,4'-diaminodiphenyl methane. The alicyclic diamine is appropriately selected depending on the intended purpose without any limitation, and examples thereof include 4,4'-diamino-3,3'-dimethyldicyclohexyl methane, diaminocyclohexane, and isophorone diamine. The alicyclic diamine is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
The trivalent or higher amine is appropriately selected depending on the intended purpose without any limitation, and examples thereof include diethylene triamine, and triethylene tetraamine.
The amino alcohol is appropriately selected depending on the intended purpose without any limitation, and examples thereof include aminoethylmercaptan, and aminopropylmercaptan.
The amino acid is appropriately selected depending on the intended purpose without any limitation, and examples thereof include aminopropionic acid and aminocaproic acid.
The product blocked on the amine group is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a ketimine compound and an oxazoline compound, which are obtained by blocking the amino group with ketone (for example, acetone, methyl ethyl ketone, and methyl isobutyl ketone).
A molecular structure of a non-crystalline polyether resin A can be confirmed by a liquid or solid NMR, X-ray diffraction, GC/MS, LC/MS, or IR spectroscopy. For example, a simple method thereof includes a method for detecting a component that has no CH (flat outward folding) olefin-derived absorption beads at 965 ± 10 cm-1 and 990 ± 10 cm-1 in the absorption spectrum infrared (IR) as a non-crystalline polyether resin A.
An amount of a non-crystalline polyester resin A used as the prepolymer is appropriately selected depending on the intended purpose without any limitation, and the amount thereof is preferably 5 parts by mass to 25 parts by mass, more preferably 10 parts by mass to 20 parts by mass, relative to 100 parts by mass of toner. When the quantity of the same is less than 5 parts by mass, the low temperature fixing ability and the resistance to hot drift can be impaired. When the amount of the same is greater than 25 parts by mass, the stability in heat resistant storage may be impaired, or the brightness of an image obtained after fixation may be impaired. The amount thereof within the above-mentioned preferable range is preferable, as a resulting toner exceeds all in low temperature fixing ability, hot drift resistance and anti-blocking property.
The crystalline polyester resin preferably contains two or more polyester resins, and preferably contains an unmodified polyester resin in addition to the urea or urethane modified polyester resin. Unmodified polyester resin is a polyester resin obtained from polyhydric alcohol and polycarboxylic acid (eg polycarboxylic acid, polycarboxylic anhydride and polycarboxylic acid ester) or a derivative thereof, and is a polyester resin that is unmodified with an isocyanate compound or the like.
Examples of the polyhydric alcohol include diolExamples of the diol include: an alkylene oxide (C2C3) bisphenol A (average number of moles added: 1 to 10) adduct such as polyocypropylene(2,2)-2,2-bis(4 - hydroxyphenyl)propane; ethylene glycol; propylene glycol; hydrogenated bisphenol A; and a hydrogenated bisphenol A (C2-C3) alkylene oxide (average number of moles added: 1 to 10) adduct. These can be used alone or in combination. Examples of polycarboxylic acid include dicarboxylic acid.
Examples of the dicarboxylic acid include: adipic acid, phthalic acid, isophthalic acid, terephthalic acid; maleic acid; and succinic acid substituted with C1-C20 alkyl group or C2-C20 alkenyl group, such as dodecenyl succinic acid and octyl succinic acid. These can be used alone or in combination.
Furthermore, the unmodified polyester resin contains trivalent or higher carboxylic acid, trihydric or higher alcohol, or both at one end of the molecular chain of the resin for the purpose of setting an acid value and/or a hydroxyl value thereof.
Examples of trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid and acid anhydride thereof. Examples of trihydric or higher alcohol include pentaerythritol and trimethylol propane.
A molecular weight of an unmodified polyester resin is appropriately selected depending on the intended purpose without any limitation. When the molecular weight of the same is excessively low, the viscoelasticity of a resulting toner during fusing becomes high and thus the low temperature fixing ability of the toner may be impaired. Thus, the weight average molecular weight (Mw) of the unmodified polyester resin as measured by gel permeation chromatography (GPC) is preferably from 3,000 to 10,000, more preferably from 4,000 to 7,000. Furthermore, the number average molecular weight (Mn) thereof is preferably from 1,000 to 4,000, more preferably from 1,500 to 3,000. A preferably from 1.0 to 3.5.
An acid value of the unmodified polyester resin is appropriately selected depending on the intended purpose without any limitation, but the acid value thereof is preferably 1 mgKOH/g to 50 mgKOH/g, more preferably 5 mgKOH/g to 30 mgKOH/g. When the acid value of the same is 1 mgKOH/g or more, a resulting toner tends to be negatively charged, improves the affinity for the paper as fixed to the paper, and can improve its high temperature fixing ability. When its acid value is greater than 50 mgKOH/g, the charge stability of a resulting toner, especially the charge stability of the toner against fluctuating environmental conditions, may be impaired.
A hydroxyl value of the unmodified polyester resin is appropriately selected depending on the intended purpose without any limitation, and the hydroxyl value of the same is preferably 5 mgKOH/g or more.
The glass transition temperature (Tg) of the unmodified polyester resin is preferably 40°C to 70°C. When the glass transition temperature is lower than 40°C, the blocking resistance of a resulting toner and the resistance of it against stress such as agitation is impaired, and the anti-film property of the same may be impaired. When the glass transition temperature of the same is higher than 70oC, on the other hand, the deformation of a resulting toner by heat or pressure applied during fixing is insufficient, which can lead to the toner's insufficient low temperature fixing ability.
A molecular structure of the unmodified polyester resin can be confirmed by liquid or solid NMR, X-ray diffraction, GC/MS, LC/MS, or IR spectroscopy. For example, a simple method thereof includes a method to detect, as a non-crystalline resin, a component that has no absorption peaks derived from δCH (off-plane folding) of olefin at 965 ± 10 cm-1 and 990 ± 10 cm-1 in the infrared (IR) absorption spectrum.
An amount of the unmodified polyester resin is appropriately selected depending on the intended purpose without any limitation, but the amount thereof is preferably 50 parts by mass to 90 parts by mass, more preferably 60 parts by mass to 80 parts by mass with respect to 100 parts by mass of a toner. When the amount of the same is less than 50 parts by mass, the dispersability of the pigment or release agent in the toner is impaired, which can cause blurring or disturbance in a resulting image. When the amount thereof is greater than 90 parts by mass, the low temperature setting ability of a resulting toner may be impaired, since the amounts of crystalline polyester resin and modified polyester resin are small. The use of the modified polyester resin in an amount of the most preferable range mentioned above is advantageous because a resulting toner achieves both excellent image quality and low temperature fixing capability.
Furthermore, the toner of the present invention preferably contains a non-crystalline polyester A and a crystalline polyester B as a binder resin A. As for the non-crystalline polyester A, the non-crystalline polyether resin A mentioned above is used. <Crystal polyester resin A B>
Crystalline polyester resin A B preferably has a melting point of 50°C to 100°C, more preferably 60°C to 80°C. The viscosity of a crystalline polyester resin A B drops sharply at its melting point. When a resulting toner is stored at a temperature equal to or greater than the melting point of a crystalline polyester resin A B, the toner is aggregated and blocking occurs. Consequently, the melting point of a crystalline polyester resin A B is preferably a temperature higher than the temperature at which a resulting toner is stored or used. Specifically, the melting point of a crystalline polyester resin A B is preferably 50°C or higher. Furthermore, the melting point thereof is preferably 100°C or lower to obtain the low temperature setting ability of a resulting toner.
The melting point of a crystalline polyester resin A B can be determined as the peak melting temperature as measured by energy compensation differential scanning calorimetry specified in JISK-7121. Note that, there is a case where a crystalline resin A has a plurality of melting peaks. In this case, its maximum peak is determined as a melting point.
Crystalline polyester resin A B is preferably obtained by allowing a mixture of divalent or trivalent or higher unsaturated carboxylic acid containing an unsaturated double bond and divalent or trivalent or higher saturated carboxylic acid to react with dihydric or trihydric or higher alcohol through a condensation reaction . Such cross-linked crystalline polyester resin A is not particularly limited, and can be selected from commercial products, or can be suitably synthesized for use.
Examples of divalent unsaturated carboxylic acid include maleic acid, maleic anhydride, fumaric citraconic acid and itaconic acid.
Examples of divalent saturated carboxylic acid include: dibasic acid such as oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid , naphthalene-2,7-dicarboxylic acid, cyclohexane dicarboxylic acid, malonic acid, and mesaconic acid; and anhydride thereof and lower alkyl ester thereof.
Examples of trivalent or higher carboxylic acid include 1,2,4-benzene tricarboxylic acid, 1,2,5-benzene tricarboxylic acid, 1,2,4-naphthalene tricarboxylic acid, and anhydrides thereof, and lower alkyl esters thereof. These carboxylic acids can be used alone or in combination.
Examples of dihydric alcohol include bisphenol A, hydrogenated bisphenol A, ethylene oxide and/or bisphenol A propylene oxide adduct, 1,4-cyclohexanediol, 1,4-cyclohexane dimethanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and xylylene glycol.
Examples of trihydric or higher alcohols include glycerin, trimethylol ethane, trimethylol propane, and pentaerythritol. These alcohols can be used alone, or in combination.
For the purpose of controlling an acid value or hydroxyl value of a toner, a monovalent acid, such as acetic acid, and benzoic acid, or a monohydric alcohol, such as cyclohexanol, and benzyl alcohol, is also optionally used.
In the present invention, one or a plurality of polyester resin As containing the unsaturated double bond mentioned above is used as a crystalline polyester resin A B, but other non-crosslinked resin A can be added thereto. Non-crosslinked resin A can be appropriately selected from those known in the art.
Note that, a crystal core agent can be added, or a post-cure treatment, such as annealing, can be performed to increase a crystalline grade of a crystalline polyester resin A B, as long as an effect achievable of the present invention does not be harmed.
Crystalline polyester resin A B preferably contains C4-C12 linear unsaturated aliphatic dicarboxylic acid in an amount of 80% mol or greater with respect to the total acid components, and C2-C12 linear saturated aliphatic diol in an amount of 80% mol or higher with respect to the total alcohol components. Toner containing such crystalline polyester resin A B improves its crystallinity to thereby improve sharp melting characteristics, and demonstrates excellent low temperature fixing ability.-Fixing Aid Component-
The toner of the present invention preferably contains a fixing aid component. Fixing aid component present as a crystal domain in the toner in a non-compatible state before the toner is fixed. The setting aid component melts with the heat applied during setting, and becomes compatible with the binder resin A to be plasticized, therefore, the anti-blocking property and low temperature setting ability of a resulting toner can be improved. The setting aid component is suitably selected from one having a function of plasticizing a resin A, but is preferably one that can increase a 1st Tg and 2nd Tg difference of the toner, which will be described below. Examples of the fixing aid component include fatty acid ester, aliphatic amide, fatty acid, and aliphatic alcohol. However, the crystalline polyester resin A mentioned above in binder resin A thus has an excellent function of a setting aiding component, as well as a function of a binder resin A. The 1st Tg and 2nd Tg of the toner of the present invention will be explained below.
The toner is a sample, and is subjected to measurement using the DSC system mentioned below. In the present invention, the glass transition temperature determined from the first heat is determined as 1st Tg, and the glass transition temperature determined from the second heat is determined as 2nd Tg. <Method for Measuring Melting Point and Glass Transition Temperature (Tg)>
The melting point and glass transition temperature (Tg) of the present invention can be measured by means of a DSC system (a differential scanning calorimeter) (Q-200, manufactured by TA Instruments Japan Inc.).
Specifically, a melting point and glass transition temperature of a sample, such as a toner, can be measured as follows.-Pretreatment-
The toner of the present invention has 1st Tg from 25°C to 50°C, but the 1st Tg thereof varies easily due to the thermal history of the toner, or the morphological exchange of a binder resin A, which is, for example, an exchange of a state compatible with a third component, such as a fastening aid component. In order to erase the toner's thermal history, therefore, the toner is stored for 24 hours at 50°C. Within 24 hours from the end of storage, DSC is performed to calculate the 1st Tg. When performing the above mentioned pre-treatment, the thermal history of the toner is cleared, and in the 1st Tg a 1st Tg of the toner can be calculated.-Measurement-
For the measurement, first a sample (about 5.0 mg) is placed in an aluminum sample container, and the contained sample is placed in a holding unit, which is then placed in an electric oven. Subsequently, the sample is heated from -80°C to 150°C at the heating rate of 10°C/min in a nitrogen atmosphere (first heating). Thereafter, sample is cooled from 150°C to -80°C at a cooling rate of 10°C/min, followed by heating the sample to 150°C at a heating rate of 10°C/min (second heating ). For each of the first heat and the second heat, a DSC curve is measured by means of a differential scanning calorimeter (Q-200, manufactured by TA Instruments Japan Inc.).
When using an analysis program stored in the Q-200 system, a DSC curve from the first heat is selected from the DSC curve obtained to thereby determine the glass transition temperature of the sample from the first heat. Similarly, a DSC curve from the second heat is selected, and the sample's glass transition temperature from the second heat can be determined.
Furthermore, the DSC curve from the first heat is selected from the DSC curve using an analysis program in the Q-200 system, and the top temperature of the sample absorption peak from the first heat can be determined as a melting point of the sample. Similarly, the DSC curve from the second heat is selected, the top temperature of the sample absorption peak from the second heat can be determined as a melting point of the sample. The thermal characteristics of the toner of the present invention are explained.
As for the thermal characteristics of the toner, the obtained toner base particles preferably have a glass transition temperature Tg of 25°C to 45°C. When the Tg of the toner is lower than 25°C, the toner can cause blockage in a developing device, or film formation for a photoconductor. When the Tg of the toner is higher than 45°C, the toner may have poor fixing ability at low temperature.
In addition to the Tg mentioned above, the toner has a TMA compressive strain ratio (TMA%) of 10% or lower at 50°C under a condition having a relative humidity of 70%. TMA% thereof is preferably 7% or lower. A TMA% value greater than 10% means that the toner is easily deformed in case it is transported in summer, or transported by ship, and even if such toner has excellent static stability as measured by a penetration depth test, or excellent shelf stability under dry conditions, it has poor shelf stability under dynamic conditions including error factors, therefore, the anti-blocking property of it is poor. Considering transporting or storing it in a storage bin during the summer, the toner base particles are easily fused together, which imparts transportability and transfer property and forms defective images. By satisfying the above mentioned conditions of Tg and TMA%, the toner of the present invention can realize both heat-resistant storage stability (anti-blocking property) and low-temperature fixability. <TMA Compressive Deformation Rate (TMA%)>
The (TMA%) can be measured as follows. The particulate toner (5 mg) is formed into a tablet by means of a pellet press (manufactured by Shimadzu Corporation) having a diameter of 3 mm. The obtained tablet sample is provided to a thermomechanical measuring device (EXSTAR7000, manufactured by Hitachi High-Tech Science Corporation). The measurement is carried out with a compression mode heating from 0°C to 80°C at the heating rate of 2°C/min under the condition of 70%RH. The compressive force for the measurement is fixed at 100 mN. From the graph of the sample temperature and the compression displacement (strain rate), the compression displacement (strain rate) corresponding to 50°C is read, and this value is determined as TMA%. In the toner of the present invention , the content of crystalline polyester resin A B in a binder resin A is preferably 3% by mass to 20% by mass. When the content of a crystalline polyester resin A B is within the range mentioned above, the resulting toner is not melted in a storage environment, or by stirring in a developing device, and its viscoelasticity drops sharply over a certain temperature range . Consequently, both the low temperature fixing capability and the anti-blocking property can be realized. When the above-mentioned content is less than 3% by mass, the low temperature fixing capacity is not obtained and the desirable fixing capacity cannot be achieved. When the above-mentioned content is greater than 20% by mass, on the other hand, the toner has insufficient anti-blocking property, and thus toner aggregations are formed inside an imaging apparatus.
In order to improve the anti-blocking property and the low temperature setting ability, a difference between the 1st Tg and the 2nd Tg of the toner of the present invention is preferably large, more preferably 10°C or greater.
Furthermore, the glass transition temperature (2° Tg’) of a THF-insoluble toner component of the present invention, which is extracted from the toner, such as by Soxhlet extraction, is preferably -40°C to 30°C. Furthermore, the THF-insoluble component preferably has the elastic storage modulus G’ of 106 to 108 at 40°C, and the elastic storage modulus G’ of 105 to 107 at 100°C.
The toner of the present invention contains polyester resin A, which has a crosslinking structure having a rubber elasticity, and therefore, the toner can obtain anti-blocking property and anti-film-forming property, having low glass transition temperature (1a Tg) . Polyester resin A, which demonstrates the elasticity of rubber to toner, is preferably cross-linked and polymerized to have a high molecular weight to the level that it is insoluble in a solvent such as THF.
When the 2nd Tg thereof is lower than -40°C, it is difficult to prevent deformation of a resulting toner in the storage temperature range, even when crosslinks in the temperature range are formed, which can lead to an anti-blocking property and anti-film properties of unwanted toner. When the 2nd Tg of the same is higher than 30°C, the toner does not melt sufficiently in the fixing temperature range, leading to poor fixing ability at low temperature.
When the elastic storage modulus G’ of the THF-insoluble component at 40°C is less than 106, it is storage temperature, which can lead to poor anti-blocking property and anti-film forming property. When the elastic storage modulus G’ of the THF-insoluble component at 40°C is greater than 108, the toner does not melt sufficiently in the temperature range, leading to poor holding capacity at low temperature.
When the elastic modulus of storage G' of the THF-insoluble component at 100°C is less than 105, the elasticity of the toner is insufficient in the fixing temperature range, which can lead to poor resistance to the toner's hot drift during drying. fixation. When the elastic storage modulus G' of the THF-insoluble component at 100°C is greater than 107, toner deformation is insufficient in the fixing temperature range, which can lead to insufficient low temperature fixing capacity, and to a low brightness of an image. <Loss Tangent tanδ>
The loss tangent tanδ (i.e. a ratio of G"/G' of elastic modulus of loss G" to store elastic modulus G') preferably has the maximum value in the range of 20°C to 70°C, more preferably in the range of 40°C to 60oC.
When a maximum tanδ loss tangent value is less than 20oC, the toner will become easier to deform in response to external stress in its storage environment, and may be insufficient in heat resistant storage stability. When the maximum tanδ loss tangent value is more than 70oC, the toner will deform insufficiently in response to external stress when fixing, and may be insufficient in low temperature fixing ability. <Method of Measurement of Elastic Storage Modulus G’ and Loss Tangent tanδ>
The elastic storage modulus G' and the loss tangent tanδ of the toner and the THF-insoluble component and the THF-soluble component of the toner can be measured by means of a viscoelastometer can be measured by means of a dynamic viscoelastometer (for example, ARES of TA Instruments Japan Inc.). The frequency used for measurement is 1 Hz.
Specifically, the sample is formed into a pellet having a diameter of 8 mm, and a thickness of 1 mm to 2 mm, and the pellet sample is fixed to a parallel plate having a diameter of 8 mm. Subsequently, the sample is adhered to the parallel plate at a temperature higher than the 1st Tg of the toner for 0°C to 5°C, and the temperature is held for 60 minutes. Then, the sample is cooled to 60°C keeping the load applied to the sample above the plate constant and the sample is held for 60 minutes at 60°C.
As for the measurement, the sample is heated to 200°C at the heating rate of 2.0°C/min with 0.1% deformation (in a deformation control mode) to thereby measure the elastic modulus storage G' of the sample.
As for the colorant, any of the dyes and pigments used for a colorant for a toner can be used appropriately. Specific examples thereof include carbon black, iron black, Sudan Black SM, Fast Yellow G, yellow benzidine, Solvent Yellow (21, 77, 114, etc.), Pigment Yellow (12, 14, 17, 83, etc.) , India Fast Orange, Irgazine Red, p-nitroaniline red, toluidine red, Solvent Red (17, 49, 128, 5, 13, 22, 482, etc.), scattered red, Carmine FB, Pigment Orange R, Lake Red 2G , Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Solvent Blue (25, 94, 60, 153, etc.), Pigment Blue, Bright Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orasol Brown B , and Oil Pink OP. These can be used alone, or in combination.
Furthermore, magnetic powder (eg, ferromagnetic metal powder such as iron, cobalt and nickel, and a compound such as magnetite, hematite and ferrite) also serving as a colorant may optionally be contained. preferably 0.1 parts by mass to 40 parts by mass, more preferably 0.5 parts by mass to 10 parts by mass, relative to 100 parts by mass of a binder resin A. Note that, in the case where a magnetic powder is used, the amount of colorant is preferably 20 parts by mass to 150 parts by mass, more preferably 40 parts by mass to 120 parts by mass.
The release agent is preferably a release agent having a softening point of 50°C to 170°C. Examples thereof include polyolefin wax, natural wax (eg carnauba wax, montan wax, paraffin wax and rice wax), C30-C50 aliphatic alcohol (eg triacontanol), C30-C50 fatty acid (eg , triacontane carboxylic acid), and a mixture thereof. Except those listed above, usable as the release agent are polymethylene (eg Fischer-Tropsch wax, such as Sasol wax), fatty acid metal salt (eg calcium stearate), and fatty acid ester (eg example, beenyl behenate).
Examples of polyolefin wax include: an olefin (co)polymer (eg, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and a mixture thereof) [including olefin compounds obtained by (co)polymerization, and thermal degradation polyolefin]; (co)polymer of olefin oxide with oxygen and/or ozone; a maleic acid modified product [e.g. maleic acid modified products and a derivative thereof (e.g. maleic anhydride, monomethyl maleate, monobutyl maleate and dimethyl maleate)] of olefin (co)polymer; and a copolymer of olefin, unsaturated carboxylic acid [(meth)acrylic acid, itaconic acid, and maleic anhydride], and/or unsaturated carboxylic acid alkyl ester [e.g., alkyl (meth)acrylate (C1-C18 alkyl), and alkyl maleate (C1-C18 alkyl)].
In the toner of the present invention, except for the materials listed above, additives such as a charge control agent and a flow improving agent may optionally be contained.
Examples of the charge control agent include a nigrosine dye, a dye based on triphenyl methane having tertiary amine in a side chain thereof, quaternary ammonium salt, a polyamine resin A, imidazole derivative, polymer containing salt group of quaternary ammonium, a metal-containing azo dye, a copper phthalocyanine dye, salicylic acid metal salt, a benzylic acid boron complex, sulfonic acid group-containing polymer, fluorine-containing polymer, halogen-substituted aromatic ring-containing polymer , a metal complex of an alkyl derivative of salicylic acid and cetyltrimethyl ammonium bromide.
Examples of the flux improving agent include colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, quartz sand , clay, mica, wollastonite, diatomaceous earth, chromic oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate and barium carbonate.
As for the mixing ratio of each toner component, the binder resin A is preferably 30% by mass to 97% by mass, more preferably 40% by mass to 95% by mass, and even more preferably 45% by mass to 92% in large scale; the colorant is preferably 0.05% by mass to 60% by mass, more preferably 0.1% by mass to 55% by mass, and even more preferably 0.5% by mass to 50% by mass; among the additives, the release agent is preferably 0% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, and even more preferably 1% by mass to 10% by mass; the charge control agent is preferably 0% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, and even more preferably 0.5% by mass to 7.5% by mass; and the flow-enhancing agent is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, and even more preferably 0.1% by mass to 4% by mass. Furthermore, a total amount of the additives is preferably 3% by mass to 70% by mass, more preferably 4% by mass to 58% by mass, and even more preferably 5% by mass to 50% by mass.
A toner having excellent charge capacity can be easily obtained when its components are mixed in the ranges mentioned above.
As for the toner production method mentioned above, a conventional method such as a kneading spray method, a suspension polymerization method, an emulsification polymerization aggregation method and a phase inversion method can be used.
The kneading spray method is a method containing, after melt kneading a binder resin A together with a colorant etc., finally spraying the kneaded product, and grading to thereby produce a toner. For example, after the dry mix components constituting a unique toner of a flow improving agent, the resulting mix is melt kneaded, the kneaded product is coarsely pulverized, the pulverized product is finally finely pulverized by a mill sprayer. jet or fine particle-like, and then the resulting particles are classified into particles having the volume average particle diameter of about 5 µm to about 20 µm. Finally, the resultant is mixed with a flow-enhancing agent to produce a toner. Note that the volume mean particle diameter can be measured using a Coulter Counter [eg, product name: Multisizer III (manufactured by Beckman Coulter, Inc.)].
The suspension polymerization method is a method containing the addition of a monomer, an onset of polymerization, a colorant, a release agent, etc., to a phase containing an agitated dispersion stabilizer, to form oil droplets, and then heat to carry out a polymerization reaction of the oil droplets to thereby obtain toner particles.
The emulsification polymerization aggregation method is a method, for example, using a polyester resin A as a binder resin A, in which the particles obtained by removing a solvent, after emulsifying and dispersing in an aqueous phase, are aggregated with elements disperses formed by dispersing a colorant, a release agent (wax), etc., into the aqueous phase, and the resultant is heated and melted to thereby produce toner particles.
The emulsification phase inversion method is a method containing, after dissolving or dispersing the components constituting a unique toner of a flow-enhancing agent in an organic solvent, adding water or the like to the resulting solution or dispersion liquid to forming an emulsion, followed by separation and classification to thereby produce a toner. Furthermore, a toner can be produced by a method using organic particles disclosed in JP-A no 2002-284881. The volume average particle diameter of the toner is preferably 3 µm to 15 µm. <<Separation Unit for Constitutional Toner Components>>
An example of a separation unit for each component to analyze toner is explained.
First, 1 g of a toner is added to 100 ml of tetrahydrofuran (THF), and the resultant is stirred for 30 minutes at 25°C to thereby obtain a solution in which the soluble components are dissolved. The solution is filtered through a membrane filter having an opening size of 0.2 µm, to thereby obtain a THF-soluble component is dissolved in THF to thereby prepare a sample for GPC. The sample is provided with a GPC used for a measurement of a molecular weight of each resin A mentioned above.
However, a fraction collector is provided with a GPC eluate output, and the eluate is fractionated by predetermined counting to thereby obtain an eluate by 5% based on the area ratio from the start of the elution curve (increase on the curve). Then, as for each eluate of the fraction, 30 g of the sample is dissolved in 1 ml of deuterated chloroform, to which 0.05% by volume of tetramethylsilane (TMS) is added as a standard substance. The resulting solution is poured into a glass tube for measuring NMR, having a diameter of 5 mm, and the multiplication was performed 128 times by means of a nuclear magnetic resonance apparatus (JNM-AL400, manufactured by JEOL Ltd.) à temperature from 23°C to 25°C to thereby obtain a spectrum.
Monomeric compositions, constitutional relations, etc. of a non-crystalline polyether resin A and a crystalline polyester resin A contained in the toner can be determined from a peak integration ratio of the obtained spectrum.
For example, the peak assignment is performed as follows, and a constitutional monomer ratio is determined from the integration ratio. The peak assignment is, for example, as follows: • the proximity of 8.25 ppm: originated from a benzene ring of trimellitic acid (for a hydrogen atom) • the proximity of 8.07 ppm to 8.10 ppm: originated from a benzene ring of terephthalic acid (for 4 hydrogen atoms)• the proximity of 7.1 ppm to 7.25 ppm: originated from a benzene ring of bisphenol A (for 4 hydrogen atoms)• the proximity of 6.8 ppm: originated from a benzene ring of bisphenol A (for 4 hydrogen atoms) and originated from a fumaric acid double bond (for 2 hydrogen atoms) • the proximity of 5.2 ppm to 5.4 ppm: originated from propylene oxide adduct methine of bisphenol A (for 1 hydrogen atom)• the proximity of 3.7 ppm to 4.7 ppm: originated from propylene oxide adduct methylene of bisphenol A (for 2 hydrogen atoms) hydrogen), and originated from methylene of ethylene oxide adduct of bisphenol A (for 4 hydrogen atoms) • the proximity of 1.6 ppm: originated from a methyl group of bisf enol A (for 6 hydrogen atoms)
From these results, for example, an extract collected from a fraction in which non-crystalline polyether resin A occupies 90% by mass or more, treated as a non-crystalline polyether resin A. Furthermore, an extract collected from the fraction in which crystalline polyester resin A B occupies 90% by mass or more is treated as a crystalline polyester resin A B.- Extraction of Insoluble Component in THF by Soxhlet Extraction -A extraction of the THF-insoluble component from the toner of the present invention is carried out as follows.
The toner (1 g) is refluxed for 12 hours with 100 g of THF to thereby be separated into a component insoluble in THF and a component soluble in THF. The solids obtained by removing THF from the THF-soluble component, and the solids obtained by removing THF from the THF-insoluble component are dried for 20 hours at 40°C under atmospheric pressure, followed by vacuum drying of the solids for 20 hours at 23°C. The resultants are used respectively as a THF-soluble component, and THF-insoluble component. (Developer) The developer of the present invention contains the toner of the present invention, and a carrier.
The toner is optionally mixed with carrier particles (eg iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with an A resin (eg an acrylic resin A and an A resin silicone)) and used as a developer for an electrical imaging.
Furthermore, instead of carrier particles, the toner can be abraded with a charge blade to cause friction to reveal an electrical latent image. Then, the developed electrical latent image is fixed onto a backing (eg, paper, and a polyester film) by a conventional hot cylinder fixation method.
The developer of the present invention can be suitably used for imaging in various conventional electrophotographic methods, such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. of developer]
The developer container configured to house the developer of the present invention is suitably chosen as examples thereof include a container having a container main body and a lid. The size, shape, structure and material of the developer container main body are selected appropriately depending on the intended purpose without any limitation. The shape of the main body of the developer container is, for example, preferably a cylinder, and particularly preferably a configuration of the main body of the container, wherein the recess (a convex-concave shape) is spirally formed in the inner circumference surface to, in this way, enabling the content, which is the developer, to move to the discharge outlet side by rotation of the main body of the container, and the part or the entire spiral section works as below. The material of the container is appropriately selected depending on the intended purpose without any limitation, but is preferably selected from materials which are excellent in dimensional accuracy over production. Examples thereof include a polyester resin A, a polyethylene resin A, a polypropylene resin A, a polystyrene resin A, a polyvinyl chloride resin A, polyacrylic acid, a polycarbonate resin A, an ABS resin A , and a polyacetal resin A. The developer container is easy to store and transport, excellent in handling, and can be used appropriately in the process cartridge or imaging apparatus mentioned below to supply a developer by detachably mounting the container. developer in it.(Image formation method)
The imaging method using the toner of the present invention preferably contains at least one electrostatic latent imaging step, a development step, a transfer step, and a fixation step, more preferably still contains a cleaning step, and may also contain a de-electrification step, a recycling step, and a control step, if necessary.
Furthermore, an imaging apparatus for use in the present invention preferably contains at least one electrostatic latent imaging support member, an electrostatic latent imaging unit, a developing unit, a transfer unit, and a unit. The fixing unit, more preferably further contains a cleaning unit, and may further contain a de-electrification unit, a recycling unit and a control unit, if necessary. The imaging method can be performed by the imaging apparatus. The latent electrostatic imaging step can be performed by the latent electrostatic forming unit, the development step can be performed by the imaging unit, the transfer step can be performed by the transfer unit, the fixation unit can be performed by the clamping unit, and other steps can be performed by other units. <Latent Electrostatic Imaging Step>
The electrostatic latent imaging step is forming an electrostatic latent image on an electrostatic latent image support member, such as a photoconductive insulator, and a photoconductor. The material, shape, structure, and size of the electrostatic latent image support member are appropriately selected from those known in the art without any limitation. The shape thereof is preferably a drum shape. Furthermore, examples of the photoconductor include inorganic photoconductor (eg, amorphous silicon, and selenium) and organic photoconductor (eg, polysilane, and phthalopolymethine). Among them, amorphous silicon is preferable in view of the long service life. Electrostatic latent image can be formed, for example, by uniformly charging the surface of the electrostatic latent image support member, and applying a clear image mode, and can be formed through the forming unit of the electrostatic latent image forming unit. The electrostatic latent imaging unit contains, for example, at least one charger configured to apply voltage to a surface of the electrostatic latent image support member to uniformly charge the surface, and an exposure unit configured to apply an imaging mode light to the surface of the electrostatic latent imaging support member.
The charger is not particularly limited, and examples of it include: conventional contact charging units equipped with an electrically or semiconductive conductive cylinder, brush, rubber film or sheet; and non-contact chargers utilizing corona discharge such as corotron and scorotron.
The exposure unit is not particularly limited, with the proviso that it is capable of applying clear image mode corresponding to an image to be formed, on the surface of the supporting member of the latent electrostatic image carried by the charger. Examples of the display unit include various display units, such as a reproducing optical display device, a lens rod array device, a laser optical display device, and a liquid crystal shutter optical device. Note that, the exposure unit may employ a black light system, where the exposure of the image type is carried out from the black side of the latent electrostatic image support member. <Revelation Step>
The developing step is developing a latent electrostatic image with the developer of the present invention to thereby form a toner image. The toner image (visible image) can be formed using the developer unit. The developing unit is not particularly limited, provided that it can perform the development using the developer of the present invention, and examples thereof include a unit, which houses the developer of the present invention therein, and contains at least one device developer capable of applying a toner to the electrostatic latent image in a contact or non-contact mode. The developer unit is preferably a developing device equipped with the developer container.
The developing device may employ either a dry developing system or a wet developing system, and may be a single color developing device or a multi color developing device. Examples thereof include an agitator-containing device configured to charge the developer of the present invention by the frictions of agitation, and a rotating magnetic cylinder. In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction from the stirring. Charged toner is retained on the surface of the rotating magnetic cylinder in the form of a brush to form a magnetic brush. The magnetic cylinder is provided adjacent to the electrostatic latent image support member, part of the toner forming the magnetic brush on the surface of the magnetic cylinder is moved to the surface of the electrostatic latent image support member by the force of electrical attraction. As a result, the electrostatic latent image is developed with toner to form a toner image on the surface of the electrostatic latent image support member. Note that the developer housed in the developing device is the developer of the present invention, which may be a one-component developer, or a two-component developer. <Transfer Step>
The transfer step is loading the latent electrostatic image support member, on which the toner image is formed, by means of a transfer charger to thereby transfer the toner image to a recording medium, and the transfer can be performed by means of the transfer unit. The transfer step preferably contains a first transfer step, which contains the transfer of the toner image onto an intermediate transfer member, and a second transfer step, which contains the transfer of the toner image, which is transferred over the transfer member. intermediate transfer, to a recording medium. The transfer step more preferably contains a first transfer step, which contains the transfer of toner images of each color, which are formed with a two or more color toner, or a multi-color toner, onto an intermediate transfer member. to form a composite toner image, and a second transfer step, which contains the transfer of the composite toner image formed on the intermediate transfer member onto a recording medium.
The transfer unit preferably contains a first transfer unit configured to transfer the toner image onto an intermediate transfer member to form a toner image configured to transfer the composite toner image formed on the intermediate transfer member to a recording medium . Note that the intermediate transfer member is not particularly limited, and examples thereof include an endless transfer belt. Furthermore, the transfer unit (first transfer unit, second transfer unit) preferably contains at least one transfer device configured to load the toner image formed on the electrostatic latent image support member to release the toner image to from the photoconductor to the recording medium side. Note that the transfer unit may have one, or two or more transfer devices.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer cylinder, a heat transfer cylinder, and an adhesion transfer member.
Note that the recording medium is properly selected from conventional recording media (recording paper) without any limitation. <Fixing Step>
The fixing step is fixing the transferred toner image onto the recording medium, and fixing can be performed by means of the fixing unit. Note that in the case where two or more colors of toner are used, fixing can be performed every time a formed toner image of each color is transferred onto the recording medium. Alternatively, fixation can be performed after full color toners are transferred to the recording medium in a laminated state. The clamping unit is not particularly limited, and any one of the conventional heating and pressurizing units can be used as the clamping unit. Examples of a heating and pressurizing unit include a combination of a hot cylinder and a compression cylinder, and a combination of a hot cylinder, a compression cylinder and an endless belt. The heating temperature for fixation is typically 80°C to 200°C. Note that if required, for example, a conventional optical fixation unit can be used together with or instead of the fixation unit. <De-electrification step>
The de-electrification step is applying a de-electrification bias to the latent electrostatic image support member to de-electrify the latter, and the de-electrification. The de-electrification unit is not particularly limited, as long as it is capable of applying a de-selection bias to the electrostatic latent image support member, and examples thereof include a de-selection lamp. <Cleaning Step>
The cleaning step is removing the toner remaining on the electrostatic latent image support member, and the cleaning step can be performed through the cleaning unit. The cleaning unit is not particularly limited, as long as it is capable of removing the toner remaining on the electrostatic latent image support member, and examples thereof include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic drum cleaner , a blade cleaner, a brush cleaner, and a weft cleaner. <Recycling Step>
The recycling step is recycling the toner, which was removed in a cleaning step, to the developer unit, and the recycling step can be carried out through the recycling unit. The recycling unit is not particularly limited, and examples of it include conventional transport units. <Control Step>
The control step is controlling each step, and the control step can be performed by the control unit. The control unit is not particularly limited as long as it can control the operations of each unit, and examples of it include devices such as a sequencer and a computer.
An example of the imaging apparatus for use in the present invention is illustrated in Figure 1. The imaging apparatus 100A is equipped with a photoconductor 10 serving as the latent electrostatic image support member, a charging device 20 serving as a loading unit, a display device serving as is a display unit (not shown), developing devices 45 (K, Y, M, C), each serving as the developing unit, an intermediate transfer member 50 , a cleaning device 60 serving as a cleaning unit, and a de-electrifying lamp 70 serving as a de-electrifying unit.
The intermediate transfer member 50 is an endless belt, and is designed to rotate in the direction indicated with an arrow by three cylinders 51 disposed within the intermediate transfer member 50 to support the intermediate transfer member 50. Part of the three cylinders 51 it also functions as a transfer bias cylinder capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50.
In the area surrounding the intermediate transfer member 50, the cleaning device 90 having a cleaning blade is provided, and the transfer cylinder 80 serving as the transfer unit capable of applying a transfer bias to transfer (secondary transfer) an image. of toner to the recording medium 95 is provided to face the intermediate transfer member 50.
In the area surrounding the intermediate transfer member 50, the corona charger 52, which is configured to apply a charge to the toner image on the intermediate transfer member 50, is provided in the area between the contact area of the photoconductor 10 and the member. intermediate transfer member 50, and intermediate transfer member contact area 50 and recording medium 95.
The development device 45 of each color, black(K), yellow (Y), magenta (M), and cyan (C), is equipped with a development container 42 (K, Y, M, C), a cylinder developer supply 43, and a developer cylinder 44.
In the image forming apparatus 100A, the charging roller 20 uniformly charges the photoconductor drum 10, followed by exposing the photoconductor drum in exposure imaging mode L by the exposure device (where shown) to thereby form a latent electrostatic image. Then, the latent electrostatic image formed on the photoconductor drum 10 is developed by supplying the developer from the developing device 45 to form a toner image. Thereafter, a transfer bias is applied from drum 51 to transfer the toner image onto the intermediate transfer member (first transfer). The toner image on the intermediate transfer member 50 is then provided with electrical charges from the corona charger 52, followed by being transferred onto the recording paper 95 (secondary transfer). Note that, the toner remaining on the photoconductor drum 10 is removed by the cleaning device 60, and the photoconductor drum 10 is de-electrified by a de-electrifying lamp 70.
Figure 2 illustrates another exemplary imaging apparatus of the present invention. An imaging apparatus 100B in Figure 2 is a tandem color imaging apparatus, and includes a main body of the copy device 150, a paper feed table 200, a scanner 300 and an automatic document feeder ( ADF) 400.
The main body of the copy device 150 is provided at its central portion with an intermediate transfer member in the form of an endless belt 50. The intermediate transfer member 50 can be rotated with being stretched by the support rollers 14, 15 and 16 in a direction indicated by the arrow.
The cleaning unit 17 configured to remove toner particles remaining on the intermediate transfer member 50 is disposed in a proximity to the support roller 15. Around the intermediate transfer member 50 stretched by the support rollers 14 and 15 a tandem developing device 120 wherein four imaging units 18 for yellow, cyan, magenta and black toners are arranged in a row along the direction of movement of the intermediate transfer member.
As illustrated in Figure 3, each of the imaging units 18 includes: a photoconductor drum 10; a charging cylinder 160 that uniformly charges the photoconductor drum 10; a developer device 70 which forms a toner image by developing the electrostatic latent image formed on the drum of photoconductor 10 with a black (K), yellow (Y), magenta (M) or cyan (C) developer; a transfer roller 62 which transfers the toner image onto intermediate transfer member 50; a cleaning device 60; and a deselection lamp 70.
In the imaging apparatus illustrated in Figure 2, an exposure device (not shown) is provided adjacent to a tandem developing device 120. The exposure device is configured to apply an exposure light onto the photoconductive drum 10 to, in this way, form a latent electrostatic image.
Furthermore, a secondary transfer device 22 is provided on the opposite side of the intermediate transfer member 50 to the side thereof where the tandem developing device 120 is provided. The secondary transfer device 22 is composed of a secondary transfer belt 24, which is an endless belt supported by a pair of rollers 23, and is designed so that the recording paper supported on the secondary transfer belt 24 and the intermediate transfer member 50 may be in contact with each other.
The clamping device 25 is provided adjacent to the secondary transfer device 22. The clamping device 25 contains a clamping strap 26, which is an endless belt, and a compression cylinder 27, which is provided to press against the clamping strap 26.
Furthermore, an inverter 28 configured to invert the paper and embossing is provided adjacent to the secondary transfer device 22 and the clamping device 25.
Next, the formation of a multi-color image (color copy) in image forming apparatus 100B is explained. First, a document is placed on a document table 130 of automatic document feeder (ADF) 400. Alternatively, automatic document feeder (ADF) 400 is opened, a document is fixed on a glass and contact 32 of scanner 300, and then the ADF 400 is closed. In the case where the document is placed on the ADF 400, once a start switch (not shown) is compressed, the document is transported over the contact glass 32, and then the scanner 300 is triggered to scan the document with a first car 33 equipped with a light source and a second car 34 equipped with a mirror. In the case where the document is placed on the contact glass 32, the scanner 300 is immediately activated in the same way as mentioned. During this scanning operation, light applied from a light source of the first carriage 33 is reflected onto the surface of the document, light reflected from the document is further reflected by a mirror of the second carriage 34, and passed through an image forming lens 35, which is then received by a read sensor 36. In this way, the color document (color image) is read, and black, yellow, magenta and cyan image information is obtained.
The latent electrostatic image of each color is formed on the photoconductor drum 10 by the display device based on the image information obtained from each color. Thereafter, the electrostatic latent image of each color is developed with the developer supplied from the developing device 120 for each color to thereby form a toner image of each color. Toner images formed from these colors are sequentially transferred (first transferred) to the intermediate transfer member 50, which is rotated by support rollers 14, 15, and 16, to thereby form a composite toner image on the transfer member intermediary.
At the feed table 200, one of the feed rollers 142 is selectively rotated to eject a sheet (recording paper) from multiple feeder cassettes 144 of a paper bank 143, the ejected sheets are separated one by one by a roller. sheets 145 to send a feed path 146, and then are transported by a transport roller 147 into the feeder path 148 within the apparatus main body 150. The sheet transported on the feeder path 148 is then tapped against a roller. from record 49 to stop. Alternatively, sheets (recording paper) on a manual feed tray 54 are ejected, separated one by one by a separator roller 58 to guide into a lane of the manual feeder 53, and then tapped against the recording roller 49 to stop. Note that the recording cylinder 49 is generally grounded at the time of use, but it can be skewed to remove paper dust from the recording paper.
Thereafter, the recording cylinder 49 is rotated simultaneously with the movement of the composite toner image superimposed on the intermediate transfer member 50 to send a recording paper between the intermediate transfer member 50 and the secondary transfer device 22 to thereby transfer the composite toner image onto the recording paper (secondary transfer).
The recording paper onto which the composite toner image is transferred is conveyed by a secondary transfer device 22 to send to the holder 25. In the holder 25, the composite toner image is heated and pressurized by the belt. clamp 26 and the pinch roller thereby fix the composite toner image onto the recording paper. Thereafter, the recording paper is switched to its direction of travel by a CRAW switch 55, ejected by an eject cylinder 56, and then stacked onto an output tray 57. Alternatively, the recording paper is switched in its direction of path by CRAW switch 55, reversed by inverter 28 to send to a transfer position to thereby record an image on the black side thereof. Then, the recording paper is ejected from the eject cylinder 56, and stacked on the output tray 57.
Note that, the toner remains on the intermediate transfer member 50 after the composite toner image is transferred and is removed by the cleaning device 17. (Process Cartridge) The process cartridge of the present invention is designed so that it is assembled from detachable mode in various imaging apparatus, and contains at least one electrostatic latent image support member configured to support the electrostatic latent image thereon, and a developer unit configured to reveal the electrostatic latent image on the support member of the latent electrostatic imaging with the developer of the present invention to form a toner image. Note that the process cartridge of the present invention may contain further units if necessary.
The developer unit contains at least one developer container configured to house the developer of the present invention therein, and a developer support member configured to support the developer housed in the developer container and carry the developer. Note that the developer unit may further contain an adjustment member configured to adjust a thickness of the developer originating from the developer support member. Figure 4 illustrates an example of the process cartridge of the present invention.
Process cartridge 110 contains a photoconductor drum 10, a corona charger 52, a developing device 40, a transfer roller 80, and a cleaning device 90. EXAMPLES
The present invention will be specifically explained by way of Examples and Comparative Examples below, but the examples are not to be interpreted to limit the scope of the present invention. Note that, “part(s)” and “%” in the description below are all bulk basis.
The toners for the examples and comparative examples were produced in the following ways. <Toner Production> -Synthesis of the Cetimine Compound -
A reaction vessel, equipped with a stir bar and a thermometer, was charged with 170 parts of isophorone diamine, and 75 parts of methyl ethyl ketone, and the resulting mixture allowed to react for 5 hours at 50°C to thereby get the ketimine compound. The ketimine compound had an amine value of 418.-Master Batch Preparation (MB)-
At 1,200 parts of water, 540 parts of carbon black (Printex35, manufactured by Evonik Degussa Japan Co., Ltd.) [DBP oil absorption value = 42 ml/100mg, pH = 9.5], and 1,200 parts of non-crystalline polyether resin A A, and the resulting mixture was blended by HENSCHEL MIXER (manufactured by Nippon Cole & Engineering Co., Ltd.). The resulting mixture was kneaded by a two-roll mill for 30 minutes at 150°C, followed by rolling and cooled. Then the resultant was pulverized by a sprayer to, in this way, obtain the master batch.-Production of Liquid Pigment-Wax Dispersion-
A vessel equipped with a stir bar and a thermoset was loaded with 220 parts crystalline polyester resin A B containing unsaturated double bond, 50 parts paraffin wax (HNP-9, manufactured by NIPPON SEIRO CO., LTD., wax based in hydrocarbon, melting point: 75°C, SP value: 8.8) as a release agent, 22 parts of CCA (E-84 salicylic acid metal complex, manufactured by Orient Chemical Industries, Ltd.), and 947 parts of ethyl acetate, and the resulting mixture was heated to 80°C with stirring, the temperature of which was maintained at 80°C for 5 hours, followed by cooling to 30°C for 1 hour. Subsequently, 500 parts of master batch and 500 parts of ethyl acetate were added to the vessel, and the resulting mixture was mixed for 1 hour to thereby obtain the crude material solution.
The raw material solution (1,324 parts) was transferred into a vessel, and dispersed through a bead mill (ULTRA VISCOMILL, manufactured by AIMEX CO., Ltd.) under the conditions: a net feed rate of 1 kg/h, circumferential disc speed 6 m/s, 0.5 mm zirconia beads packed at 80% by volume, and 3 passes. Subsequently, 1042.3 parts of an ethyl acetate A solution of 65% non-crystalline polyether resin A A was added thereto, and the resultant was passed through the bead mill once under the same conditions as above for, in this way to obtain the liquid pigment-wax dispersion. The solids content (130°C, 30 min) of the liquid pigment-wax dispersion was 50%.-Preparation of the Oil Phase -
A vessel was loaded with 664 parts of liquid pigment-wax dispersion, 80 parts of prepolymer, and 4.6 parts of ketimine compound, and the resulting mixture was mixed by means of a Homomixer (manufactured by PRIMIX Corporation) at 5,000 rpm for 1 minute to thereby obtain the oil phase. In the present document, the prepolymer was a 1-1 polyester A resin A containing a reactive group described later.-Organic Particle Emulsion Synthesis (Liquid Particle Dispersion) -
A vessel equipped with a stir bar and thermometer was charged with 683 parts of water, 11 parts of methacrylic acid-ethylene oxide adduct sulfuric acid ester sodium salt (ELEMINOL RS-30, manufactured by Sanyo Chemical Industries , Ltd.), 138 parts of styrene, 138 parts of methacrylic acid, and 1 part of ammonium persulfate, and the resulting mixture was stirred for 15 minutes at 400 rpm to thereby obtain a white emulsion. The obtained emulsion was heated until the temperature of the internal system reached 75°C, and allowed to react for 5 hours. To this, 30 parts of a 1% aqueous ammonium persulfate solution was added and the resulting mixture was aged for 5 hours at 75°C to thereby obtain an aqueous liquid dispersion of a vinyl-based resin A (styrene -methacrylic acid -sulfuric acid ester sodium salt of methacrylic acid-ethylene oxide copolymer adduct), ie, liquid pigment dispersion. The volume average particle diameter of the liquid pigment dispersion as measured by LA-920 (manufactured by HORIBA, Ltd.) was 0.14 µm. Part of the liquid pigment dispersion was dried to separate a resin component A.-Preparation of the Aqueous Phase -
Water (990 parts), 83 parts of liquid pigment dispersion, 37 parts of an aqueous solution of 48.5% sodium dodecyldiphenyl ether disulfonate (ELEMINOL MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate love mixed together and agitated to thereby obtain a milky white fluid, which has been used as an aqueous phase.- Emulsification and Solvent Removal -
To the vessel into which the oil phase was charged, 1200 parts of the aqueous phase were added, and the resulting mixture was mixed by means of TK Homomixer at 13,000 rpm for 20 minutes to thereby obtain an emulsified suspension.
A vessel equipped with an agitator and a thermometer was charged with the emulsified suspension, and the solvent was removed therefrom at 30°C for 8 hours.- Unsaturated Group Reaction Process-
To the suspension obtained from the solvent which was removed, an amount of catalyst from a water-soluble radical polymerization initiator (V-44, manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the resultant was aged for 5 hours at 50°C, to carry out a reaction with the unsaturated double bonds of crystalline polyester resin A B to thereby obtain the dispersion suspension.-Washing and Drying -
After filtering 100 parts of the suspension, subjected to the following steps (1) to (5). (1): To the filter cake, 100 parts by mass of ion exchange water were added, and the mixture was mixed (at 12,000 rpm for 10 minutes) by the TK Homomixer, followed by filtration of the mixture. (2): To the cake of filtration obtained in (1), 100 parts by mass of a 10% by mass aqueous solution of sodium hydroxide were added, and the mixture was mixed (at 12,000 rpm for 30 minutes) by the TK Homomixer, followed by filtration of the mixture. under reduced pressure. (3): To the filter cake obtained in (2), 100 parts by mass of 10% by mass hydrochloric acid were added, and the mixture was mixed (at 12,000 rpm for 10 minutes) by the TK Homomixer , followed by filtration of the mixture. (4): To the filter cake obtained in (3), 300 parts by mass of ion exchange water were added, and the mixture was mixed (at 12,000 rpm for 10 minutes) by the TK Homomixer, followed by filtration of the mixture. The series of operations from (1) to (4) were carried out twice to thereby obtain the filter cake. (5): The filter cake (4) was dried with a circulating air dryer for 48 hours at 45°C, and then passed through a sieve with a mesh size of 75 µm to thereby obtain a toner.(SYNTHESIS EXAMPLE 1)-Synthesis of Non-Linear Polyester A-1-1 Resin A containing reactive group-
A reaction vessel equipped with a cooling tube, an agitator, and a nitrogen inlet tube was charged with a mixture containing 3-methyl-1,5-pentanediol and trimethylol propane at a molar ratio of 97:3 (components of alcohol), and adipic acid (an acid component) in amounts satisfying OH:COOH = 1.1:1, together with titanium tetraisopropoxide (300 ppm relative to resin component A). Thereafter, the mixture was heated to 200°C for about 4 hours, followed by heating to 230°C for 2 hours, and the mixture was allowed to react until the effluent ran off. Thereafter, the resultant was further allowed to react for 5 hours under the reduced pressure of 10 mmHg to 15 mmHg to thereby obtain the intermediate polyester. Then, a reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with the intermediate polyester and isophorone diisocyanate at a molar ratio of 2.1:1, and the mixture was diluted with 48% ethyl acetate by mass. Thereafter, the resultant was allowed to react for 5 hours at 100°C to thereby obtain the non-linear A-1-1 polyester resin A containing reactive group. Nonlinear A-1-1 polyester resin A containing the reactive group had a number average molecular weight (Mn) of 3800, weight average molecular weight (Mw) of 17,500, and Tg of -50°C.(SYNTHESIS EXAMPLE 2)-Synthesis of nonlinear A-1-2 polyester resin A containing reactive group-
A reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with a mixture containing 3-methyl-1,5-pentanediol, an ethylene oxide adduct of bisphenol A (2 mol), and trimethylol propane at a molar ratio of 20:77:3 (alcohol components), and the mixture containing adipic acid and terephthalic acid at a molar ratio of 50:50 (acid components) in amounts that satisfied OH:COOH = 1 .1:1 together with titanium tetraisopropoxide (300 ppm relative to resin component A). Thereafter, the mixture was heated to 200°C for about 4 hours, followed by heating to 230°C for 2 hours, and the mixture was allowed to react until the effluent ran off. Thereafter, the resultant was further allowed to react for 5 hours under the reduced pressure of 10 mmHg to 15 mmHg to thereby obtain an intermediate polyester. Then, a reaction vessel equipped with a cooling tube, an agitator, and a nitrogen inlet tube was charged with the intermediate polyester and isophorone diisocyanate at a molar ratio of 2.1:1, and the mixture was diluted. with 48% ethyl acetate by mass. Thereafter, the resultant was allowed to react for 5 hours at 100°C to thereby obtain the non-linear A-1-2 polyester resin A containing reactive group. Nonlinear A-1-2 polyester resin A containing reactive group had a number average molecular weight (Mn) of 4,200, weight average molecular weight (Mw) of 18,900, and Tg of 31°C. (SYNTHESIS EXAMPLE 3) -Synthesis of non-linear polyester A-1-3 resin A containing reactive group-
A reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with a mixture containing 3-methyl-1,5-pentanediol and trimethylol propane at a molar ratio of 97:3 (component and alcohol) , and a mixture containing adipic acid and terephthalic acid at a molar ratio of 50:50 (acid components) in which amounts satisfying OH:COOH = 1.1:1, together with titanium tetraisopropoxide (300 ppm with respect to the component of resin A). Thereafter, the mixture was heated at 200°C for about 4 hours, followed by heating at 230°C for 2 hours, and the mixture was allowed to react until the effluent ran off. Thereafter, the resultant was further allowed to react for 5 hours under the reduced pressure of 10 mmHg to 15 mmHg to thereby obtain the intermediate polyester. Then, a reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with the intermediate polyester and isophorone diisocyanate at a molar ratio of 2.1:1, and the mixture was diluted with 48% ethyl acetate by mass. Thereafter, the resultant was allowed to react for 5 hours at 100°C to thereby obtain non-linear polyether resin A A-1-3 containing reactive group. Nonlinear polyether A-1-3 resin A containing reactive group had a number average molecular weight (Mn) of 5200, a weight average molecular weight (Mw) of 32,900, and Tg of -30°C. (SYNTHESIS EXAMPLE 4)-Synthesis of A-1-4 polyether resin A containing reactive group-
A reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with a mixture containing 3-methyl-1,5-pentanediol and trimethylol propane at a molar ratio of 96:4 (alcohol components ), and a mixture containing adipic acid and terephthalic acid at a molar ratio of 50:50 (acid components) in amounts that satisfy OH:COOH = 1.1:1, together with titanium tetraisopropoxide (300 ppm with respect to the component of resin A). Thereafter, the mixture was heated to 200°C for about 4 hours, followed by heating to 230°C for 2 hours, and the mixture was allowed to react until the effluent ran off. Thereafter, the resultant was further left to react for 5 hours under the reduced pressure of 10 mmHg to 15 mmHg to thereby obtain the intermediate polyester. Then, a reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with the intermediate polyester and isophorone diisocyanate at a molar ratio of 2.1:1, and the mixture was diluted with 48% ethyl acetate by mass. Thereafter, the resultant was allowed to react for 5 hours at 100°C to thereby obtain non-linear polyether A-1-4 resin A containing reactive group. Nonlinear polyether A-1-4 resin A containing reactive group had a number average molecular weight (Mn) of 5600, weight average molecular weight (Mw) of 42,000, and Tg of -27°C.(SYNTHESIS EXAMPLE 5 )-Synthesis of non-linear polyether A-1-5 resin A containing reactive group-
A reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with a mixture containing 3-methyl-1,5-pentanediol and trimethylol propane at a molar ratio of 98:2 (alcohol components ), and the mixture containing adipic acid and tephthalic acid at a molar ratio of 50:50 (acid components) in amounts that satisfied OH:COOH = 1.1:1, together with titanium tetraisopropoxide (300 ppm with respect to the component of resin A). Thereafter, the mixture was heated to 200°C for about 4 hours, followed by heating to 230°C for 2 hours, and the mixture allowed to react until the effluent ran off. Thereafter, the resultant was further allowed to react for 5 hours under the reduced pressure of 10 mmHg to 15 mmHg to thereby obtain the intermediate polyester. Then, a reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with the intermediate polyester and isophorone diisocyanate at a molar ratio of 1.9:1, and the mixture was diluted with 48% ethyl acetate by mass. Thereafter, the resultant was allowed to react for 5 hours at 100°C to thereby obtain a non-linear polyether A-1-5 resin A containing reactive group. Nonlinear A-1-5 polyester resin A containing reactive group had the number average molecular weight (Mn) of 3200, weight average molecular weight (Mw) of 15,000, and Tg of -35°C. (SYNTHESIS EXAMPLE 6) -Synthesis of non-linear polyester A-1-6 resin A containing reactive group-
A reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with a mixture containing 3-methyl-1,5-pentanediol, an ethylene oxide adduct of bisphenol A (2 mol), and trimethylol propane at a molar ratio of 27:70:3 (alcohol components), and a mixture containing adipic acid and terephthalic acid at a molar ratio of 50:50 (acid components) in amounts that satisfied OH:COOH = 1 .1:1 together with titanium tetraisopropoxide (300 ppm relative to resin component A). Thereafter, the mixture was heated to 200°C for about 4 hours, followed by heating to 230°C for 2 hours, and the mixture allowed to react until the effluent ran off. Thereafter, the resultant was further allowed to react for 5 hours under the reduced pressure of 10 mmHg to 15 mmHg to thereby obtain an intermediate polyester. Then, a reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with the intermediate polyester and isophorone diisocyanate at a molar ratio of 2.1:1, and the mixture was diluted with acetate. ethyl a48% by mass. Thereafter, the resultant was allowed to react for 5 hours at 100°C to thereby obtain the non-linear A-1-6 polyester resin A containing reactive group. Nonlinear polyether A-1-6 resin A containing reactive group had a number average molecular weight (Mn) of 4,500, weight average molecular weight (Mw) of 19,000, and Tg of 29°C. (SYNTHESIS EXAMPLE 7) -Synthesis of non-linear polyether A-1-7 resin A containing reactive group-
A reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with a mixture containing 3-methyl-1,5-pentanediol and trimethylol propane at a molar ratio of 97:3 (alcohol components ), and a mixture containing adipic acid and terephthalic acid at a molar ratio of 70:30 (acid components) in amounts that satisfied OH:COOH = 1.1:1, together with titanium tetraisopropoxide (300 ppm with respect to the component of resin A). Thereafter, the mixture was heated to 200°C for about 4 hours, followed by heating to 230°C for 2 hours, and the mixture allowed to react until the effluent ran off. Thereafter, the resultant was further allowed to react for 5 hours under the reduced pressure of 10 mmHg to 15 mmHg to thereby obtain an intermediate polyester. Then, a reaction vessel equipped with a cooling tube, an agitator and a nitrogen inlet tube was charged with the intermediate polyester and isophorone diisocyanate at a molar ratio of 2.1:1, and the mixture was diluted with 48% ethyl acetate by mass. Thereafter, the resultant was allowed to react for 5 hours at 100°C to thereby obtain a non-linear polyether A-1-7 resin A containing reactive group. Nonlinear polyether A-1-7 resin A containing reactive group has a number average molecular weight (Mn) of 4,300, weight average molecular weight (Mw) of 18,500, and Tg of -40°C. (SYNTHESIS EXAMPLE 8) - Synthesis of Polyester Resin A A-2-1-
A 5-L four-neck flask equipped with a nitrogen inlet tube, a condenser, an agitator and a thermocouple was charged with a mixture containing a bisphenol A ethylene oxide adduct (2 mol) and a propylene oxide adduct of bisphenol A (3 mol) at a molar ratio of 85:15 (alcohol components), and a mixture containing isophthalic acid and adipic acid at a molar ratio of 80:20 (acid components), and in the OH ratio :COOH=1.3:1. The resulting mixture was allowed to react together with 500 ppm of titanium tetraisopropoxide for 10 hours at 230°C under atmospheric pressure, followed with further reaction for 5 hours under a reduced pressure of 10 mmHg to 15 mmHg. Thereafter, 30 parts of trimellitic anhydride were added to the flask, and the mixture allowed to react for 3 hours at 180°C under atmospheric pressure to thereby obtain a linear polyester A-2-1 resin A. Linear A-2-1 polyester resin A had the number average molecular weight (Mn) of 2400, the weight average molecular weight (Mw) of 5400, and Tg of 48°C. (SYNTHESIS EXAMPLE 9) - Synthesis of Polyester Resin A A-2-2-
Linear A-2-2 polyester resin A was synthesized in the same way as in synthesis example 8, with the proviso that the molar ratio of isophthalic acid and adipic acid was changed to 20:80, the propylene oxide adduct of bisphenol A (3 mol) in the alcohol component was changed to propylene glycol, and the loading ratio was changed to OH:COOH=1.2:1. Linear A-2-2 polyester resin A had the number average molecular weight (Mn) of 4,000, the weight average molecular weight (Mw) of 12,000, and Tg of 29°C. (SYNTHESIS EXAMPLE 10) - Synthesis of Polyester Resin A A-2-3
A 5-L four-neck flask equipped with a nitrogen inlet tube, a condenser, an agitator and a thermocouple was charged with a mixture containing a bisphenol A ethylene oxide adduct (2 mol) and a propylene oxide adduct of bisphenol A (3 mol at a molar ratio of 60:40 (alcohol components), and a mixture containing terephthalic acid and adipic acid at a molar ratio of 90:10 (acid components), and in the ratio of OH:COOH =1.3: 1. The resulting mixture was allowed to react together with 500 ppm of titanium tetraisopropoxide for 10 hours at 230°C under atmospheric pressure, followed by further reacting for 5 hours under the reduced pressure of 10 mmHg to 15 mmHg Thereafter, 30 parts of trimellitic anhydride were added to the flask, and the mixture was allowed to react for 3 hours at 180°C under atmospheric pressure to thereby obtain linear A-2-3 polyester resin A. linear A-2-3 polyester resin A had the number average molecular weight (Mn) of 2,500. weight average molecular weight (Mw) of 5800, and Tg of 65°C. (SYNTHESIS EXAMPLE 11) - Synthesis of crystalline polyester resin A B containing unsaturated double bond -
A double-neck flask, which was heated and dried, was charged with a mixture containing dimethyl fumarate and dimethyl sebacate in a molar ratio of 90:10 (acid components), 1,6-hexanediol (an alcohol component) in an amount that was 1.15 times the amount of acid components, and Ti(OBu)4 as a catalyst. Thereafter, nitrogen purge was performed to replace the air inside the flask with an inert atmosphere of nitrogen gas by decompression, and a reflux was performed by mechanical stirring for 5 hours at 180°C. Thereafter, excess 1,6-hexanediol was removed by vacuum distillation. While gradually heating the resultant to 230°C, the resultant was stirred for 2 hours. Once the resultant became viscous, it was cooled with air to terminate the reaction. Before the reaction product solidified, tetrahydrofuran (THF) was added to the flask, and the catalyst residue was removed by a pressure filter device. As for sedimentation, the re-deposit sediment was collected using THF/MeOH, and dried under reduced pressure to thereby obtain crystalline polyester resin A B containing unsaturated double bond. Crystalline polyester resin B containing unsaturated double bond B had the number average molecular weight (Mn) of 3900, the weight average molecular weight (Mw) of 13800, and the melting point of 68°C.
A toner was prepared in the manner mentioned above using Resin A A-1-1, Resin A A-2-1 and Resin AB in the relationship shown in the column of example 1 in table 1. Specifically, Resin A A-1-1, Resin A-2-1 and Resin AB were mixed so that Resin A A-1-1 was 10%, Resin A A-2-1 was 80% and Resin AB was 10%. (EXAMPLE 2)
Crystalline polyester resin A B' was synthesized in the same way as in synthesis example 11, with the proviso that 1,6-hexanediol was replaced with ethylene. Crystalline polyester resin A B' had the number average molecular weight (Mn) of 3800, the weight average molecular weight (Mw) of 16,200, and the melting point of 77°C.
A toner was prepared in the same way as in example 1, with the proviso that resin A B was replaced with resin A B’.(EXAMPLE 3)
A toner was prepared in the same way as in example 1, with the proviso that resin A A-1-1 was not used, and resin A-2-1 was replaced with resin A-2-2.(EXAMPLE 4)
A toner was prepared in the same way as in example 1, with the proviso that the resin B content was changed to 5% by mass. (EXAMPLE 5)
A toner was prepared in the same way as in example 1, with the proviso that the resin B content was changed to 15% by mass. (EXAMPLE 6)
A toner was prepared in the same way as in example 1, with the proviso that the resin B content was changed to 20% by mass. (EXAMPLE 7)
A toner was prepared in the same way as in example 1, with the proviso that the content of resin A-1-1 was changed to 20% by mass, and the content of resin B was changed to 3% by mass.(EXAMPLE 8)
A toner was prepared in the same way as in example 1, with the proviso that the A-1-1 resin content was changed to 3% by mass, and the resin B content was changed to 3% by mass.(EXAMPLE 9)
A toner was prepared in the same way as in example 1, with the proviso that resin A-2-1 was replaced with resin A-2-2, and the content of resin B was changed to 15% by mass.
A toner was prepared in the same way as in example 1, with the proviso that resin A-1-1 was replaced with resin A-1-2.(EXAMPLE 11)
A toner was prepared in the same way as in example 1, with the proviso that resin A-1-1 was replaced with resin A-1-3.(EXAMPLE 12)
A toner was prepared in the same way as in example 1, with the proviso that resin A-1-1 was replaced with resin A-1-4.(EXAMPLE 13)
A toner was prepared in the same way as in example 1, with the proviso that resin A-1-1 was replaced with resin A-1-5.(EXAMPLE 14)
A toner was prepared in the same way as in example 11, with the proviso that resin B was replaced with stearic acid amide (Neutron-2, manufactured by NIPPON FINE CHEMICAL CO., LTD., melting point: 95°C. ).(EXAMPLE 15)
A toner was prepared in the same way as in example 11, with the proviso that the resin B content was changed to 0% by mass. (EXAMPLE 16)
A toner was prepared in the same way as in example 1, with the proviso that resin A-1-1 was replaced with resin A-1-6. (EXAMPLE 17)
A toner was prepared in the same way as in example 1, with the proviso that resin A-1-1 was replaced with resin A-1-7. (COMPARATIVE EXAMPLE 1)
Polyester A-1' resin A was synthesized in the same way as in synthesis example 1, with the proviso that the alcohol component was changed to propylene glycol and the acid composition was changed to terephthalic acid/adipic acid/acid trimellitic = 80/17.5/2.5. Polyester resin A A-1' had the number average molecular weight (Mn) of 5,500, the weight average molecular weight (Mw) of 45,000, and Tg of 56°C.
A toner was prepared in the same way as in example 1, with the proviso that resin A-1-1 was replaced with resin A-1’. (COMPARATIVE EXAMPLE 2)
A toner was prepared in the same way as in example 1, with the proviso that the content of the A-1-1 resin was changed to 30% by mass. (COMPARATIVE EXAMPLE 3)
A toner was prepared in the same way as in example 1, with the proviso that the resin B content was changed to 25% by mass. (COMPARATIVE EXAMPLE 4)
A toner was prepared in the same manner as in example 1, with the proviso that resin B was replaced with polybutylene succinate sebacate (manufactured by Sigma-Aldrich Co., LLC) which does not contain unsaturated double bonds. (COMPARATIVE EXAMPLE 5)
Crystalline polyester resin A B' was synthesized in the same way as in synthesis example 11, with the proviso that the entire acid component was switched to dimethyl sebacate. Crystalline polyester resin A B' had the number average molecular weight (Mn) of 3600, the weight average molecular weight (Mw) of 14,000, and the melting point of 63°C.
A toner was prepared in the same way as in example 1, with the proviso that resin B was replaced with resin B’’.
The properties of each toner in the examples and comparative examples were measured and evaluated as follows.
The results are shown in tables 1, 2, and 3. -Softening Point (Tm)-
After pre-heating 1 g of a measurement sample to 50°C by means of a capillary rheometer (CFT-500D, manufactured by Shimadzu Corporation), a load of 30 kg was applied to the sample by a plunger, while heating the sample in the heating rate of 5°C/min, to extrude the sample from a nozzle having a diameter of 0.5 mm, and a length of 1 mm. A graph was drawn of "a quantity dropped from the plunger" (flow value) and "temperature." The temperature corresponding to 1/2 the maximum value of the amount dropped from the plunger was read from the graph, and this value (temperature at which one half of the measuring sample was eluted) was determined as a softening point.-Anti-blocking property-
A glass vessel was charged with the toner and allowed to stand for 24 hours in a thermostat which was held at 50°C. Thereafter, the toner in the vessel was cooled to 24°C, and a degree of blockage (aggregations) was assessed based on the following criteria. [Rating criteria]
A: No locks occurred. B: Locks occurred, but they were easily dispersed as a force was applied, which was not a problem in practical use. C: Locks occurred, and they were not dispersed even when a force was applied. Blockages occurred, and the toner was completely set and could not be removed as a powder.
A developer was prepared using each toner from the examples and comparative examples as follows. -Conveyor Production -
To 100 parts of toluene, 100 parts of a silicone resin (linear organo silicone), 5 parts of -(2-aminoethyl)aminopropyl trimethoxy silane, and 10 parts of carbon black were added and the resulting mixture was dispersed by Homomixer during 20 minutes to thereby prepare a resin layer coating liquid.
Subsequently, the resin layer coating liquid was applied to spherical magnetite surfaces (1,000 parts) having an average particle diameter of 50 µm by means of a fluidized layer coater to thereby produce a carrier. -Developer Production-
By means of a ball mill, 5 parts of each toner and 95 parts of the conveyor were mixed to thereby produce a developer.
Each developer produced was evaluated in terms of color fixation property as follows. <Setting temperature>
A copy test was performed on 6200 grade paper (manufactured by Ricoh Company Limited) or by means of a modified copier (MF2200, manufactured by Ricoh Company Limited) a clamping section which was modified using a Teflon cylinder (trademark.
Specifically, the cold drift temperature (minimum setting temperature) and hot drift temperature (maximum setting temperature) were determined by varying the setting temperature.
As for the evaluation conditions for the minimum fixation temperature, the linear paper feeding speed was set at 120 mm/s to 150 mm/s, the support was set at 1.2 kgf/cm2, and the height of the tongs was set in 3 mm.
As for the evaluation conditions for the maximum fixation temperature, moreover, the linear paper feed speed was set at 50 mm/s, the support was set at 2.0 kgf/cm2, and the tong width was fixed at 4.5 mm.
In addition, the range from the cold drift temperature (minimum setting temperature) to the hot drift temperature (maximum setting temperature) was determined as a width of the setting temperature.
In the present document, as for the setting property, the minimum setting temperature of 115°C or lower, and the setting temperature width of 40°C or more are preferable in practical use. <Anti-Film Property>
A solid image was formed on a whole sheet by means of an MF2800 imaging apparatus (manufactured by Ricoh Company Limited) to give a toner deposition amount of 0.40 mg/cm2, and was printed on 10,000 sheets in total . After that, the photoconductor was visually observed, and whether or not toner components (mainly the release agent) were adhered onto the photoconductor was evaluated based on the following criteria. [Rating criteria]
A: No toner components adhesion was observed.B: Toner components adhesion was observed, but was at a level where it could be a problem in practical use.D: Toner components adhesion was observed, but it was at a level where could be a significant problem in practical use. <Transfer White Lack>
The developer was loaded into Ricoh pro 6100 (manufactured by Ricoh Company Limited), and an A4 size image having an imaging area of 5% was printed continuously onto 10,000 sheets. Subsequently, a solid image (toner deposition amount: 0.4 mg/cm2) was formed on a total area of A4-sized paper, and printed on 3 sheets in total. Thereafter, the missing white parts in the images were observed visually and under an optical microscope. Results are evaluated based on the following criteria. [Rating criteria]
A: No white absent areas were visually observed over all 3 leaves.B: White absent areas were observed over a third leaf under the light microscope, but this was not a level where there might be a problem in practical use.C: One to ten white absent areas were visually observed in total over the three leaves, and it was a level where there could be a problem in practical use.D: Eleven or more white absent areas were visually observed in total over the three leaves, and it was a level where there could be a significant problem in practical use. <Image Density>
Carrier and toner used in Imageo MP C4300 (manufactured by Ricoh Company Limited) were mixed to give a toner density of 5% by mass to thereby obtain a developer.
An Imageo MP C4300 unit (manufactured by Ricoh Company Limited) was loaded with the developer, and a rectangular solid image in the size of 2 cm x 15 cm was formed on a PPC sheet, type 6000 <70W> A4, long grain paper (manufactured by Ricoh Company Limited) to give a toner deposition amount of 0.40 mg/cm2. The surface temperature of the clamp cylinder was set at 120°C. Then, the image density (ID) in the solid image was measured by means of X-Rite 938 (manufactured by X-Rite) with a mode in state A, and light d50. [Rating criteria]
A: 1.5 or moreB: 1.4 or more but less than 1.5C: 1.2 or more but less than 1.4D: Less than 1.2 <Glow>
A print test was carried out on 6200 grade paper (manufactured by Ricoh Company Limit) by means of a device, in which the fixing unit of an MF 2200 copier (manufactured by Ricoh Company Limited) using Teflon cylinder (trademark) as a clamping cylinder was modified. Specifically, the setting temperature was set at the temperature which was the minimum setting temperature, + 20°C, where the minimum setting temperature was determined as the low temperature setting capacity was evaluated, the linear speed of the paper feed was set at 120 mm/s at 150 mm/s, the support was set at 2 kgf/cm2, and the tongs width was set at 3 mm. The 60° gloss of the image after the print test was measured using a VG-7000 glossimeter (manufactured by NIPPON DENSHOKU INDUSTRIES Co., Ltd.). Results were evaluated based on the following criteria. [Rating criteria]
A: 30% or moreB: 25% or more but less than 30%C: 20% or more but less than 25%D: Less than 20%




Note that in tables 2 and 3, “*1” and “*2” indicate, respectively, “stearic acid amide” and “polybutylene succinate sacacate”, white are used as a replacement for resin B. Their contents are both 10%, as represented in the resin content column B with a darker one.
Embodiments of the present invention are, for example, as follows:<1> A toner containing: a colorant; a binder resin A; and a release agent, wherein the toner satisfies the following (a) to (c): (a) the toner contains at least one polyester resin A as a binder resin A; (b) the toner has 1a Tg of 25° C to 50°C; and(c) toner at a TMA compressive strain rate (TMA%) of 10% or lower at 50°C under a condition that has a relative humidity of 70%, where the 1st Tg is the glass transition temperature of the toner for the first heat, as the toner is measured by a DSC system (a differential scanning calorimeter). < 2> The toner according to <1>, wherein a component of the toner insoluble in tetrahydrofuran (THF) has 2a Tg' of -40°C to 30°C as measured by differential scanning calorimetry (DSC), and The THF-insoluble component has an elastic storage modulus G' from 106 to 108 at 40°C, and an elastic storage modulus G' from 105 to 107 at 100°C.< 3> The toner according to any of <1> or <2>, where the 1st Tg of toner - 2nd Tg of toner is 10°C or more, where 2nd Tg is the toner glass transition temperature for second heat as the toner is measured by a DSC (differential scanning calorimeter) system.< 4> The toner according to any one of <1> to <3>, wherein polyester resin A contains a plurality of polyester resins A, and at least one of a polyester resin A is non-crystalline polyether resin A containing a diol component as a constitutional component, where the diol component contains C3-C10 aliphatic diol in an amount of 50 mol% u more, and trivalent or higher acid or trihydric or higher alcohol as a crosslinking component.< 5> The toner according to <4>, wherein a number of carbon atoms in a main chain of the diol component is an odd number , and the diol component has an alkyl group on a side chain thereof.< 6> The toner according to either of <4> or <5>, wherein the crosslinking component is trivalent acid or trihydric alcohol.< 7 > The toner according to any one of <1> to <3>, wherein the polyester resin A contains a plurality of polyester resin A, and at least one of a polyester resin A is non-polyether resin A crystalline is obtained by a reaction between a compound containing the active hydrogen group and a polymer that can react with the compound containing the active hydrogen group.< 8> The toner according to any one of <1> to <7>, wherein the polyester resin A is composed of a non-crystalline polyether resin A and the crystalline polyester resin A B.< 9> The toner according to <8>, wherein the content of crystalline polyester resin A B is 3% by mass to 20% by mass.< 10> The toner according to either of <8> or <9>, wherein crystalline polyester resin A B has a crosslinking structure formed from unsaturated double bond segments. < 11> The toner according to any one of <8> to <10>, wherein crystalline polyester resin A B has a melting point of 60°C to 80°C, and polyester resin A contains a C4-C12 linear saturated aliphatic dicarboxylic acid in an amount of 80% mol or more with respect to a component of total acid, and a C2-C12 linear saturated aliphatic diol in an amount of 80% mol or more with respect to a component of total alcohol.< 12> A developer, containing: the toner according to any one of <1> to <11>; and a carrier.< 13> A process cartridge, containing: a latent electrostatic imaging support member; and a developer unit configured to develop an electrostatic latent image formed on the electrostatic latent image support member with a toner to form a visible image, wherein the toner is the toner according to any one of <1> to <11> .< 14> An imaging device, containing:< process cartridge according to <13>.

权利要求:
Claims (10)
[0001]
1. Toner characterized by the fact that it comprises: a colorant; a binding resin; and a release agent, wherein the toner satisfies the following (a) to (c): (a) the toner contains at least one polyester resin as the binder resin; (b) the toner has 1a Tg from 25°C to 45°C; and(c) the toner has a TMA compressive strain ratio (TMA%) of 10% or lower at 50°C under a condition that has a relative humidity of 70%, where the 1st Tg is the toner's glass transition temperature for first heating, as the toner is measured by a DSC system (a differential scanning calorimeter), wherein the polyester resin contains at least one non-crystalline polyester resin A and a crystalline polyester resin B, in which an insoluble component in tetrahydrofuran (THF) the toner has a 2nd Tg' of -40°C to 30°C as measured by differential scanning calorimetry (DSC), and the THF-insoluble component has an elastic storage modulus G' of 106 Pa at 108 Pa at 40°C, and elastic storage modulus G' of 105 Pa to 107 Pa at 100°C, and wherein the polyester resin contains a plurality of polyester resins, and at least one of the polyester resin is a non-crystalline polyester resin containing a diol component as a constitutional component, where the component The only diol contains C3-C10 aliphatic diol in an amount of 50% mol or more, and trivalent acid or higher or trihydric alcohol or higher as a crosslinking component.
[0002]
2. Toner according to claim 1, characterized in that the 1st Tg of toner - 2nd Tg of toner is 10°C or more, where the 2nd Tg is the glass transition temperature of toner to second heating, as per toner is measured by a DSC (differential scanning calorimeter) system.
[0003]
3. Toner according to claim 1, characterized in that a number of carbon atoms in a main chain of the diol component is an odd number, and the diol component has an alkyl group in a side chain thereof.
[0004]
4. Toner according to claim 1 or 3, characterized in that the crosslinking component is trivalent acid or trihydric alcohol.
[0005]
5. Toner according to any one of claims 1 to 2, characterized in that the polyester resin contains a plurality of polyester resins, and at least one of the polyester resin is a non-crystalline polyester resin obtained through a reaction between a compound containing an active hydrogen group and a polymer that can react with the compound containing an active hydrogen group.
[0006]
6. Toner according to any one of claims 1 to 3, characterized in that the polyester resin is composed of a non-crystalline polyester resin A and a crystalline polyester resin B.
[0007]
7. Toner according to claim 6, characterized in that the content of crystalline polyester resin B is 3% by mass to 20% by mass.
[0008]
8. Toner according to claim 6, characterized in that the crystalline polyester resin B has a crosslinking structure formed from segments of unsaturated double bonds.
[0009]
9. Toner according to claim 6, characterized in that crystalline polyester resin B has a melting point of 60°C to 80°C, and polyester resin B contains a C4-C12 aliphatic dicarboxylic acid linear saturated in an amount of 80% mol or more with respect to a total acid component, and linear saturated aliphatic diol in an amount of 80% mol or more with respect to a total alcohol component.
[0010]
10. Developer characterized in that it comprises: the toner as defined in any one of claims 1 to 9; and a carrier.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

DE60120553T2|2000-04-28|2007-06-06|Ricoh Co., Ltd.|Toner, external additive, and imaging process|

---

US6660443B2|2001-03-19|2003-12-09|Ricoh Company, Ltd.|Dry toner and image forming method using same|

---

DE60223778T3|2001-11-02|2015-08-06|Ricoh Co., Ltd.|Toner for the development of electrostatic images, developers, and development processes|

---

JP4047734B2|2002-03-20|2008-02-13|株式会社リコー|Toner for electrostatic image development|

---

EP1347341B2|2002-03-22|2018-01-10|Ricoh Company, Ltd.|Use of a toner and developer for electrophotography, image-forming process cartridge, image-forming apparatus and image-forming process using the toner|

---

JP3948716B2|2002-08-26|2007-07-25|株式会社リコー|Color toner for image formation, image forming apparatus and toner container|

---

US7541128B2|2002-09-26|2009-06-02|Ricoh Company Limited|Toner, developer including the toner, and method for fixing toner image|

---

JP4079257B2|2002-10-01|2008-04-23|株式会社リコー|Toner for electrostatic image development|

---

JP4030907B2|2003-03-19|2008-01-09|株式会社リコー|Toner for electrostatic image development|

---

EP1494082B1|2003-07-01|2015-08-05|Ricoh Company, Ltd.|Toner method for preparing the toner, and image forming method and apparatus using the toner|

---

JP2005115029A|2003-10-08|2005-04-28|Ricoh Co Ltd|Toner and method for manufacturing the same, and developer, toner container, process cartridge, image forming apparatus and image forming method|

---

JP4093416B2|2004-01-06|2008-06-04|株式会社リコー|Toner for electrophotography and method for producing the same|

---

JP2005338814A|2004-04-30|2005-12-08|Ricoh Co Ltd|Image forming toner, electrophotographic fixing method, image forming method, and process cartridge|

---

US7455942B2|2004-09-17|2008-11-25|Ricoh Company, Ltd.|Toner, developer, toner container, process cartridge, image forming apparatus, and image forming method using the same|

---

US7932007B2|2004-09-21|2011-04-26|Ricoh Company, Ltd.|Toner and method for producing the same, and image-forming method using the same|

---

JP4658010B2|2006-09-15|2011-03-23|株式会社リコー|Toner and manufacturing method thereof, developer, toner-containing container, process cartridge, image forming method, and image forming apparatus|

---

JP5042889B2|2007-03-16|2012-10-03|株式会社リコー|Toner and developer, and image forming method using the same|

---

CN101681140B|2007-05-11|2012-08-22|株式会社普利司通|Electrically conductive roller|

---

EP1990683B1|2007-05-11|2012-09-05|Ricoh Company, Ltd.|Toner, image forming apparatus, image forming method and process cartridge using the toner|

---

JP5090057B2|2007-05-11|2012-12-05|株式会社リコー|Toner, and image forming apparatus and image forming method using the same|

---

JP5128858B2|2007-06-19|2013-01-23|株式会社リコー|Toner and method for producing the same|

---

JP5315808B2|2007-06-22|2013-10-16|株式会社リコー|Toner, developer, toner containing container, image forming method, image forming apparatus, and process cartridge|

---

US8034527B2|2007-08-23|2011-10-11|Xerox Corporation|Core-shell polymer nanoparticles and method for making emulsion aggregation particles using same|

---

JP5224114B2|2007-09-13|2013-07-03|株式会社リコー|Image forming apparatus and image forming method|

---

JP5036478B2|2007-10-09|2012-09-26|株式会社リコー|toner|

---

JP2009116313A|2007-10-18|2009-05-28|Ricoh Co Ltd|Toner, developer, image forming method, image forming apparatus and process cartridge|

---

JP5124308B2|2008-02-26|2013-01-23|株式会社リコー|Toner, developer using the toner, container with toner, process cartridge, and image forming method|

---

JP5568888B2|2008-05-23|2014-08-13|株式会社リコー|Toner, developer, toner container, process cartridge, and image forming method|

---

JP2010008734A|2008-06-27|2010-01-14|Ricoh Co Ltd|Toner, image forming method using the same, and process cartridge|

---

JP5157733B2|2008-08-05|2013-03-06|株式会社リコー|Toner, developer, toner container, process cartridge, and image forming method|

---

JP5273719B2|2008-12-24|2013-08-28|花王株式会社|Toner for electrophotography|

---

JP5429963B2|2009-01-26|2014-02-26|花王株式会社|Toner production method|

---

JP2010231068A|2009-03-27|2010-10-14|Fuji Xerox Co Ltd|Electrostatic charge image developing toner, electrostatic charge image developer, toner cartridge, process cartridge and image forming apparatus|

---

US8227164B2|2009-06-08|2012-07-24|Ricoh Company, Limited|Toner, and developer, developer container, process cartridge, image forming apparatus and image forming method using the toner|

---

US8679714B2|2009-09-14|2014-03-25|Ricoh Company, Ltd.|Toner, developer, and image forming method|

---

JP5106512B2|2009-10-27|2012-12-26|株式会社リコー|Toner, image forming apparatus, image forming method, and process cartridge|

---

JP2011123483A|2009-11-12|2011-06-23|Ricoh Co Ltd|Toner and image forming apparatus|

---

JP5325757B2|2009-12-18|2013-10-23|花王株式会社|Method for producing toner for electrophotography|

---

JP2011150229A|2010-01-25|2011-08-04|Konica Minolta Business Technologies Inc|Toner and method for producing toner|

---

JP5515909B2|2010-03-18|2014-06-11|株式会社リコー|Toner, developer, process cartridge, image forming method, and image forming apparatus|

---

JP5685984B2|2010-04-21|2015-03-18|株式会社リコー|Toner containing crystalline polyester|

---

JP5510026B2|2010-04-21|2014-06-04|株式会社リコー|Toner, developer, process cartridge, image forming method, and image forming apparatus|

---

JP6132455B2|2010-05-26|2017-05-24|株式会社リコー|toner|

---

JP2012008354A|2010-06-25|2012-01-12|Ricoh Co Ltd|Method for producing electrophotographic toner, toner, method for forming full-color image, and full-color image forming apparatus|

---

JP5573528B2|2010-09-15|2014-08-20|株式会社リコー|Resin for toner, toner using the resin for toner, and two-component developer|

---

JP5522540B2|2010-09-15|2014-06-18|株式会社リコー|Toner, developer, developer container, process cartridge, image forming apparatus, and image forming method|

---

JP5594591B2|2010-09-30|2014-09-24|株式会社リコー|Toner for electrophotography, developer using the toner, image forming apparatus, image forming method, process cartridge|

---

JP2012108462A|2010-10-28|2012-06-07|Ricoh Co Ltd|Toner and developer|

---

JP2012128405A|2010-11-22|2012-07-05|Ricoh Co Ltd|Toner, developer, image forming apparatus and image forming method|

---

JP5849651B2|2011-01-24|2016-01-27|株式会社リコー|Toner and developer|

---

JP5742412B2|2011-02-28|2015-07-01|株式会社リコー|Toner for electrostatic image formation and resin for toner|

---

JP5742319B2|2011-03-11|2015-07-01|株式会社リコー|Toner, developer and image forming method|

---

JP2012204162A|2011-03-25|2012-10-22|Toshiba Lighting & Technology Corp|Lighting device and lighting fixture|

---

JP5408210B2|2011-09-02|2014-02-05|株式会社リコー|Toner and developer|

---

JP5790370B2|2011-09-22|2015-10-07|富士ゼロックス株式会社|Toner for developing electrostatic image, developer for developing electrostatic image, toner cartridge, process cartridge, and image forming apparatus|

---

JP2013109142A|2011-11-21|2013-06-06|Ricoh Co Ltd|Toner and image forming method using the same and process cartridge|

---

JP6066447B2|2011-12-14|2017-01-25|株式会社リコー|Toner and image forming method using the same|

---

JP6086291B2|2011-12-15|2017-03-01|株式会社リコー|Toner, developer, and toner production method|

---

JP2013148862A|2011-12-20|2013-08-01|Ricoh Co Ltd|Toner, developer and image forming apparatus|

---

JP2013156475A|2012-01-31|2013-08-15|Ricoh Co Ltd|Toner for electrostatic image formation and developer|

---

JP2013190720A|2012-03-15|2013-09-26|Ricoh Co Ltd|Toner for image formation|JP5884797B2|2013-09-06|2016-03-15|株式会社リコー|Toner, developer, and image forming apparatus|

---

AU2014316311A1|2013-09-06|2016-02-25|Ricoh Company, Ltd.|Toner|

---

JP6273726B2|2013-09-06|2018-02-07|株式会社リコー|Toner, developer, and image forming apparatus|

---

JP6264799B2|2013-09-13|2018-01-24|株式会社リコー|Resin for toner, toner, developer, image forming apparatus, process cartridge|

---

RU2664797C1|2014-02-04|2018-08-22|Рикох Компани, Лтд.|Polyester resin for toner, toner, developer, and imaging apparatus|

---

EP3112937B1|2014-02-26|2018-10-10|Ricoh Company, Ltd.|Toner, developer, and image formation device|

---

JP6458515B2|2014-03-03|2019-01-30|株式会社リコー|Toner for electrostatic image development, developer, and image forming apparatus|

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JP2015180925A|2014-03-04|2015-10-15|株式会社リコー|Magenta toner, developer, and image forming apparatus|

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JP6582846B2|2014-10-30|2019-10-02|株式会社リコー|Toner, toner storage unit, and image forming apparatus|

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JP2017107138A|2015-01-05|2017-06-15|株式会社リコー|Toner, toner storage unit, and image forming apparatus|

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---

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---

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---

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---

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---

US9804516B2|2015-05-12|2017-10-31|Ricoh Company, Ltd.|Toner, developer, image forming apparatus, and process cartridge|

---

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---

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---

JP6551544B2|2016-01-18|2019-07-31|株式会社リコー|Toner, developer, and image forming apparatus|

---

US10303072B2|2017-02-08|2019-05-28|Ricoh Company, Ltd.|Toner, developer, and image forming device|

---

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---

US11036154B2|2017-12-05|2021-06-15|Ricoh Company, Ltd.|Toner, toner storage unit, image forming apparatus, and image forming method|

---

JP2019109544A|2019-03-08|2019-07-04|株式会社リコー|Toner, developer, and image forming apparatus|

法律状态:
2014-10-14| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|

---

2018-11-21| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2020-09-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-04-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/09/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2012-204162|2012-09-18|

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JP2012204162|2012-09-18|

---