JP5423054B2 - Toner for developing electrostatic image, method for producing the same, electrostatic image developer, toner cartridge, process cartridge, and image forming apparatus - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image, a method for producing the same, an electrostatic image developer, a toner cartridge, a process cartridge, and an image forming apparatus.

Methods for visualizing image information through an electrostatic charge image, such as electrophotography, are currently used in various fields.
In conventional electrophotography, an electrostatic latent image is formed on a photosensitive member or an electrostatic recording body by using various means, and electro-sensitive particles called toner are attached to the electrostatic latent image to form an electrostatic latent image. Generally, a method of visualizing through a plurality of steps of developing an image (toner image), transferring it to the surface of a transfer medium, and fixing it by heating or the like is generally used.

  Incidentally, as a general method for lowering the fixing temperature of toner, it is known to use a crystalline resin having a low melting temperature as a binder resin. For example, a technique is disclosed in which a crystalline polyester resin is used in a toner as a crystalline resin that is expected to improve the fixability to paper. (For example, refer to Patent Document 1.) This is a technique in which an amorphous polyester resin having a glass transition temperature of 40 ° C. or higher and a crystalline polyester resin having a melting temperature of 130 ° C. or higher and 200 ° C. or lower are mixed and used.

  In addition, a technique for obtaining low-temperature fixing by mixing a low-melting crystalline resin and an amorphous resin and controlling the degree of compatibilization has been proposed. (For example, see Patent Document 2 and Patent Document 3.) Since toners using these crystalline resins as a main component melt at a relatively low temperature as compared with conventional toners, fixing in a low temperature range or in a high temperature range is possible. Suitable for high-speed fixing.

  Further, in order to realize a low gloss image, a toner containing a resin having a specific molecular weight and a specific molecular weight distribution as a binder resin (see, for example, Patent Document 4), and a block copolymer as a binder resin. An invention having a configured polyester resin and an amorphous polyester resin (see, for example, Patent Document 5 and Patent Document 6), and using a crosslinked resin and a non-crosslinked resin as a binder resin, A defined toner is disclosed. (For example, see Patent Document 7)

  For the purpose of low-temperature fixing, a toner containing a binder resin composed mainly of a crystalline polyester having a crosslinked structure (for example, see Patent Document 8), a low softening point substance such as wax is added to the toner, A toner is disclosed that defines a ratio of storage modulus at 60 ° C. and 80 ° C. and a ratio of storage modulus at 155 ° C. and 190 ° C. (For example, refer to Patent Document 9).

  In order to realize both low-temperature fixability and anti-crushing property of a toner, a toner having a resin that is a polymer having a specific zwitterionic group and ionically crosslinked is disclosed. (For example, refer to Patent Document 10.)

  In order to achieve high image quality, the ratio of the content of trivalent metal element (A) and the content of divalent metal element (B) contained in the toner surface measured by X-ray photoelectron spectroscopy ( A / B) and a toner that defines the weight average molecular weight (Mw) of the toner are disclosed. (For example, refer to Patent Document 11.)

Japanese Examined Patent Publication No.62-39428 JP 2004-206081 A Japanese Patent Laid-Open No. 2004-50478 Japanese Patent Laid-Open No. 06-148935 JP 2008-97041 A JP 2004-138920 A JP 2008-116948 A JP 2001-117268 A JP 09-034163 A JP 2005-037429 A JP 2007-086493 A

  An object of the present invention is to solve the following problems. That is, the toner for developing an electrostatic charge image that is less likely to deteriorate the low-temperature fixability and has a low glossiness and an excellent image reproducibility as compared with the case where the aluminum content in the toner surface layer and the inside is not taken into consideration. It is another object of the present invention to provide an electrostatic charge image developer, a toner cartridge, a process cartridge, and an image forming apparatus using the toner.

The above problem is solved by the following means.
That is, the invention according to claim 1 contains a binder resin containing at least a crystalline resin, and a colorant,
The aluminum content of the toner surface layer is in the range of 0.05 to 0.15 in the Net intensity by fluorescent X-ray analysis, and the aluminum content in the toner is 0. 0 in the Net intensity by fluorescent X-ray analysis. The toner for developing an electrostatic charge image is in the range of 20 or more and 0.50 or less.

  The invention according to claim 2 is the crystalline polyester resin, wherein the crystalline resin has an acid value of 5 mgKOH / g or more and 25 mgKOH / g or less and a weight average molecular weight of 8000 or more and 40000 or less. The electrostatic charge image developing toner described.

The invention according to claim 3 is a coagulation step in which at least one resin particle dispersion and at least one colorant dispersion are mixed to form aggregated particles in the presence of aluminum ions;
A fusion step of heating the resin particles of the resin particle dispersion to a temperature equal to or higher than the glass transition temperature to fuse and coalesce the aggregated particles to form toner particles;
A cleaning step of cleaning the obtained toner particles;
The method for producing a toner for developing an electrostatic charge image according to claim 1 , wherein the washing step includes at least a step of washing the toner particles with a treatment liquid containing a chelating agent.

According to a fourth aspect of the present invention, there is provided an electrostatic image developer comprising at least the electrostatic image developing toner according to the first or second aspect.
According to a fifth aspect of the present invention, there is provided a toner to be attached to and detached from the image forming apparatus and to be supplied to a developing unit provided in the image forming apparatus, and the toner is the static according to the first or second aspect. A toner cartridge that is a toner for developing a charge image.

According to a sixth aspect of the present invention, there is provided a process cartridge comprising at least a developer holder and containing the electrostatic charge image developer according to the fourth aspect.
The invention according to claim 7 is a latent image holder, and developing means for developing the electrostatic latent image formed on the latent image holder as a toner image with the electrostatic charge image developer according to claim 4, Transfer means for transferring the toner image formed on the latent image holding member onto the transfer member, fixing means for fixing the toner image transferred onto the transfer target member, and cleaning member for cleaning the latent image holding member And an image forming apparatus having cleaning means for cleaning the transfer residual component.

  According to the first aspect of the present invention, there is provided a toner for developing an electrostatic charge image that is capable of obtaining an image in which low-temperature fixability is hardly impaired and high glossiness and image reproducibility are controlled.

  According to the second aspect of the present invention, there is provided a toner for developing an electrostatic charge image that is capable of obtaining an image in which low-temperature fixability is not easily impaired and high glossiness and image reproducibility are controlled.

  According to the third aspect of the present invention, there is provided a method for producing a toner for developing an electrostatic charge image, in which low-temperature fixability is not easily impaired, and an image with high glossiness and controlled image reproducibility can be obtained.

  According to the fourth aspect of the invention, there is provided an electrostatic charge image developer having an electrostatic charge image developing toner that can obtain an image in which low-temperature fixability is not easily impaired and high glossiness and image reproducibility are controlled. Is done.

  According to the fifth aspect of the present invention, there is provided a toner cartridge having an electrostatic charge image developing toner that can obtain an image in which low-temperature fixability is not easily impaired and high glossiness and image reproducibility are controlled.

  According to the sixth aspect of the present invention, there is provided a process cartridge having a toner for developing an electrostatic charge image that is capable of obtaining an image in which low-temperature fixability is hardly impaired and high glossiness and image reproducibility are controlled.

  According to the seventh aspect of the present invention, there is provided an image forming apparatus having an electrostatic image developing toner capable of obtaining an image in which low-temperature fixability is not easily impaired and high glossiness and image reproducibility are controlled. .

1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows an example of the process cartridge of this embodiment.

Hereinafter, embodiments of the present invention will be described in detail.
<Toner for electrostatic image development>
The electrostatic image developing toner according to the exemplary embodiment (hereinafter, simply referred to as “toner”) includes at least a binder resin including a crystalline resin and a colorant, and aluminum in a toner surface layer portion. The content is in the range of 0.05 or more and 0.15 or less in the Net intensity by fluorescent X-ray analysis, and the aluminum content in the toner is 0.20 or more and 0.50 in Net intensity by the fluorescent X-ray analysis. It is characterized by being in the following range.

Here, the toner surface layer part is obtained by mixing 1 part by mass of the toner with a solution containing 5 parts by mass of methanol and 5 parts by mass of tetrahydrofuran under the condition of 25 ° C. Shows a portion of the toner that dissolves in the solution when it is vibrated at 50 kHz for 3 minutes. Further, the inside of the toner indicates a portion of the toner that does not dissolve in the solution under the same conditions.
However, in the present embodiment, a solution containing only 5 parts by mass of methanol and 5 parts by mass of tetrahydrofuran is applied as a solution containing 5 parts by mass of methanol and 5 parts by mass of tetrahydrofuran. The toner mixed in this solution is 1 part by mass.

  The toner according to the present embodiment has the above-described configuration, so that the low-temperature fixability is not easily impaired and the glossiness is low and the image reproducibility is lower than that in the case where the toner surface layer portion and the internal aluminum content are not considered. An excellent image can be obtained. The reason for this is not clear, but is thought to be due to the following reasons.

  Since the toner contains a crystalline resin, the toner is fixed in a low temperature range (for example, a temperature range of 80 ° C. or higher and 120 ° C. or lower). This is because the crystalline resin has a lower melting temperature than the amorphous resin, so that the viscosity is greatly reduced at a specific temperature, and the crystalline resin molecules are thermally activated when the toner is heated during fixing. This is considered to be because the temperature difference from the start to the temperature range where fixing is performed can be reduced.

  On the other hand, in order to obtain an image having a low glossiness, it is required to increase the viscosity of the toner by increasing the crosslink density of the toner and to provide unevenness on the surface of the fixed image. A toner using a crystalline resin as a binder resin has a large decrease in viscosity at the time of fixing, and it is difficult to obtain a low gloss image. However, by increasing the aluminum content in the toner, the toner has a low glossiness. An image can be obtained. That is, by increasing the aluminum content in the toner, many ionic crosslinks are formed between the binder resins, so that the resin melt viscosity at the time of fixing increases, and as a result, an image with low glossiness can be obtained. it is conceivable that.

  However, when the viscosity of the toner is increased, the apparent glass transition temperature of the toner increases, and the low-temperature fixability tends to be impaired. Furthermore, when the toner is high in viscosity, for example, when pressure is applied by the fixing member, it takes time until the toner melts. Therefore, the image is shifted in the opposite direction to the process due to the fixing pressure, and the image reproducibility is improved. May fall. This is particularly noticeable when images of fine characters, lines, and diagonal lines are fixed. In addition, this phenomenon is remarkable when a low-pressure roll is used as a fixing member because heat energy is not easily transmitted to the toner. Especially when paper containing water is used in a high-temperature and high-humidity environment, moisture evaporates during fixing. Therefore, it is considered that the force to move the toner in the opposite direction to the process works and becomes more remarkable.

  Therefore, in the toner of the present embodiment in which the aluminum content in the toner surface layer part and the aluminum content in the toner are controlled within a specific range, the aluminum content in the toner surface layer part is smaller than the aluminum content in the toner, Since the toner surface layer has little ionic cross-linking and thus has a low viscosity, it is easily melted during fixing. Accordingly, at the time of fixing, the toner surface layer portion is rapidly melted and sufficient heat is transmitted to the inside of the toner, so that the low temperature fixing property is prevented from being impaired.

  In addition, since the inside of the toner has many ionic crosslinks due to aluminum and is highly viscous, it is difficult to melt, so that irregularities are easily formed on the surface of the fixed image, and an image with low gloss is obtained. In addition, even when fixing an image (particularly fine characters, lines, and diagonal lines), it is considered that the inner part of the toner that is difficult to melt has an affinity with the surface layer of the toner that melts quickly. As a result, excellent image reproducibility can be realized.

  Note that the toner of the present embodiment has an effect of reducing non-visual offset on the fixing roll side due to a fixing failure (adhesion of toner that does not affect the image to be formed). Adherence of the toner component to the (medium peeling nail) is reduced, and as a result, there is an effect of suppressing scratches on the roll surface, contributing to high image quality and high reliability.

  In order to reduce the cost of the fixing member and to shorten the warm-up time (time until the fixing member reaches the fixing temperature), there is a method of reducing the diameter of the fixing roll. Since the pressure applied to the toner is reduced, heat is not easily transferred to the toner, and it is often used at a low process speed. However, with the toner of this embodiment, the low-temperature fixability is hardly impaired, that is, low-energy fixing is realized, so that printing can be performed at a high process speed even when the fixing nip pressure is low.

  The aluminum content in the toner surface layer portion of the present embodiment needs to be in the range of 0.05 to 0.15, preferably 0.06 to 0.12 in terms of Net intensity by fluorescent X-ray analysis. Yes, more preferably 0.07 or more and 0.10 or less. When the aluminum content is less than 0.05 in the Net strength, the ionic crosslinking becomes too weak, and the offset at high temperature may deteriorate. On the other hand, when the aluminum content is more than 0.15 in the Net strength, the ionic crosslinking becomes too strong, the heat transfer property to the inside of the toner is deteriorated, and the low-temperature fixability may be impaired.

Further, the aluminum content in the toner of the present embodiment needs to be in the range of 0.20 or more and 0.50 or less, preferably 0.25 or more and 0.45 or less, in the Net intensity by fluorescent X-ray analysis. More preferably, it is 0.30 or more and 0.40 or less. When the aluminum content is less than 0.20 in the Net strength, the ionic crosslinking becomes weak and the viscosity becomes low, so that the glossiness may be increased. Further, when the aluminum content is more than 0.50 in the Net strength, the ionic crosslinking becomes too strong and the viscosity is too high, so that the affinity with the fixing member becomes higher than that of the toner surface layer portion, and image misalignment, etc. May occur.

  Separation of the surface layer portion of the toner and the inside of the toner is performed as follows. That is, 1 part of the toner was mixed with a solution containing 5 parts by mass of methanol and 5 parts by mass of tetrahydrofuran under the condition of 25 ° C., and the mixture was vibrated at 50 kHz for 3 minutes with an ultrasonic disperser Tetora 150 (manufactured by Nikka Ki Bios). The components dissolved in the solution are separated into solid and liquid. Here, the component dissolved in the solution is defined as the toner surface layer portion, and the component not dissolved is defined as the toner inside.

  The aluminum content in the toner surface layer and the toner is determined by quantitative analysis of the fluorescent X-ray intensity. Specifically, for example, first, 200 mg of a mixture of polyester resin and aluminum sulfate having a known concentration is pelleted using an IR tablet molding machine having a diameter of 13 mm, and the mass is precisely weighed. Measurement was performed to determine the peak intensity. Similarly, measurement is performed on a sample in which the amount of aluminum sulfate added is changed, a calibration curve is created from these results, and quantitative analysis of the aluminum content in the actual measurement sample is performed using the calibration curve.

Next, the configuration of the electrostatic image developing toner of the present embodiment will be described.
The toner for developing an electrostatic charge image according to the exemplary embodiment contains at least a binder resin containing a crystalline resin and a colorant, and if necessary, contains other components such as a release agent. The toner according to the exemplary embodiment will be described in detail with respect to each component.

(Binder resin)
In the toner of this embodiment, a crystalline resin is used as a binder resin. In addition, it is preferable to use an amorphous resin in combination as necessary.
“Crystalline resin” means a resin having a clear endothermic peak (a peak where the half-value width of the endothermic peak is 10 ° C. or less) in differential scanning calorimetry (DSC). Means not having the above-mentioned clear peak. Moreover, it is preferable that the weight average molecular weight of binder resin is 10,000 or more, and it is more preferable that it is the range of 15000 or more and 50000 or less regardless of crystalline resin and non-crystalline resin.

-Crystalline resin-
Examples of the crystalline resin include crystalline polyester resins, crystalline vinyl resins, and crystalline polyamide resins, and crystalline polyester resins are preferred from the viewpoint of low-temperature fixability.

An optimal crystalline resin that can be used in the toner of the exemplary embodiment is a crystalline polyester resin having an acid value of 5 mgKOH / g to 25 mgKOH / g and a weight average molecular weight of 8000 to 40000. More preferably, the acid value is 6 mgKOH / g or more and 23 mgKOH / g or less, the weight average molecular weight is 10000 or more and 35000 or less, more preferably the acid value is 8 mgKOH / g or more and 20 mgKOH / g or less, and the weight average molecular weight. Is a crystalline polyester resin of 12000 or more and 30000 or less.
By setting the acid value and the weight average molecular weight of the resin in the above ranges, sharp melt properties are ensured and excellent low-temperature fixability can be obtained without adversely affecting the environmental dependency of charging.

As the crystalline polyester resin, one synthesized from a carboxylic acid (dicarboxylic acid) component and an alcohol (diol) component is used.
Hereinafter, the carboxylic acid component and the alcohol component will be described in more detail. In the present specification, the “crystalline polyester resin” includes a copolymer obtained by copolymerizing other components in a proportion of 50% by mass or less with respect to the main chain of the crystalline polyester resin.

  The carboxylic acid component is preferably an aliphatic dicarboxylic acid, and particularly preferably a linear carboxylic acid. For example, succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid Acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc., or lower alkyl esters thereof, Acid anhydrides can be mentioned but are not limited to these.

In addition to the aliphatic dicarboxylic acid component described above, the carboxylic acid component preferably contains constituent components such as a dicarboxylic acid component having a double bond and a dicarboxylic acid component having a sulfonic acid group. The dicarboxylic acid component having a double bond is derived from a lower alkyl ester of a dicarboxylic acid having a double bond, or an acid anhydride, in addition to a component derived from a dicarboxylic acid having a double bond. Components are also included.
Further, the dicarboxylic acid component having a sulfonic acid group is derived from a lower alkyl ester of a dicarboxylic acid having a sulfonic acid group, an acid anhydride, or the like in addition to a component derived from a dicarboxylic acid having a sulfonic acid group. Components are also included.

The dicarboxylic acid having a double bond can be suitably used to prevent hot offset at the time of fixing because the entire resin can be crosslinked using the double bond.
Examples of the dicarboxylic acid having a double bond include, but are not limited to, fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, fumaric acid, maleic acid and the like are preferable in terms of cost.

The dicarboxylic acid having a sulfonic acid group is effective in that the colorant such as a pigment can be well dispersed. Further, if a sulfonic acid group is present when the entire resin is emulsified or suspended in water to produce particles, it can be emulsified or suspended without using a surfactant as described later.
Examples of the dicarboxylic acid having a sulfonic acid group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, 5-sulfoisophthalic acid sodium salt and the like are preferable in terms of cost.

The carboxylic acid component other than the aliphatic dicarboxylic acid component (dicarboxylic acid component having a double bond and / or dicarboxylic acid component having a sulfonic acid group) in the total carboxylic acid component is 1 component mol% or more and 20 components It is preferably at most 2 mol%, more preferably at least 2 mol% and at most 10 mol%.
When the content is less than 1 mol%, the dispersibility of the pigment in the toner base particles may deteriorate when a pigment is used as the colorant. Further, when a toner is produced using the emulsion polymerization aggregation method, the emulsion particle diameter in the dispersion becomes large, and it may be difficult to adjust the toner diameter by aggregation. On the other hand, if it exceeds 20 component mol%, the crystallinity of the crystalline polyester resin is lowered, the melting point is lowered, and the storage stability of the image may be deteriorated. Further, when a toner is produced using an emulsion polymerization aggregation method, the emulsion particle size in the dispersion may be too small to dissolve in water, and latex may not be generated. In the present invention, “constituent mol%” refers to a percentage when each constituent component (carboxylic acid component, alcohol component) in the polyester resin is 1 unit (mol).

  On the other hand, the alcohol component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7. -Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14 -Tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol and the like are exemplified, but not limited thereto.

The alcohol component preferably has an aliphatic diol component content of 80 constituent mol% or more, and includes other components as necessary. As the alcohol component, the content of the aliphatic diol component is more preferably 90 constituent mol% or more.
If the content of the aliphatic diol component is less than 80 constituent mol%, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, image storage stability and low-temperature fixability are deteriorated. There is a case. On the other hand, examples of other components included as necessary include constituent components such as a diol component having a double bond and a diol component having a sulfonic acid group.

  Examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol, and the like. On the other hand, examples of the diol having a sulfonic acid group include 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, and 2-sulfo-1,4. -Butanediol sodium salt and the like.

  The content of alcohol components other than these linear aliphatic diol components (a diol component having a double bond and / or a diol component having a sulfonic acid group) in all alcohol components is 1 component mol% or more and 20 components. It is preferably at most 2 mol%, more preferably at least 2 mol% and at most 10 mol%. When the content is less than 1 constituent mol%, pigment dispersion may be poor, the emulsified particle diameter may be large, and adjustment of the toner diameter by aggregation may be difficult. On the other hand, if it exceeds 20 component mol%, the crystallinity of the polyester resin is lowered, the melting point is lowered, the image storage stability is deteriorated, or the emulsion particle size is too small to dissolve in water, and no latex is produced. There is a case.

  There is no restriction | limiting in particular as a manufacturing method of crystalline polyester resin, It manufactures by the general polyester polymerization method which makes a carboxylic acid component and an alcohol component react. For example, direct polycondensation, transesterification, and the like can be mentioned. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The crystalline polyester resin is produced at a polymerization temperature in the range of 180 ° C. or higher and 230 ° C. or lower, and the reaction system is reacted under reduced pressure as necessary to remove water and alcohol generated during condensation. When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. The polycondensation reaction is carried out while the solubilizing solvent is distilled off. If a monomer with poor compatibility exists in the copolymerization reaction, the monomer with poor compatibility and the monomer and the carboxylic acid component or alcohol component to be polycondensed are condensed in advance and then polycondensed together with the main component. Good.

  Examples of the catalyst used in the production of the crystalline polyester resin include alkali metal compounds such as sodium and lithium; alkaline earth metal compounds such as magnesium and calcium; zinc, manganese, antimony, titanium, tin, zirconium, germanium and the like. Metal compounds; phosphorous acid compounds, phosphoric acid compounds, amine compounds, and the like. Specific examples include the following compounds.

For example, sodium acetate, sodium carbonate, lithium acetate, calcium acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetra Butoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate , Zirconyl octylate, germanium oxide, triphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite Ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.
Among the catalysts containing metal elements capable of taking the valences of 2 or more listed above, calcium acetate is preferred from the viewpoint that it is easier to achieve both low-temperature fixability and gloss unevenness suppressing effect at a high level. It is preferable to use manganese acetate.

As described above, a crystalline polyester resin is suitable as the crystalline resin, but a crystalline vinyl resin can also be used.
Examples of the crystalline vinyl resin include amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, and (meth) acrylic acid. Decyl, undecyl (meth) acrylate, tridecyl (meth) acrylate, myristyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, oleyl (meth) acrylate, behenyl (meth) acrylate And vinyl resins using long-chain alkyl and alkenyl (meth) acrylic acid esters. In the present specification, the description “(meth) acryl” means that both “acryl” and “methacryl” are included.

In addition to the polymerizable monomer described above for the purpose of adjusting the melting temperature and molecular weight of the crystalline resin, a compound having a shorter chain alkyl group, alkenyl group, aromatic ring or the like may be used.
Specific examples include, for example, dicarboxylic acids, alkyldicarboxylic acids such as succinic acid, malonic acid, and oxalic acid, and phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, 4,4′-bibenzoic acid, 2, Aromatic dicarboxylic acids such as 6-naphthalenedicarboxylic acid and 1,4-naphthalenedicarboxylic acid, nitrogen-containing aromatic dicarboxylic acids such as dipicolinic acid, dinicotinic acid, quinolinic acid, and 2,3-pyrazinedicarboxylic acid, and diols In the case of short chain alkyl diols such as succinic acid, malonic acid, acetone dicarboxylic acid, diglycolic acid, etc., and in the case of short chain alkyl vinyl polymerizable monomers, methyl (meth) acrylate, ( Short chain alkyls such as ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and alkenyl (Meth) acrylic acid esters, vinyl nitriles such as acrylonitrile and methacrylonitrile, vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketones, ethylene, propylene, butadiene And olefins such as isoprene. These polymerizable monomers may be used individually by 1 type, and may use 2 or more types together.

The melting temperature of the crystalline resin is preferably in the range of 45 ° C. to 110 ° C., more preferably in the range of 50 ° C. to 100 ° C., and still more preferably in the range of 55 ° C. to 90 ° C.
When the melting point is lower than 45 ° C., it becomes difficult to store the toner, and when it exceeds 110 ° C., fixing in a low temperature region may be difficult. In addition, the melting temperature of crystalline resin means what was calculated | required by the method based on ASTMD3418-8.

  The number average molecular weight (Mn) of the crystalline resin is preferably 5000 or more, and more preferably 7000 or more. If the number average molecular weight (Mn) is less than 5000, the toner may penetrate into the surface of a recording medium such as paper at the time of fixing to cause uneven fixing, or the resistance to bending of the fixed image may be reduced. .

  The content of the crystalline resin contained in the toner base particles is preferably in the range of 2% by mass to 30% by mass, and more preferably in the range of 3% by mass to 15% by mass. When the content of the crystalline resin is less than 2% by mass, fixing in a low temperature region may be difficult. In addition, when the content of the crystalline resin exceeds 30% by mass, gloss unevenness is likely to occur or filming is likely to occur particularly when fixing is performed in an intermediate temperature range or a high temperature range.

-Amorphous resin-
In addition to the crystalline resin described above, an amorphous resin can be used in combination as the binder resin for the toner of this embodiment.
Examples of the amorphous resin include known resin materials, and examples thereof include polyester resins, polyurethane resins, epoxy resins, polyol resins, and the like, and amorphous polyester resins are preferable.

  The molecular weight of the amorphous resin that can be used is not particularly limited. However, when a toner is produced by using an emulsion polymerization aggregation method described later, an amorphous resin (high weight average molecular weight (Mw)) is high. It is preferable to use a non-crystalline resin (low molecular weight component) having a low molecular weight component and a molecular weight component.

  In this case, Mw of the high molecular weight component is preferably 30000 or more and 300000 or less, more preferably 30000 or more and 200000 or less, and further preferably 35000 or more and 150,000 or less. By controlling the Mw of the high molecular weight component within the above range, the crystalline resin can be more efficiently compatible with the crystalline resin, and separation of the crystalline resin once compatible can be suppressed.

On the other hand, the Mw of the low molecular weight component is preferably 8000 or more and 25000 or less, more preferably 8000 or more and 22000 or less, and further preferably 9000 or more and 20000 or less.
By controlling the Mw of the low molecular weight component within the above range, the inclusion of the high molecular weight component in the toner base particles is good when the aggregated particles obtained by aggregating the raw material components by the emulsion polymerization aggregation method are heated and fused. Thus, exposure of the crystalline resin to the surface of the toner base particles can be prevented.

  As described above, when the high molecular weight component and the low molecular weight component are mixed and used, the blending ratio of both is preferably in the range of high molecular weight component / low molecular weight component = 35/65 to 95/5, and 40/60 The range of thru | or 90/10 is more preferable, and the range of 50/50 thru | or 85/15 is still more preferable.

  The high molecular weight component preferably contains alkenyl succinic acid or its anhydride and trimellitic acid or its anhydride as its constituent monomers. Alkenyl succinic acid or its anhydride can be more easily compatible with the crystalline resin due to the presence of highly hydrophobic alkenyl groups.

  Examples of the alkenyl succinic acid component include n-dodecenyl succinic acid, isododecenyl succinic acid, n-octenyl succinic acid, acid anhydrides, acid chlorides thereof, and lower alkyl esters having 1 to 3 carbon atoms. By containing a trivalent or higher polyvalent carboxylic acid, the polymer chain has a crosslinked structure. By having a cross-linked structure, it is possible to obtain an effect of fixing the crystalline resin once compatible and making it difficult to separate.

  Examples of trivalent or higher polyvalent carboxylic acids include hemimellitic acid, trimellitic acid, trimesic acid, merophanic acid, planitic acid, pyromellitic acid, merit acid, 1,2,3,4-butanetetracarboxylic acid and These acid anhydrides, acid chlorides and lower alkyl esters having 1 to 3 carbon atoms can be mentioned.

  There is no restriction | limiting in particular in the manufacturing method of an amorphous polyester resin, It manufactures with the above-mentioned general polyester polymerization method. As the carboxylic acid component used for the synthesis of the amorphous polyester resin, various dicarboxylic acids mentioned for the crystalline polyester resin can be used. As the alcohol component, various diols used for the synthesis of the crystalline polyester resin can be used. In addition to the aliphatic diols mentioned for the crystalline polyester resin, for example, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene An oxide adduct, hydrogenated bisphenol A, bisphenol S, bisphenol S ethylene oxide adduct, bisphenol S propylene oxide adduct, or the like can be used. Furthermore, it is particularly preferable to use bisphenol S derivatives such as bisphenol S, bisphenol S ethylene oxide adduct, and bisphenol S propylene oxide adduct from the viewpoints of toner manufacturability, heat resistance, and transparency. Further, both the carboxylic acid component and the alcohol component may contain a plurality of components, and in particular, bisphenol S has an effect of improving heat resistance.

  The content ratio between the crystalline resin and the amorphous resin of the toner according to the exemplary embodiment is a mass ratio, and the ratio of crystalline resin: noncrystalline resin is preferably 2:98 or more and 16:84 or less, but 3:97. It is more preferably 16:84 or less, and still more preferably 4:96 or more and 15:85 or less.

-Crosslinking treatment of binder resin-
Next, the crystalline resin used as the binder resin, the crosslinking treatment of the non-crystalline resin used as necessary, and the copolymerization component that can be used in the synthesis of the binder resin will be described.

  In the synthesis of the binder resin, a compound having a hydrophilic polar group capable of copolymerizing other components can be used. As a specific example, when the binder resin is a polyester resin, for example, dicarboxylic acid compounds in which an aromatic ring such as sulfonyl-terephthalic acid sodium salt or 3-sulfonylisophthalic acid sodium salt is directly substituted are mentioned. When the binder resin is a vinyl resin, for example, unsaturated aliphatic carboxylic acids such as (meth) acrylic acid and itaconic acid, glycerin mono (meth) acrylate, fatty acid-modified glycidyl (meth) acrylate, and zinc mono (meth) acrylate , Zinc di (meth) acrylate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, esters of (meth) acrylic acid and alcohols such as polypropylene glycol (meth) acrylate, ortho, meta, para Examples include styrene derivatives having a sulfonyl group at any of the positions, sulfonyl group-substituted aromatic vinyls such as sulfonyl group-containing vinyl naphthalene, and the like.

In addition, a crosslinking agent may be added to the binder resin as necessary for the purpose of preventing uneven glossiness, uneven color development, hot offset, and the like during fixing in a high temperature region.

  In particular, in the crystalline polyester resin, for example, unsaturated polycarboxylic acids such as fumaric acid, maleic acid, itaconic acid, trans-aconitic acid, etc. are copolymerized in the polyester, and then the multiple bond portions in the resin are bonded together, Or you may use the method of bridge | crosslinking using another vinyl type compound. In addition, these crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more types.

  As a method of cross-linking with these cross-linking agents, a method of polymerizing and cross-linking with a cross-linking agent at the time of polymerization of the polymerizable monomer (monomer) may be used, or the unsaturated portion is left in the binder resin to polymerize the binder resin. Alternatively, the unsaturated portion may be cross-linked by a cross-linking reaction after toner preparation or after toner preparation.

When the binder resin is a polyester resin, the polymerizable monomer can be polymerized by condensation polymerization. As the polycondensation catalyst, known ones can be used. Specific examples include titanium tetrabutoxide, dibutyltin oxide, germanium dioxide, antimony trioxide, tin acetate, zinc acetate, tin disulfide and the like. It is done. When the binder resin is a vinyl resin, the polymerizable monomer can be polymerized by radical polymerization.

  In addition to the crystalline polyester resin, the binder resin has mainly been described above mainly for the non-crystalline polyester resin, but in addition, for example, styrene, parachlorostyrene, α-methylstyrene, etc. Styrenes; acrylic monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate; methyl methacrylate, ethyl methacrylate, n methacrylate -Methacrylic monomers such as propyl, lauryl methacrylate, 2-ethylhexyl methacrylate; and ethylenically unsaturated acid monomers such as acrylic acid, methacrylic acid, sodium styrenesulfonate; and acrylonitrile, methacrylonitrile, etc. Vinyl nitriles; vinyl methyl ether, vinyl Vinyl ethers such as ruisobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; homopolymers of olefin monomers such as ethylene, propylene and butadiene, and two of these monomers Copolymers combined with the above, or a mixture thereof, and further, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, etc., non-vinyl condensation resin, or those and the vinyl resin Or a graft polymer obtained by polymerizing a vinyl monomer in the presence of these.

  As will be described later, when the toner of this embodiment is produced by an emulsion polymerization aggregation method, the binder resin is prepared as a resin particle dispersion. This resin particle dispersion can be easily obtained by an emulsion polymerization method and a similar polymerization method in a heterogeneous dispersion system. Further, it can be obtained by a method in which a polymer polymerized uniformly by a solution polymerization method, a cage polymerization method or the like is added together with a stabilizer into a solvent in which the polymer is not dissolved and mechanically mixed and dispersed.

  For example, when a vinyl monomer is used, an ionic surfactant or the like is used, and resin particles are preferably obtained by emulsion polymerization or seed polymerization using an ionic surfactant and a nonionic surfactant in combination. A dispersion can be made.

  Examples of the surfactant used herein include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; Nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, alkyl alcohol ethylene oxide adducts, polyhydric alcohols, and various graft polymers, etc., are not particularly limited. Absent.

When preparing a resin particle dispersion by emulsion polymerization, a small amount of unsaturated acid such as acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid, etc. is added as a part of the monomer component to the particle surface. A protective colloid layer can be formed and soap-free polymerization is performed, which is particularly preferable.
The volume average particle size of the resin particles in the resin particle dispersion is preferably 1 μm or less, more preferably 0.01 μm or more and 1 μm or less. If the average particle size of the resin particles exceeds 1 μm, the particle size distribution of the finally obtained toner may be broadened, or free particles may be generated, leading to a decrease in performance and reliability.
On the other hand, if the volume average particle size of the resin particles is within the above range, the above disadvantages are eliminated, uneven distribution among the toners is reduced, dispersion in the toners is improved, and variations in performance and reliability are reduced. Is advantageous. The volume average particle diameter of the resin particles is measured using, for example, a laser diffraction particle size distribution measuring device (manufactured by Shimadzu Corporation, SALD2000A).

(Coloring agent)
The colorant used in the toner of the exemplary embodiment is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner.
For example, examples of the black pigment include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, and magnetite.

Examples of yellow pigments include yellow lead, zinc yellow, yellow iron oxide, cadmium yellow, chrome yellow, Hansa yellow, Hansa yellow 10G, benzidine yellow G, benzidine yellow GR, selenium yellow, quinoline yellow, and permanent yellow NCG. Is mentioned.
Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene brilliant orange RK, indanthrene brilliant orange GK and the like.

Red pigments include Bengala, cadmium red, red lead, mercury sulfide, watch young red, permanent red 4R, risor red, brilliantamine 3B, brilliantamine 6B, dapon oil red, pyrazolone red, rhodamine B rake, lake red C , Rose bengal, oxin red, alizarin lake and the like.
Blue pigments include bitumen, cobalt blue, alkali blue rake, Victoria blue rake, fast sky blue, induslen blue BC, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxare. Rate and so on.

Examples of purple pigments include manganese purple, fast violet B, and methyl violet lake.
Examples of the green pigment include chromium oxide, chromium green, pigment green, malachite green lake, final yellow green G, and the like.

Examples of white pigments include zinc white, titanium oxide, antimony white, and zinc sulfide.
Examples of extender pigments include barite powder, barium carbonate, clay, silica, white carbon, talc, and alumina white. Examples of the dye include various dyes such as basic, acidic, dispersed, and direct dyes, such as nigrosine.

These colorants are used alone or in combination, and further used in the form of a solid solution. These colorants are dispersed by a known method, and for example, a rotary shear type homogenizer, a media type dispersing machine such as a ball mill, a sand mill, or an attritor, a high-pressure opposed collision type dispersing machine, or the like is preferably used.
Further, when these colorants are used in the emulsion aggregation method described later, a polar surfactant is used and dispersed in an aqueous system by the homogenizer.

  In the exemplary embodiment, the amount of the colorant dispersed in the toner is preferably in the range of 4% by mass to 15% by mass with respect to the total mass of the toner, and in the range of 5% by mass to 10% by mass. More preferably.

Further, when the toner is used as magnetism, magnetic powder may be contained. As the magnetic powder, a material that is magnetized in a magnetic field is used, and it is a ferromagnetic powder such as iron, cobalt, or nickel, or a compound such as ferrite or magnetite. In particular, when a toner is obtained in an aqueous phase, it is necessary to pay attention to the water layer's ability to migrate to the water layer, solubility, and oxidation. .
When a magnetic material is used as the black colorant, it is added in the range of 30% by mass to 100% by mass with respect to the binder resin, unlike other colorants.

(Release agent)
A release agent is preferably used for the toner of this embodiment.
Specific examples of release agents that can be used include low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; silicones having a softening point; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide. Plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc. Mineral and petroleum waxes; ester waxes of higher alcohols with higher fatty acids such as stearyl stearate and behenyl behenate; butyl stearate, propyl oleate, glyceryl monostearate, diste Ester waxes of higher fatty acids such as phosphate glycerides and pentaerythritol tetrabehenate and unit price or polyhydric lower alcohols; higher esters such as diethylene glycol monostearate, dipropylene glycol distearate, distearic diglyceride, tetrastearic acid triglyceride Examples include ester waxes composed of fatty acids and polyhydric alcohol multimers; higher sorbitan fatty acid ester waxes such as sorbitan monostearate; higher cholesterol fatty acid ester waxes such as cholesteryl stearate.
In this embodiment, these mold release agents may be used individually by 1 type, and may be used in combination of 2 or more types.

  The addition amount of the release agent is preferably in the range of 5 to 25 parts by mass, more preferably in the range of 7 to 20 parts by mass with respect to 100 parts by mass of the binder resin. If the amount of release agent added is small, the releasability from the fixing member at the time of fixing may be insufficient, and offset may easily occur. Further, when the amount of the release agent added is large, there are cases where adverse effects such as deterioration of color developability and reduction of transparency are likely to occur.

(Other ingredients)
In the present embodiment, other components (particles) such as external additives, internal additives, charge control agents, and inorganic particles are added as necessary in addition to the binder resin, colorant, and release agent described above. Let

The toner of the exemplary embodiment preferably has at least one or more kinds of metal oxide particles and organic particles on the surface as an external additive for the purpose of imparting fluidity and improving cleaning properties.
Specific examples of the metal oxide particles include silica, titania, zinc oxide, strontium oxide, aluminum oxide, calcium oxide, magnesium oxide, cerium oxide, and composite oxides thereof. Of these, silica and titania are preferably used from the viewpoints of particle size, particle size distribution, and manufacturability. These metal oxide particles are preferably subjected to surface modification such as hydrophobization, and conventionally known methods are used as means for surface modification. Specific examples include coupling treatments such as silane, titanate, and aluminate.

Examples of organic particles include resin particles such as vinyl resin, polyester, and silicone. These particles may be used alone or as a mixture of plural kinds. The amount of addition to these toners is not particularly limited, but is preferably in the range of 0.1% by mass to 10% by mass, and more preferably in the range of 0.2% by mass to 8% by mass.
The gold oxide particles and organic particles are preferably added to the toner particle surfaces while being sheared.

  Examples of internal additives include metals such as ferrite, magnetite, reduced iron, cobalt, manganese, and nickel, alloys, and magnetic materials such as compounds containing these metals, and inhibit charging properties as toner characteristics. An amount not used is used.

  The charge control agent is not particularly limited, but when a color toner is used, a colorless or light color is preferably used. Examples include quaternary ammonium salt compounds, nigrosine compounds, dyes composed of complexes of aluminum, iron, chromium, and triphenylmethane pigments. From the viewpoint of controlling strength and reducing wastewater contamination, a material that is difficult to dissolve in water is preferred.

  In addition, inorganic particles may be added to the toner of the present embodiment in a wet manner in order to stabilize the chargeability. As the inorganic particles to be added, any of those usually used as external additives on the toner surface such as silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate can be used. It is preferable to use it dispersed in an acid or a polymer base.

  The content of the other components may be a level that does not hinder the purpose of the toner of the present embodiment, and is generally extremely small. Specifically, the content is 0.01% by mass or more and 5% by mass or less. It is a range, Preferably it is the range of 0.5 mass% or more and 2 mass% or less.

<Toner characteristics>
The volume average particle size of the toner of the exemplary embodiment is preferably in the range of 3 μm to 9 μm, and more preferably in the range of 3 μm to 8 μm. When the volume average particle diameter of the toner particles exceeds 9 μm, the ratio of coarse particles increases, and the reproducibility and gradation of fine lines and fine dots of the image obtained through the fixing process may be lowered. On the other hand, if the volume average particle size of the toner particles is less than 3 μm, the powder fluidity, developability, or transferability of the toner deteriorates, and the cleaning properties of the toner remaining on the surface of the image carrier deteriorate. Various troubles in other processes may occur due to the characteristic deterioration.

  Further, as the particle size distribution index of the toner particles used in the present invention, the volume average particle size distribution index GSDv is preferably 1.30 or less, and the ratio GSDv / GSDp to the number average particle size distribution index GSDp is 0.95 or more. It is more preferable that When the volume distribution index GSDv exceeds 1.30, the unevenness of the fixed image described above becomes large, and uneven glossiness may easily occur. Further, when the ratio between the volume average particle size distribution index GSDv and the number average particle size distribution index GSDp is less than 0.95, the amount of small particle size toner increases, and the amount of release agent contained per toner is uneven. May occur, and as a result, peeling failure may occur and a desired glossiness may not be obtained.

  The volume average particle size and the particle size distribution index were measured and calculated as follows. First, with respect to the divided particle size range (channel) of the toner particle size distribution measured using a Coulter Multisizer-II (manufactured by Beckman-Coulter) as a measuring device, the smaller diameter side of the volume and number of individual toner particles Draw the cumulative distribution, define the 16% cumulative particle size as the volume average particle size D16v and the number average particle size D16p, and the 50% cumulative particle size as the volume average particle size D50v (this value is the volume average Defined as D50p). Similarly, particle diameters that are 84% cumulative are defined as volume average particle diameters D84v and D84p. Using these, the volume average particle size distribution index GSDv is defined as (D84v / D16v) 1/2, and the number average particle size distribution index GSDp is defined as (D84p / D16p) 1/2.

  Furthermore, the toner shape factor SF1 in the present embodiment is preferably in the range of 110 to 145. If the shape factor SF1 is less than 110, the blade cleaning property of the transfer residual toner on the photoreceptor may be impaired. If the shape factor SF1 exceeds 145, the fluidity of the toner may be deteriorated, and the transfer property may be adversely affected from the beginning. .

Here, the shape factor SF1 is obtained by the following equation (1).
SF1 = (ML ² / A) × (π / 4) × 100 (1)
In the above formula (1), ML represents the absolute maximum length of the toner particles, and A represents the projected area of the toner particles.

  The SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image using an image analyzer, and is calculated as follows, for example. That is, an optical microscope image of the toner spread on the surface of the slide glass is taken into a Luzex image analyzer through a video camera, the maximum length and the projected area of 50 or more toner particles are obtained, calculated by the above formula (1), and the average Obtained by determining the value.

<Method for producing toner for developing electrostatic image>
The method for producing the electrostatic image developing toner of the present embodiment is not particularly limited, but as described above, the characteristics of the toner of the present embodiment limit the aluminum content in the toner surface layer portion and the toner, In view of the ease of controllability, a method of producing by an emulsion aggregation method is preferred.
Hereinafter, a method for producing the toner for developing an electrostatic charge image of the exemplary embodiment will be described in detail by an emulsion aggregation method.

In the method for producing a toner for developing an electrostatic charge image according to this embodiment, at least one resin particle dispersion and at least one colorant dispersion are mixed to form aggregated particles in the presence of aluminum ions. An aggregating step, a fusing step of heating the resin particles of the resin particle dispersion to a temperature equal to or higher than the glass transition temperature of the resin particles to fuse and coalesce the agglomerated particles to form toner particles, and washing the obtained toner particles And a cleaning step.
The manufacturing method is a manufacturing method for obtaining the electrostatic image developing toner according to the exemplary embodiment described above, in which the cleaning step includes at least a step of cleaning the toner particles with a treatment liquid containing a chelating agent. .

  That is, the above production method generally uses a dispersion of resin particles produced by emulsion polymerization or the like using an ionic surfactant, and a colorant dispersion dispersed in an ionic surfactant of the opposite polarity. In this method, heteroaggregation is caused, aggregated particles corresponding to the toner diameter are formed, and then the aggregated particles are fused and coalesced by heating to a temperature higher than the glass transition temperature of the resin, followed by washing and drying. The toner shape can be manufactured from an irregular shape to a spherical shape. In the toner of this embodiment, a release agent particle dispersion can be added.

The manufacturing method is a method of mixing raw material dispersions in a lump, and aggregating and fusing them, but shifting the balance of the amount of the polar ionic dispersant in the initial stage of the aggregation process, For example, an inorganic metal salt containing at least aluminum or a polymer containing at least aluminum is ionically neutralized to form core agglomerated particles below the glass transition temperature. After stabilization by slightly heating at a high temperature below the glass transition temperature or melting temperature of the resin contained in the core agglomerated particles or additional particles, if necessary, compensate for the above-mentioned balance deviation as the second step Add a particle dispersion with the polarity and amount to be added, and if necessary, slightly increase the temperature below the glass transition temperature of the resin contained in the core aggregated particles or additional particles. After stabilizing by heating, fusing and coalescing remain adhered to the surface of the second stage added particles of core aggregated particles is heated above the glass transition temperature.
In the following, description will be given in order.

  The resin particle dispersion is formed by applying a shearing force to a solution obtained by mixing an aqueous medium and a mixed liquid (polymer liquid) containing a resin and, if necessary, a colorant. At that time, by heating to a temperature higher than the softening point of the resin, the viscosity of the polymer liquid is lowered to form a particle dispersion.

Examples of the disperser used when forming the resin particle dispersion include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser.
Examples of the dispersion medium in the resin particle dispersion, the colorant dispersion described later, the release agent dispersion, and other components in the present embodiment include an aqueous medium.

Examples of the aqueous medium include water such as distilled water and ion exchange water, alcohol, and the like. These may be used alone or in combination of two or more.
Further, a surfactant can be used for the purpose of stabilizing the dispersion of each dispersion.
Examples of the surfactant include anionic surfactants such as sulfate, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable.

  In the toner according to the exemplary embodiment, an anionic surfactant generally has a strong dispersion force and is excellent in dispersion of resin particles and a colorant. Therefore, an anionic surfactant is used as a surfactant for dispersing a release agent. It is advantageous to use a system surfactant.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate , Sodium alkylnaphthalene sulfonate such as dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate; sulfones such as naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Acid salts; lauryl phosphate, isopropyl phosphate, nonylphenyl ether Phosphoric acid esters such as Sufeto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate; sulfosuccinate salts such as sulfosuccinate lauryl disodium; and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyldimethylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleylbispolyoxyethylenemethylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene Trimethylammonium chloride, Quaternary ammonium salts such as quilts trimethyl ammonium chloride; and the like.

The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant.
Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Alkyl phenyl ethers such as ethylene nonyl phenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene Alkylamines such as oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate And so on.

Surfactant may be used individually by 1 type and may be used in combination of 2 or more type.
The content of the surfactant in each dispersion is generally a small amount, specifically in the range of 0.01% by mass to 10% by mass, more preferably 0.05% by mass or more. It is the range of 5 mass% or less, More preferably, it is the range of 0.1 mass% or more and 2 mass% or less. When the content is less than 0.01% by mass, each dispersion such as a resin particle dispersion, a colorant dispersion, and a release agent dispersion becomes unstable, so that aggregation occurs, and each particle during aggregation Since the stability of the particles differs, problems such as the release of specific particles may occur. When the amount exceeds 10% by mass, the particle size distribution of the particles becomes wide, and the control of the particle size becomes difficult. It is not preferable for reasons such as the above. In general, a suspension polymerization toner dispersion having a large particle size is stable even if the amount of the surfactant used is small.

  Moreover, a room temperature (25 degreeC) solid aqueous polymer etc. can also be used. Specifically, cellulose compounds such as carboxymethyl cellulose and hydroxypropyl cellulose, polyvinyl alcohol, gelatin, starch, gum arabic and the like are used.

  In addition, the colorant dispersion is prepared by using an ionic surfactant having a polarity opposite to that of the ionic surfactant used in the preparation of the resin particle dispersion to remove the colorant particles of a desired color such as blue, red, and yellow. Prepare by dispersing in.

  Furthermore, the release agent dispersion liquid is a homogenizer that disperses the release agent in water together with a polymer electrolyte such as an ionic surfactant, a polymer acid, or a polymer base, and heats above the melting point and applies strong shear. Or by granulating with a pressure discharge type disperser.

  The resin particle diameter of the resin particle dispersion in the present embodiment is 1 μm or less in terms of volume average particle diameter, and is preferably in the range of 100 nm to 300 nm. When the volume average particle size exceeds 1 μm, the particle size distribution of toner particles obtained by agglomeration and fusion may be broadened, or free particles may be generated, resulting in a decrease in toner performance and reliability. If it is less than 100 nm, it may take time to coagulate and grow the toner, which may not be industrially suitable. If it exceeds 300 nm, the dispersion of the release agent and the colorant becomes non-uniform and control of the toner surface properties. May be difficult.

  In the aggregation step, the resin particle dispersion, the colorant dispersion, and, if necessary, the particles in the release agent dispersion are aggregated to form aggregated particles. The agglomerated particles are formed by heteroaggregation or the like. For the purpose of stabilizing the agglomerated particles and controlling the particle size / particle size distribution, the ionic surfactant having a polarity different from that of the agglomerated particles, or a monovalent or more monovalent metal salt or the like is used. A charged compound is added.

  Further, even if the process is performed by mixing and agglomerating all at once, in the agglomeration step, the initial balance of the amount of the ionic dispersant of each polarity is shifted in advance, and the ionic surfactant is Alternatively, a compound having a monovalent or higher charge, such as a metal salt, is ionically neutralized to form and stabilize the first-stage matrix aggregation below the glass transition temperature, and then as the second stage. After adding and coating a resin particle dispersion treated with a polar and quantity dispersing agent to compensate for the balance deviation, further heating below the glass transition temperature of the resin contained in the matrix or additional particles as necessary. Even after being stabilized at a high temperature, the particles added in the second stage of agglomeration by heating above the glass transition temperature are combined in a state of adhering to the surface of the agglomerated particles (attached particles). Good. Furthermore, the stepwise operation of aggregation may be repeated several times.

In the method for producing a toner for developing an electrostatic charge image of the present invention, particles can be prepared by causing aggregation by pH change in the aggregation step. At the same time, a flocculant is added in order to stably and rapidly aggregate the particles, or to obtain agglomerated particles having a narrower particle size distribution.
The flocculant is not particularly limited, and a metal salt of an inorganic acid is used as the flocculant in consideration of the stability of the flocculent particles, the stability of the flocculant with respect to heat and time, and removal during washing. Specific examples include metal salts of inorganic acids such as magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, and sodium carbonate. In the present invention, final toner particles From the viewpoint of controlling the viscosity at the time of fixing, an aggregating agent containing aluminum (for example, polyaluminum chloride, aluminum sulfate, potassium alum, etc.) is used.
The amount of the flocculant added varies depending on the valence of the electric charge, but all of them are small, and in the case of trivalent such as aluminum, it is about 0.5% by mass or less. Since the amount of the flocculant is preferably small, it is preferable to use a compound having a large valence.

  As the means for controlling the aluminum content in the toner in this embodiment, a method of controlling the aluminum content in the toner by adjusting the amount of the aluminum-containing flocculant such as polyaluminum chloride and aluminum sulfate used in the aggregation step. At the end of the agglomeration process, an appropriate amount of a so-called chelating agent such as EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), NTA (nitrilotriacetic acid) is added, and aluminum ions are trapped and formed in the washing process, etc. And a method of removing the complex salt.

  After passing through the aggregating step, an attaching step may be performed if necessary. In the attaching step, the coating layer is formed by attaching the resin particles to the surface of the aggregated particles formed through the aggregation step. Thus, a toner having a so-called core layer and a core / shell structure covering the core layer is obtained.

  The coating layer is usually formed by additionally adding a resin particle dispersion containing amorphous resin particles to the dispersion in which aggregated particles (core particles) are formed in the aggregation step. When an amorphous resin is used in addition to the crystalline resin in the aggregation process, the amorphous resin used in the adhesion process may be the same as or different from that used in the aggregation process.

  In general, the adhesion process is used when a toner having a so-called core / shell structure in which a crystalline resin as a main component is contained as a binder resin together with a release agent, and the main purpose thereof is the core layer. The purpose is to suppress the exposure of the release agent and the crystalline resin contained on the toner surface, and to supplement the strength of the toner particles, which is insufficient with the core layer alone.

  After the aggregation process, or the aggregation process and the adhesion process, the aggregated particles are united in the fusion process. In the fusion step, under the same agitation as in the aggregation step, the pH of the suspension of the aggregated particles is set in the range of 5 to 10 to stop the progress of aggregation, and in the aggregated particles in the solution. If the melting temperature of the crystalline resin contained is higher than the highest temperature, or if amorphous resin particles (including the shell layer constituting resin) are included, the glass transition temperature of the amorphous resin particles (type of resin) In the case of two or more types, the toner particles are obtained by heating to the glass transition temperature of the resin having the highest glass point transition temperature) and fusing and coalescing.

  The heating temperature is not a problem as long as it is equal to or higher than the glass transition temperature of the resin. The fusion and coalescence can be promoted preferably by carrying out at a glass transition temperature of the resin + 10 ° C. or higher, more preferably + 15 ° C. or higher.

  In addition, the heating time may be performed so as to be united, and may be performed for 0.2 hours or more and 10 hours or less. Thereafter, when the temperature is lowered to the glass transition temperature or lower of the resin to solidify the particles, the particle shape and surface properties may change depending on the temperature lowering rate. For example, when the temperature is lowered at a high speed, the spheroidization and the surface are easily smoothed. On the other hand, when the temperature is slowly lowered, the particle shape becomes indefinite and irregularities are easily generated on the particle surface. Therefore, it is preferable to lower the temperature at a rate of at least 0.5 ° C./min, preferably at a rate of 1.0 ° C./min.

  After completion of the aggregation process and the fusion process, toner is obtained as fused particles. The fused particles (toner) obtained by fusing need to be washed through a solid-liquid separation process such as filtration, as will be described later.

  As described above, in the toner of this embodiment, the aluminum content in the toner surface layer is in the range of 0.05 to 0.15 in the Net intensity by fluorescent X-ray analysis, and the aluminum content inside the toner. However, in the Net intensity | strength by a fluorescent X ray analysis, it is the range of 0.20 or more and 0.50 or less. In order to obtain this toner, the cleaning step includes a step of cleaning the toner with a treatment liquid containing a chelating agent.

  Examples of the chelating agent include EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), NTA (nitrilotriacetic acid), TTHA (triethylenetetraaminehexaacetic acid), HIDA (hydroxyethyliminodiacetic acid), and HEDTA (hydroxyethyl). Ethylenediamine triacetic acid), HEDP (hydroxyethylidene diphosphonic acid), and HIDS (3-hydroxy-2,2′-iminodisuccinic acid), and acids having a polar group and salts thereof, or acids having a hydroxy group and their A salt is more preferred.

In the present embodiment, it is preferable to include at least a step of washing with a treatment liquid containing 3-hydroxy-2,2′-iminodisuccinic acid.
The reason why the constituent requirements of the present invention can be satisfied by including at least a step of washing with a treatment liquid containing 3-hydroxy-2,2′-iminodisuccinic acid is not clear, but is considered as follows. 3-Hydroxy-2,2′-iminodisuccinic acid is a so-called chelating agent having the ability to complex metal ions. Since this material has a hydroxyl group in the molecular structure, it has high hydrophilicity and does not complex up to aluminum inside the toner, and tends to chelate only the toner surface layer portion. Therefore, it is considered that the ionic crosslinking can be reduced only in the toner surface layer portion while leaving many ionic crosslinking inside the toner.
In other words, in the toner surface layer portion, the aluminum content is reduced and the ionic cross-linking structure is reduced, so that the thermal fluidity is improved, and inside the toner, the aluminum content is high and the ionic cross-linking structure is maintained, so that the viscosity is increased. High, resulting in low gloss.

Hereinafter, although the suitable example of a washing | cleaning process is described, this embodiment is not limited to this.
The toner obtained through the fusing step is washed with a treatment liquid containing 3-hydroxy-2,2′-iminodisuccinic acid. Specifically, 3-hydroxy-2,2′-iminodisuccinic acid is dissolved in 5 to 10 parts by mass of ion exchange water with respect to 100 parts by mass of the toner, and the pH is adjusted to 10 or more and 12 or less. A method in which the toner is dispersed and washed with stirring is preferred.

  If the treatment liquid contains 5 parts or more of 3-hydroxy-2,2′-iminodisuccinic acid with respect to 100 parts of the toner, the aluminum content of the toner surface layer part can be sufficiently reduced and controlled within a predetermined range. Yes. In addition, if it is 10 parts or less of 3-hydroxy-2,2′-iminodisuccinic acid, the aluminum content of the toner surface layer can be controlled within a predetermined range without excessively reducing, and the environmental load due to waste water after treatment Can be reduced.

  If the pH is in the range of 10 or more and 12 or less, the chelating ability of 3-hydroxy-2,2′-iminodisuccinic acid is maintained, and it is suitable for controlling the aluminum content of the toner surface layer portion to a predetermined range. It is.

  More preferably, the washing step of the present invention includes at least a step of washing with a treatment solution containing 3-hydroxy-2,2′-iminodisuccinic acid. You may add the process of carrying out displacement washing with exchange water.

  The toner that has undergone the washing step obtains desired toner particles through a solid-liquid separation step and a drying step. Although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity.

  The toner for developing an electrostatic charge image of the present invention can be produced by preparing toner particles (base particles) as described above, adding the inorganic particles to the toner particles, and mixing with a Henschel mixer or the like.

<Electrostatic image developer>
The electrostatic charge image developer of the present embodiment is not particularly limited except that it contains the electrostatic latent image developing toner of the present embodiment, and can take a component composition according to the purpose. The electrostatic image developer of this embodiment becomes a one-component electrostatic image developer when the electrostatic image developing toner is used alone, and a two-component electrostatic image developer when used in combination with a carrier. It becomes.

For example, when the carrier is used, the carrier is not particularly limited, and examples thereof include known carriers, such as those described in JP-A Nos. 62-39879 and 56-11461. A known carrier such as a resin-coated carrier can be used.
Specific examples of the carrier include the following resin-coated carriers. Examples of the core particle of the carrier include normal iron powder, ferrite, magnetite molding, and the like, and the volume average particle diameter is in the range of 30 μm to 200 μm.

  Examples of the coating resin for the resin-coated carrier include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, acrylic acid 2 -Α-methylene fatty acid monocarboxylic acids such as ethylhexyl, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; nitrogen-containing acrylics such as dimethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, etc. Vinyl nitriles; vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine;

Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; Olefins such as ethylene and propylene; Vinylidene fluoride, tetrafluoroethylene, hexafluoroethylene and the like Homopolymers such as vinyl-based fluorine-containing monomers; copolymers comprising two or more types of monomers; silicone resins including methylsilicone and methylphenylsilicone; polyesters including bisphenol and glycol; epoxy Examples thereof include resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and polycarbonate resins.
These resins may be used alone or in combination of two or more.

  The coating amount of the coating resin is preferably in the range of 0.1 to 10 parts by mass and more preferably in the range of 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the core particles. .

  For the production of the carrier, a heating type kneader, a heating type Henschel mixer, a UM mixer, or the like is used. Depending on the amount of the coating resin, a heating type fluidized rolling bed, a heating type kiln, or the like is used.

  The mixing ratio (mass ratio) of the electrostatic charge image developing toner of the present embodiment and the carrier in the two-component developer is not particularly limited and is selected according to the purpose, but toner: carrier = 1: 100. The range of about 30: 100 is desirable, and the range of about 3: 100 to 20: 100 is more desirable.

<Image forming apparatus>
Next, an image forming apparatus according to this embodiment using the electrostatic image developing toner according to this embodiment will be described.
The image forming apparatus according to the present embodiment includes a latent image holding member, a developing unit that develops an electrostatic latent image formed on the latent image holding member as a toner image with a developer, and a latent image holding member on the latent image holding member. Transfer means for transferring the formed toner image onto the transfer body, fixing means for fixing the toner image transferred onto the transfer body, and the latent image holding body by rubbing with a cleaning member to transfer residual components And the electrostatic charge image developer according to this embodiment is used as the developer. Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. The main parts shown in the figure will be described, and the description of the other parts will be omitted.

  In this image forming apparatus, for example, the part including the developing unit may be a cartridge structure (process cartridge) that is detachable from the main body of the image forming apparatus. As the process cartridge, a developer holding body is used. A process cartridge according to this embodiment that is provided at least and contains the electrostatic charge image developer according to this embodiment is preferably used.

  FIG. 1 is a schematic configuration diagram illustrating a four-tandem color image forming apparatus which is an example of an image forming apparatus according to the present embodiment. The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter simply referred to as “units”) 10Y, 10M, 10C, and 10K are juxtaposed at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that can be attached to and detached from the main body of the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a driving roller 22 and a support roller 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other from the left to the right in the drawing. It is designed to travel in the direction toward 10K. The support roller 24 is urged away from the drive roller 22 by a spring or the like (not shown), and a predetermined tension is applied to the intermediate transfer belt 20 wound around the support roller 24. An intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the drive roller 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K includes yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The four colors of toner can be supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K described above have the same configuration, here, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction. 10Y will be described as a representative. Note that the second to fourth units are denoted by reference numerals with magenta (M), cyan (C), and black (K) instead of yellow (Y) in the same parts as the first unit 10Y. Description of 10M, 10C, 10K is omitted.

The first unit 10Y has a photoreceptor 1Y that functions as a latent image holding member. Around the photosensitive member 1Y, a charging roller 2Y for charging the surface of the photosensitive member 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on a color-separated image signal to form an electrostatic latent image. An exposure device 3 to be formed, a developing device (developing means) 4Y for supplying the electrostatic latent image with charged toner and developing the electrostatic latent image, and a primary transfer roller for transferring the developed toner image onto the intermediate transfer belt 20 5Y (primary transfer unit) and a photoconductor cleaning device (cleaning unit) 6Y for removing toner remaining on the surface of the photoconductor 1Y after the primary transfer are sequentially arranged.
The primary transfer roller 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roller under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described. First, prior to the operation, the surface of the photoreceptor 1Y is charged to a potential of about −600V to −800V by the charging roller 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate. Here, conductivity refers to conductivity having a volume resistivity of less than 10 ⁷ Ω · cm measured based on JIS K 7194 “Resistivity Test Method for Conductive Plastics by Four-Probe Method”. This photosensitive layer usually has a high resistance (a resistance equivalent to that of a general resin), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic latent image of a yellow print pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic latent image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y is reduced. On the other hand, it is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic latent image formed on the photoreceptor 1Y in this way is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic latent image on the photoreceptor 1Y is converted into a visible image (toner image) by the developing device 4Y.

  In the developing device 4Y, yellow toner according to the present embodiment is accommodated. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged charge on the photoreceptor 1Y, and a developer roll (developer holder). Is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a predetermined primary transfer bias is applied to the primary transfer roller 5Y, and the electrostatic force directed from the photoreceptor 1Y to the primary transfer roller 5Y generates toner. By acting on the image, the toner image on the photoreceptor 1 </ b> Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time is a (+) polarity opposite to the polarity (−) of the toner, and is controlled to about +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rollers 5M, 5C, and 5K after the second unit 10M is also controlled according to the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner.

  The intermediate transfer belt 20 onto which the four color toner images have been transferred through the first to fourth units is arranged on the image transfer surface side of the intermediate transfer belt 20 and the support roller 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roller (secondary transfer means) 26 is connected to a secondary transfer portion. On the other hand, a recording paper (transfer object) P is fed at a predetermined timing into a gap where the secondary transfer roller 26 and the intermediate transfer belt 20 are pressed against each other via a supply mechanism, and a predetermined secondary transfer bias is provided. Is applied to the support roller 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, and the transfer bias is applied to the intermediate transfer belt 20. The toner image is transferred onto the recording paper P. Note that the secondary transfer bias at this time is determined according to the resistance detected by a resistance detecting means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

Thereafter, the recording paper P is sent to a fixing device (fixing means) 28, where the toner image is heated, and the color-superposed toner image is melted and fixed on the recording paper P. The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.
The image forming apparatus exemplified above is configured to transfer the toner image onto the recording paper P via the intermediate transfer belt 20, but the present invention is not limited to this configuration, and the toner image is directly transferred from the photoconductor. It may be a structure that is transferred to a recording sheet.

Since the image forming apparatus of the present embodiment uses the electrostatic image developing toner of the present embodiment,
Compared to the case where the toner surface layer and the aluminum content in the interior are not taken into consideration, the low-temperature fixability is hardly impaired, and an image having low gloss and excellent image reproducibility can be obtained.

<Process cartridge, toner cartridge>
FIG. 2 is a schematic configuration diagram showing a preferred example of a process cartridge containing the electrostatic charge image developer according to the present embodiment. In the process cartridge 200, a charging roller 108, a developing device 111, a photosensitive member cleaning device (cleaning means) 113, an opening 118 for exposure, and an opening 117 for static elimination exposure are attached to a rail 116 together with the photosensitive member 107. Are combined and integrated with each other. In FIG. 2, reference numeral 300 represents a transfer object.
The process cartridge 200 is detachable from an image forming apparatus main body including a transfer device 112, a fixing device 115, and other components (not shown). It forms a forming apparatus.

  The process cartridge shown in FIG. 2 includes a charging roller 108, a developing device 111, a cleaning device (cleaning means) 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. Are combined selectively. In the processel cartridge according to the present embodiment, in addition to the photoconductor 107, the charging roller 108, the developing device 111, the photoconductor cleaning device (cleaning means) 113, the opening 118 for exposure, and the discharge exposure. You may provide at least 1 sort (s) selected from the group comprised from the opening part 117. FIG.

  Next, the toner cartridge according to this embodiment will be described. The toner cartridge according to the present exemplary embodiment is a toner cartridge that is attached to and detached from the image forming apparatus and stores at least toner to be supplied to a developing unit provided in the image forming apparatus. The toner according to the embodiment is used. Note that the toner cartridge according to the present embodiment only needs to contain at least toner, and may contain developer, for example, depending on the mechanism of the image forming apparatus.

  Therefore, in the image forming apparatus having a configuration in which the toner cartridge can be attached and detached, the toner according to the present embodiment can be easily supplied to the developing device by using the toner cartridge containing the toner according to the present embodiment.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which the toner cartridges 8Y, 8M, 8C, and 8K can be attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are each developing devices (colors). And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge is low, the toner cartridge can be replaced.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. In the following description, “part” represents “part by mass” and “%” represents “% by mass” unless otherwise specified.

  Each toner used in the examples and comparative examples is prepared by preparing the following resin particle dispersion and colorant dispersion, respectively, mixing them at a predetermined ratio, stirring them, and mixing them with an inorganic metal salt containing at least aluminum. The polymer was added and ionically neutralized to form aggregated particles. Thereafter, the pH of the system was adjusted from weakly acidic to neutral with an inorganic hydroxide, and then heated to a temperature higher than the glass transition temperature of the resin particles to be fused and united. Then, the desired toner was obtained through sufficient steps of washing, solid-liquid separation, and drying.

<Measuring method of various characteristics>
First, methods for measuring physical properties of toners and the like used in Examples and Comparative Examples will be described.

(Measurement method of weight average molecular weight of resin)
The molecular weight distribution of the resin was performed under the following conditions. GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)”, and the column uses two “TSKgel, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)” THF (tetrahydrofuran) was used as an eluent. As experimental conditions, an experiment was performed using a sample concentration of 0.5%, a flow rate of 0.6 ml / min, a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

(Measurement of acid value of resin)
Weigh accurately 1 to 20 g of the sample (resin), add 100 ml of the ethyl ether-ethyl alcohol mixture or benzene-ethyl alcohol mixture, and a few drops of phenolphthalein solution as an indicator, and make sure that the sample is completely dissolved. Shake.
After the sample is dissolved, titrate with the alcoholic potassium hydroxide solution, and when the indicator is light red for 30 seconds, the end point of neutralization is obtained. From the amount used at that time, the acid value (AV) is obtained by the following formula. It was.
AV = (B × 5.61) ÷ M
Here, AV represents the acid value (mg KOH / g), B represents the amount of use of 0.1 mol / liter potassium hydroxide ethyl alcohol solution (ml), and M represents the mass (g) of the sample.

(Measuring method of resin melting temperature and glass transition temperature)
The melting temperature of the toner and the crystalline resin, and the glass transition temperature of the toner and the amorphous resin were determined from each maximum peak measured according to ASTM D3418-8. The glass transition temperature was the temperature at the intersection of the extension line of the base line and the rising line in the endothermic part, and the melting temperature was the temperature at the top of the endothermic peak.
For the measurement, a differential scanning calorimeter (DSC-60A with automatic cooler, manufactured by Shimadzu Corporation) was used.

(Measurement method of volume average particle diameter of resin particles and colorant particles)
Volume average particle diameters of resin particles, colorant particles, and the like were measured with a laser diffraction particle size analyzer (manufactured by Shimadzu Corporation, SALD2000A).

(Measurement method of aluminum content)
The content of the aluminum element in the toner surface layer portion and in the toner according to the present embodiment is obtained from element designation analysis using a fluorescent X-ray apparatus. The sample was 6 g of toner, pressure-molded with a pressure molder with a load of 10 t and a pressurization time of 1 minute. Using a fluorescent X-ray (XRF-1500) manufactured by Shimadzu Corporation, the measurement conditions were a tube voltage of 40 kV, It is obtained from the elemental composition ratio measured at a tube current of 90 mA and a measurement time of 30 minutes.
Here, the toner surface layer part is obtained by mixing 1 part of the toner with a solution containing 5 parts of methanol and 5 parts of tetrahydrofuran at 25 ° C., and using an ultrasonic disperser Tetora 150 (manufactured by Nikka Ki Bios). The portion of the toner that dissolves in the solution when vibrated at 50 kHz for 3 minutes is indicated, and the inside of the toner indicates the portion of the toner that does not dissolve in the solution under the same conditions.

  In this embodiment, an unfixed image was prepared using a Fuji Xerox Co., Ltd. DocuCenter Color 400 CP remodeling machine, and an unfixed image was formed using a Premiere 80 manufactured by Xerox Co., Ltd. as a transfer sheet. For fixing the unfixed image, the fixing device for DucPrint 340 was removed, and the heating roller temperature and the pressure roller temperature could be freely set, and an offline fixing device modified to be monitored was used. The image fixing property, gloss, and image disturbance were evaluated according to the following methods while increasing the fixing temperature stepwise from 100 ° C. to 160 ° C.

(Measurement method of fixing temperature)
The image surface of each obtained fixed image was valley-folded to observe the degree of peeling of the image at the crease portion, and the width of the paper appearing at the fold portion as a result of the image peeling was measured. The fixing temperature at which the width was 0.5 mm or less was defined as MFT (minimum fixing temperature, ° C.). The allowable range is 140 ° C. or less.

(Gloss measurement method)
The glossiness at a light incident angle of 75 degrees with respect to the fixed image thus fixed was determined using Gloss Meter GM-26D (manufactured by Murakami Color Research Laboratory). The allowable range is 10% or less.

(Image disturbance evaluation method)
The image disturbance was evaluated by visual evaluation according to the following evaluation criteria.
◎: Solid image has no density unevenness and fine line reproducibility is good. △: Slight density unevenness is observed on solid image or fine line unevenness is observed. ×: Density unevenness is clearly observed on solid image. Or uneven thin lines are noticeable

<Toner production method>
-Preparation of crystalline polyester resin dispersion-
60 parts by weight of methyl ethyl ketone and 15 parts by weight of isopropyl alcohol (IPA) were added to a 2 L separable flask equipped with an anchor blade for supplying stirring power, a reflux device, and a decompression device using a vacuum pump, and nitrogen was added at 0.2 L / m. The air was supplied at a speed, and the air in the system was replaced with nitrogen. Next, 100 parts by weight of the crystalline polyester resin was slowly added while being heated to 60 ° C. by an in-system oil bath device, and dissolved while stirring. Next, 5 parts by weight of 10% aqueous ammonia was added thereto, and then 300 parts by weight of ion-exchanged water was added thereto at a rate of 9.6 g / m with stirring using a metering pump. Emulsification was completed when the emulsification system was milky white and the stirring viscosity was reduced.
Subsequently, this was decompressed to -700 Torr and stirred. When the reflux amount reached 210 parts by weight, this was taken as the end point, and overheating was stopped and the mixture was cooled to room temperature (25 ° C.) while stirring. The particle size of the obtained resin particles was measured using a laser diffraction / scattering particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.). The obtained emulsion resin particles had an average particle size of 180 nm and a solid content of 30%. The acid value of the crystalline polyester resin was 17.4 mgKOH / g, and the weight average molecular weight was 24300.

-Preparation of non-crystalline polyester resin dispersion-
60 parts by weight of methyl ethyl ketone and 15 parts by weight of isopropyl alcohol (IPA) were added to a 2 L separable flask equipped with an anchor blade for supplying stirring power, a reflux device, and a decompression device using a vacuum pump, and nitrogen was added at 0.2 L / m. The air was supplied at a speed, and the air in the system was replaced with nitrogen. Next, 100 parts by weight of an amorphous polyester resin was slowly added while being heated to 60 ° C. by an in-system oil bath device, and dissolved while stirring. Next, 5 parts by weight of 10% aqueous ammonia was added thereto, and then 300 parts by weight of ion-exchanged water was added thereto at a rate of 9.6 g / m with stirring using a metering pump. Emulsification was completed when the emulsification system was milky white and the stirring viscosity was reduced.
Subsequently, this was decompressed to -700 Torr and stirred. When the reflux amount reached 210 parts by weight, this was taken as the end point, and overheating was stopped and the mixture was cooled to room temperature (25 ° C.) while stirring. The particle size of the obtained resin particles was measured using a laser diffraction / scattering particle size distribution measuring device (LA-920, manufactured by Horiba, Ltd.). The obtained emulsion resin particles had an average particle size of 180 nm and a solid content of 30%.

-Preparation of colorant dispersion-
Black pigment (NIPex35: manufactured by DEGUSSA) 45.0 parts by weight Ionic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5.0 parts by weight Ion-exchanged water 200 parts by weight ) To obtain a colorant dispersion having a center particle size of 168 nm and a solid content of 25%.

-Preparation of release agent dispersion-
Paraffin wax FNP92 (manufactured by Nippon Seiwa Co., Ltd.) 45 parts by weight Cationic surfactant Neogen RK (Daiichi Kogyo Seiyaku) 5 parts by weight Ion exchange 200 parts by weight The above is heated to 60 ° C. to make an ultra-Turrax T50 made by IKA After dispersion, the mixture was dispersed with a pressure discharge type gorin homogenizer to obtain a release agent dispersion having a center diameter of 170 nm and a solid content of 25%.

-Production of Toner 1-
In a polymerization kettle equipped with a pH meter, a stirring blade, and a thermometer, among the above raw materials, 340 parts of an amorphous polyester resin particle dispersion, 46 parts of a crystalline polyester resin particle dispersion, 430 parts of ion-exchanged water, After 51 parts of the colorant dispersion and 74 parts of the release agent dispersion were added and mixed, the pH of the raw material mixture was adjusted to 2.7 by adding a 0.3 M nitric acid aqueous solution.
Subsequently, 100 parts of 10% aqueous solution of aluminum sulfate was added dropwise as a flocculant while applying a shearing force at 1000 rpm with Ultraturrax (manufactured by IKA Japan). In addition, since the viscosity of the raw material mixture increases during the dropping of the flocculant, the dropping speed was reduced when the viscosity increased, so that the flocculant was not biased to one place. When the dropping of the flocculant was completed, the rotational speed was further increased to 6000 rpm and the mixture was stirred for 5 minutes to sufficiently mix the flocculant and the raw material mixture.
Next, the raw material mixture was stirred at 550 rpm or more and 650 rpm or less while heating to 30 ° C. with a mantle heater. After stirring for 60 minutes, it was confirmed that the primary particle size was stably formed using Multisizer II type (aperture diameter: 50 μm, manufactured by Beckman-Coulter), and then 0.5 ° C / The temperature was raised to 45 ° C in minutes. The growth of the agglomerated particles is confirmed at any time using Multisizer II type, and the agglomeration temperature and the number of rotations of stirring are changed depending on the agglomeration speed.

  On the other hand, for coating aggregated particles, a coating resin particle dispersion prepared in advance by adjusting pH to 2.7 was prepared by adding 38 parts of ion-exchanged water to 190 parts of an amorphous polyester resin dispersion. When the aggregated particles grew to 5.8 μm in the aggregation step, the coating resin particle dispersion was added and held for 10 minutes with stirring. Thereafter, in order to stop the growth of the coated aggregated particles (adhered particles), a 1M aqueous sodium hydroxide solution was added to control the pH of the raw material mixture to 8.0. Subsequently, in order to fuse the aggregated particles, the temperature was raised to 85 ° C. at a temperature raising rate of 1 ° C./min while controlling the pH to 8.0. After confirming that the aggregated particles were fused with an optical microscope, ice water was injected and rapidly cooled at a cooling rate of 100 ° C./min.

  Next, the obtained particles were stirred for 20 minutes with a treatment solution (pH 10.5) obtained by adding 8 parts of 3-hydroxy-2,2'-iminodisuccinic acid to 100 parts of the toner, and sieved once with a 20 μm mesh. Thereafter, about 10 times the amount of ion-exchanged water (25 ° C.) with respect to the solid content was added, stirred for 20 minutes, and dried to obtain toner base particles 1 having a volume average particle size of 6.6 μm.

  To the toner base particles 1 obtained above, silica fine powder (particle size: 50 nm) and titania fine powder (particle size: 40 nm) as external additives were added in an amount of 0.9 parts and 0 parts per 100 parts of toner base particles, respectively. 6 parts were added and mixed with a Henschel mixer to obtain toner 1.

-Production of Toner 2-
Toner 1 was prepared in the same manner except that 100 parts of a 10% aqueous solution of aluminum sulfate was replaced with 80 parts and 8 parts of 3-hydroxy-2,2′-iminodisuccinic acid was replaced with 5 parts.

-Manufacture of toner 3-
Toner 1 was produced in the same manner except that 100 parts of a 10% aqueous solution of aluminum sulfate was replaced with 120 parts and 8 parts of 3-hydroxy-2,2′-iminodisuccinic acid was replaced with 10 parts.

-Manufacture of toner 4-
The particles were agglomerated, fused and quenched in the same manner as toner 1 and then stirred for 20 minutes and sieved once with a 20 μm mesh. Thereafter, approximately 10 times the amount of ion-exchanged water (25 ° C.) was added to the solid content, stirred for 20 minutes, washed, and once filtered. Further, the solid content remaining on the filter paper was dispersed in a slurry, repeatedly washed with ion exchange water at 25 ° C. four times, and dried to obtain toner base particles 4 having a volume average particle diameter of 6.6 μm.
To the toner base particles 4 obtained above, silica fine powder (particle diameter: 50 nm) and titania fine powder (particle diameter: 40 nm) as external additives were added in an amount of 0.9 parts and 0 parts per 100 parts of toner base particles, respectively. 6 parts were added and mixed with a Henschel mixer to obtain toner 4.

-Production of Toner 5-
Toner 5 was produced in the same manner as in the production of toner 1 except that 100 parts of a 10% aluminum sulfate aqueous solution was replaced with 70 parts.

-Manufacture of toner 6-
Toner 6 was produced in the same manner except that 100 parts of a 10% aqueous solution of aluminum sulfate was replaced with 70 parts and 8 parts of 3-hydroxy-2,2′-iminodisuccinic acid was replaced with 4 parts.

-Manufacture of toner 7-
Toner 1 was produced in the same manner as in the production of toner 1, except that 100 parts of 10% aqueous solution of aluminum sulfate was replaced with 140 parts and 8 parts of 3-hydroxy-2,2′-iminodisuccinic acid was replaced with 13 parts.

-Production of Toner 8-
In the production of toner 1, toner 8 was obtained in the same manner as in the production of toner 1 except that 46 parts of the crystalline polyester resin particle dispersion was not included.

-Manufacture of toner 9-
Toner 1 was produced in the same manner except that the crystalline polyester resin used was changed to a crystalline polyester resin having an acid value of 5.1 mg KOH / g and a weight average molecular weight of 8200.

-Production of Toner 10-
Toner 10 was produced in the same manner except that the crystalline polyester resin used in the production of toner 1 was replaced with a crystalline polyester resin having an acid value of 13.5 mg KOH / g and a weight average molecular weight of 21,500.

-Manufacture of toner 11-
Toner 11 was produced in the same manner except that the crystalline polyester resin used was changed to a crystalline polyester resin having an acid value of 24.8 mgKOH / g and a weight average molecular weight of 39000.

1Y, 1M, 1C, 1K, 107 photoconductor (latent image holder)
2Y, 2M, 2C, 2K, 108 Charging roller 3Y, 3M, 3C, 3K Laser beam 3 Exposure device 4Y, 4M, 4C, 4K, 111 Developing device (developing means)
5Y, 5M, 5C, 5K Primary transfer rollers 6Y, 6M, 6C, 6K, 113 Photoconductor cleaning device (cleaning means)
8Y, 8M, 8C, 8K Toner cartridge 10Y, 10M, 10C, 10K Image forming unit 20 Intermediate transfer belt 22 Drive roller 24 Support roller 26 Secondary transfer roller (transfer means)
28, 115 Fixing device (fixing means)
30 Intermediate transfer member cleaning device 112 Transfer device 116 Mounting rail 117 Opening portion 118 for static elimination exposure Opening portion 200 for exposure Process cartridge P, 300 Recording paper (transfer object)

Claims (7)

A binder resin containing at least a crystalline resin, and a colorant,
The aluminum content of the toner surface layer is in the range of 0.05 to 0.15 in the Net intensity by fluorescent X-ray analysis, and the aluminum content in the toner is 0. 0 in the Net intensity by fluorescent X-ray analysis. An electrostatic image developing toner having a range of 20 or more and 0.50 or less.
(Herein, the toner surface layer portion, under conditions of 25 ° C., to a solution containing only methanol 5 parts by mass of tetrahydrofuran 5 parts by mass, the toner was mixed 1 part by mass, ultrasonic disperser Tetora150 (Nikka The toner part dissolved in the solution when it is vibrated at 50 kHz for 3 minutes using the machine Bios Co., Ltd. The inside of the toner indicates the part of the toner not dissolved in the solution under the same conditions.)   2. The electrostatic image developing toner according to claim 1, wherein the crystalline resin is a crystalline polyester resin having an acid value of 5 mgKOH / g or more and 25 mgKOH / g or less and a weight average molecular weight of 8000 or more and 40000 or less. . An aggregating step of mixing at least one resin particle dispersion and at least one colorant dispersion to form aggregated particles in the presence of aluminum ions;
A fusion step of heating the resin particles of the resin particle dispersion to a temperature equal to or higher than the glass transition temperature to fuse and coalesce the aggregated particles to form toner particles;
A cleaning step of cleaning the obtained toner particles;
The method for producing a toner for developing an electrostatic charge image according to claim 1 , wherein the washing step includes at least a step of washing the toner particles with a treatment liquid containing a chelating agent.   An electrostatic charge image developer comprising at least the electrostatic charge image developing toner according to claim 1.   A toner which is attached to and detached from an image forming apparatus and contains toner to be supplied to a developing unit provided in the image forming apparatus, wherein the toner is the electrostatic charge image developing toner according to claim 1. cartridge.   A process cartridge comprising at least a developer holder and containing the electrostatic charge image developer according to claim 4.   A latent image holding member, a developing unit that develops the electrostatic latent image formed on the latent image holding member as a toner image with the electrostatic charge image developer according to claim 4, and formed on the latent image holding member. A transfer unit that transfers the toner image transferred onto the transfer member, a fixing unit that fixes the toner image transferred onto the transfer member, and the latent image holder is rubbed with a cleaning member to remove residual transfer components. An image forming apparatus comprising: a cleaning unit for cleaning.

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