JP2012203124A - Toner, fixing method, image forming method and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having extremely low energy consumption in a fixing process in an image forming method and capable of forming a high-quality image with high image strength immediately after fixed and high strength against rubbing even in a halftone image.SOLUTION: The toner is to be used in a process of applying a fixing solution containing a diluent and a plasticizer that at least partially softens or swells the toner to a toner on a recording medium to fix the toner to the recording medium. The toner contains at least a binder resin, a colorant and a polyalkyleneglycol ester compound expressed by general formula (I). In the general formula (I), both of Rand Rrepresent a straight-chain or branched-chain alkyl group having 1 to 24 carbon atoms; Rxm and Rym may be the same or different from each other and represent a hydrogen atom or a straight-chain or branched-chain alkyl group having 1 to 6 carbon atoms; n is an integer of 2 or more; and m is an integer of 2 or more and 4 or less.

Description

  The present invention relates to a toner, a fixing method, an image forming method, and an image forming apparatus.

  In an electrophotographic image forming apparatus, a thermal fixing system in which toner on a recording medium is fixed by heating and melting and pressurizing is widely used from the viewpoint of fixing speed, fixed image quality, and the like. However, about half or more of the power consumption in such an electrophotographic image forming apparatus is consumed for heating the toner. From the viewpoint of environmental problems, a low power consumption (energy saving) fixing device is desired. Yes.

As such a fixing device, for example, Patent Document 1 proposes a method of fixing a toner by dissolving or swelling the toner with a fixing solution and drying it.
Patent Document 2 discloses a method of preparing a foam-like fixing solution containing a plasticizer that dissolves or swells a toner resin, and uniformly applying the foam-like fixing solution to fix the toner image without disturbing the toner image. Has been proposed.
This fixing method is a fixing method that is low in power consumption and excellent as an energy saving measure because a heat treatment for melting the toner is not required unlike the heat fixing method.

  However, when the conventional fixing methods are used, there is a problem that the progress of softening of the toner is slow, and it is insufficient to fix the toner on the recording medium in a short fixing process. In particular, when a halftone image is fixed on a recording medium, there is a problem that the fixing strength is insufficient and the image is easily peeled off when the image portion of the recording medium is rubbed by some contact.

Further, Patent Document 3 provides a fixing method capable of fixing toner at high speed and in a small amount in a fixing method in which toner is fixed to a recording medium using a fixing liquid containing a plasticizer that softens the toner. Thus, a fixing method using a plasticizer and a toner, in which the shift width ΔT of the endothermic shoulder of the toner is 30 ° C. or more when a DSC measurement is performed by adding 3% by mass of the plasticizer to the toner mass, is proposed. ing. In this proposal, by using a toner and a plasticizer that satisfy the above conditions, the compatibility between the toner and the plasticizer is sufficient even when the amount of the plasticizer is small, so that the toner can be sufficiently softened, and the fixing speed can be reduced. It is possible to cope with high speed.
However, in this proposal, the penetration of the plasticizer into the toner is biased to the vicinity of the toner surface, and the softening portion of the toner that contributes to fixing is only in the vicinity of the toner surface, so that the fixing strength is lowered, and particularly strong fixing strength is required. In a halftone image in which the toner to be fixed is fixed alone, there is a problem that the fixed toner is peeled off by rubbing.

  Accordingly, a toner capable of forming a high-quality image with extremely low energy consumption in the fixing step of the image forming method, high image strength immediately after fixing, and being strong against rubbing even in a halftone image, and fixing using the toner The present situation is that prompt provision of a method, an image forming method, and an image forming apparatus is desired.

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention relates to a toner capable of forming a high-quality image with extremely low energy consumption in the fixing step of the image forming method, high image strength immediately after fixing, and strong against rubbing even in a halftone image, and the toner It is an object of the present invention to provide a fixing method, an image forming method, and an image forming apparatus using the above.

As a result of intensive studies by the present inventors in order to solve the above-described problems, the present invention contains a predetermined polyalkylene glycol ester compound having a high affinity with a plasticizer that softens or swells at least a part of the toner, and is disposed inside the toner. With this configuration, when a fixing solution is applied to the toner, the penetration of the plasticizer into the toner is accelerated, so that the toner softens sufficiently immediately after fixing, and the fixing strength to the recording medium is sufficient. It was found that a fixing strength strong against rubbing can be obtained even in a halftone image.
Further, since the penetration of the plasticizer into the toner starts from the surface of the toner particles where the plasticizer and the toner come into contact, when the toner is softened in a short time by the contact between the toner and the fixing liquid, the vicinity of the surface of the toner particles Then, softening is fast, and softening is slow in the vicinity of the center of the toner particles. Therefore, immediately after fixing in a short time, the softening portion is only in the vicinity of the surface of the toner particles, and the fixing strength of the toner particles to the recording medium becomes insufficient, and peeling due to rubbing occurs. .
Therefore, in the image forming method and the image forming apparatus of the present invention, the toner is fixed by using a fixing solution containing a plasticizer that softens or swells at least a part of the toner. Therefore, the plasticizer in the fixing solution is added to the toner. It has been found that softening is achieved by permeation, and then good fixing of the toner to the recording medium can be achieved by pressing against the recording medium with a pressure roller.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A toner used for fixing a toner onto a recording medium by applying a fixing liquid containing a diluent and a plasticizer that softens or swells at least a part of the toner to the toner on the recording medium. And
A toner comprising at least a binder resin, a colorant, and a polyalkylene glycol ester compound represented by the following general formula (I).
However, the general formula (I), ^{R 1} and ^{R 2} are both represent a linear or branched alkyl group having 1 to 24 carbon atoms. Rxm and Rym may be the same as or different from each other, and represent either a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. n represents an integer of 2 or more. m represents an integer of 2 or more and 4 or less.
<2> The toner according to <1>, wherein the polyalkylene glycol ester compound has a weight average molecular weight of 3,600 to 20,500.
<3> The toner according to any one of <1> to <2>, wherein the polyalkylene glycol ester compound has a melting point of 50 ° C. or higher.
<4> The toner according to any one of <1> to <3>, wherein the content of the polyalkylene glycol ester compound is 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the binder resin.
<5> The toner according to any one of <1> to <4>, wherein the polyalkylene glycol ester compound includes polyethylene glycol as a structural unit.
<6> A fixing method for fixing a toner image formed on a recording medium using the toner according to any one of <1> to <5>,
A foamed fixing solution generating step for producing a foamed fixing solution by foaming a fixing solution containing a diluent containing water, a foaming agent, and a plasticizer;
A film thickness adjusting step for forming the foamy fixer to a desired thickness on the contact surface of the foamy fixer applying means,
A foam-like fixing solution applying step for applying the foam-like fixing solution formed in the desired thickness to the toner layer on the recording medium;
A fixing method comprising:
<7> The fixing method according to <6>, wherein the plasticizer is diethoxyethoxyethyl aliphatic dicarboxylate.
<8> The fixing method according to <6>, wherein the plasticizer is a compound represented by the following general formula.
R ⁸ (COO— (R ⁹ —O) _n —R ¹⁰ ) ₂
In the general formula, n is 1 to 3, R ⁸ is an alkylene group having 2 to 8 carbon atoms, R ⁹ is an alkylene group having 1 to 3 carbon atoms, R ¹⁰ Is an alkyl group having 1 to 4 carbon atoms.
<9> an electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
Developing the electrostatic latent image using a developer containing toner to form a visible image;
A transfer step of transferring the visible image to a recording medium;
A fixing step of fixing the transferred image transferred to the recording medium;
An image forming method comprising:
An image forming method, wherein the fixing step is performed by the fixing method according to any one of <6> to <8>.
<10> an electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
A developer carrying member for carrying a developer to be supplied to the electrostatic latent image carrier, a developer supplying member for supplying the developer to the surface of the developer carrying member, and a developer containing a developer containing toner A developing unit that develops the electrostatic latent image using a developer containing toner and forms a visible image;
Transfer means for transferring the visible image to a recording medium;
Fixing means for fixing the transferred image transferred to the recording medium;
An image forming apparatus having
The fixing unit includes a fixing solution applying unit that applies a fixing solution to a toner layer on a recording medium,
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <5>.
<11> an electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
A developer carrying member for carrying a developer containing toner to be supplied to the electrostatic latent image carrier, a developer supplying member for supplying the developer to the surface of the developer carrying member, and a developer containing toner. A developer container for storing, and developing means for developing the electrostatic latent image with a developer containing toner to form a visible image;
Transfer means for transferring the visible image to a recording medium;
Fixing means for fixing the transferred image transferred to the recording medium;
An image forming apparatus having
A foaming fixer generating means for generating a foamy fixer by foaming a fixer containing a diluent containing water, a foaming agent, and a plasticizer;
Film thickness adjusting means for forming the foamy fixer on the contact surface of the foamy fixer applying means to a desired thickness;
A foam-like fixing solution applying means for applying the foam-like fixing solution formed in the desired thickness to the toner layer on the recording medium;
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <5>.

  According to the present invention, conventional problems can be solved, energy consumption in the fixing step of the image forming method is extremely small, image strength immediately after fixing is high, and halftone images are also resistant to rubbing. A toner that can be used, and a fixing method, an image forming method, and an image forming apparatus using the toner can be provided.

FIG. 1 is a schematic cross-sectional view showing how toner is fixed after the fixing solution is applied. FIG. 2 is a schematic diagram showing a layer configuration example of the foamy fixing solution at the time of application. FIG. 3 is a schematic diagram showing the configuration of the foamy fixing solution generating means in the fixing device. FIG. 4A is a schematic configuration diagram illustrating an example of a film thickness adjusting unit and a foamy fixing solution applying unit in the fixing device. FIG. 4B is an enlarged schematic view of a coating roller and a film thickness adjusting blade in the fixing device. FIG. 5A is a schematic diagram illustrating a method for adjusting the film thickness of the foamy fixing solution on the application roller. FIG. 5B is a schematic diagram showing a method for adjusting the film thickness of the foamy fixing solution on the application roller. FIG. 6 is a schematic diagram illustrating an example of a fixing device. FIG. 7 is a schematic diagram illustrating another example of the fixing device. FIG. 8 is a schematic view showing another example of a fixing device provided with a heating means. FIG. 9 is a schematic view showing an example of the image forming apparatus of the present invention. FIG. 10 is a schematic view showing another example of the image forming apparatus of the present invention. FIG. 11 is a schematic diagram of one image forming unit provided in the image forming apparatus shown in FIG. 12 is an enlarged view of the fixing device of the image forming apparatus shown in FIG. FIG. 13 is a schematic diagram illustrating an example of an image forming apparatus including a fixing unit. FIG. 14 is a schematic diagram illustrating an example of an image forming apparatus.

(toner)
The toner of the present invention is used to fix a toner on a recording medium by applying a fixing liquid containing a diluent and a plasticizer that softens or swells at least a part of the toner to the toner on the recording medium. ,
It contains at least a binder resin, a colorant, and a polyalkylene glycol ester compound represented by the following general formula (I), and further contains other components as necessary.
However, the general formula (I), ^{R 1} and ^{R 2} are both represent a linear or branched alkyl group having 1 to 24 carbon atoms. Rxm and Rym may be the same as or different from each other, and represent either a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. n represents an integer of 2 or more. m represents an integer of 2 or more and 4 or less.

<Polyalkylene glycol ester compound>
The polyalkylene glycol ester compound represented by the general formula (I) includes one or more carboxylic acids represented by the following general formula (i) and a polyalkylene represented by the following general formula (ii). It is a compound obtained by esterifying glycol.
However, in said general formula (i), X represents a C1-C24 linear or branched alkyl group.
However, in the said general formula (ii), Rxm and Rym both represent either a hydrogen atom and a C1-C6 linear or branched alkyl group. n represents an integer of 2 or more. m represents an integer of 2 or more and 4 or less.

  Examples of the carboxylic acid represented by the general formula (i) include linear, branched or cyclic aliphatic saturated carboxylic acids. Specific examples include propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, and montanic acid. Among these, palmitic acid, stearic acid, behenic acid, and montanic acid are preferable, and behenic acid is particularly preferable.

Rxm and Rym in the general formula (ii) represent a linear or branched alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Can be mentioned.
n represents an integer of 2 or more, and preferably 28 to 408.
m represents an integer of 2 or more and 4 or less.
There is no restriction | limiting in particular as polyalkylene glycol represented by the said general formula (ii), According to the objective, it can select suitably, For example, polyethyleneglycol, polypropylene glycol, polybutylene glycol etc. are mentioned. Among these, polyethylene glycol is particularly preferable.

  Examples of the polyalkylene glycol ester compound represented by the general formula (I) include polyethylene glycol dibehenic acid, polyethylene glycol distearic acid, polyethylene glycol dimyristic acid, polyethylene glycol dimontanoic acid, polypropylene glycol dibehenic acid, Polypropylene glycol distearic acid, polypropylene glycol dimyristic acid, polypropylene glycol dimontanic acid, polypropylene glycol dimontanic acid, polybutylene glycol dibehenic acid, polybutylene glycol distearic acid, polybutylene glycol dimyristic acid, polybutylene glycol dimontanic acid Etc.

The weight average molecular weight Mw of the polyalkylene glycol ester compound represented by the general formula (I) is preferably 3,600 to 20,500, and more preferably 4,000 to 12,000. When the weight average molecular weight is less than 3,600, the heat resistant storage stability of the toner may be deteriorated, and when it exceeds 20,500, sufficient fixing ability may not be exhibited.
Here, the weight average molecular weight of the polyalkylene glycol ester compound can be measured by, for example, a gel permeation chromatography (GPC) measuring device.

The polyalkylene glycol ester compound has a melting point of preferably 50 ° C or higher, more preferably 55 ° C to 65 ° C. When the melting point is less than 50 ° C., the heat resistant storage stability of the toner may be deteriorated.
Here, the melting point can be measured by, for example, a differential scanning calorimeter.

  As the polyalkylene glycol ester compound represented by the general formula (I), an appropriately synthesized product or a commercially available product may be used. Examples of the commercially available products include Unistar E275 (manufactured by NOF Corporation), Nonion DS-60HN (manufactured by NOF Corporation), Unisafe NKL-9520 (manufactured by NOF Corporation), Emanon 3299V (manufactured by Kao Corporation), and Emanon 3299RV (Kao Corporation). Etc.).

  The content of the polyalkylene glycol ester compound in the toner is preferably 1 part by mass to 15 parts by mass and more preferably 2 parts by mass to 10 parts by mass with respect to 100 parts by mass of the binder resin. When the content is less than 1 part by mass, the amount of the polyalkylene glycol ester compound is small, so that the toner may be insufficiently softened and the fixing strength may be inferior. There is a possibility that copy blocking occurs in which the softening proceeds excessively and the images after fixing are bonded to each other.

<Binder resin>
The binder resin is not particularly limited, and can be appropriately selected from known ones according to the purpose. Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-methacrylic acid copolymer Copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer Polymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl keto Copolymer, styrene-butadiene copolymer, styrene-isopropyl copolymer, styrene-based copolymer such as styrene-maleic acid ester copolymer, polythyme methacrylate resin, polybutyl methacrylate resin, polyvinyl chloride resin, Polyvinyl acetate resin, polyethylene resin, polyester resin, polyurethane resin, epoxy resin, polyvinyl butyral resin, polyacrylic acid resin, rosin resin, modified rosin resin, terpene resin, phenol resin, aliphatic or aromatic hydrocarbon resin, aromatic Based petroleum resins. These may be used individually by 1 type and may use 2 or more types together. Among these, it is particularly preferable to use a polyester resin because of its affinity with the recording medium to be fixed.

The following are mentioned as a monomer which comprises the said polyester resin.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned. In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol together.
Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , Etc.

Examples of the acid component constituting the polyester resin include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, and alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or anhydrides thereof. , Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. And unsaturated dibasic acid anhydride.
Examples of the trivalent or higher polyvalent carboxylic acid component include trimellitic acid, pyrometic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and 2,5,7-naphthalenetricarboxylic acid. Acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (Methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, emporic trimer acid, or their anhydrides, partial lower alkyl esters, and the like.

-Modified polyester (prepolymer) capable of reacting with active hydrogen group-containing compound-
The binder resin may contain a modified polyester capable of reacting with an active hydrogen group-containing compound (hereinafter sometimes referred to as a polyester prepolymer). The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when the polyester capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the toner production process. When the polyester prepolymer is subjected to an extension reaction to increase the molecular weight, the heat resistant storage stability of the toner and the stickiness of the image after fixing can be effectively reduced. In this case, the polyester prepolymer is not particularly limited as long as it can react with the active hydrogen group-containing compound, and can be appropriately selected according to the purpose. For example, an isocyanate group, an epoxy group, a carboxylic acid, an acid chloride group, And the like. Among these, a modified polyester containing an isocyanate group is particularly preferable.

  The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. For example, a modified polyester capable of reacting with the active hydrogen group-containing compound is an isocyanate. In the case of a group-containing modified polyester, amines are preferred because they can be made to have a high molecular weight by a reaction such as an extension reaction or a crosslinking reaction with the isocyanate group-containing modified polyester.

  There is no restriction | limiting in particular as said amines, According to the objective, it can select suitably, For example, phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'- Dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, hydroxyethylaniline, aminoethyl mercaptan, aminopropyl mercaptan, aminopropionic acid, aminocaproic acid, etc. Can be mentioned. In addition, ketimine compounds, oxazolidone compounds, and the like in which these amino groups are blocked with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) may be mentioned.

<Colorant>
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G , G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR ), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cadmium Mummer Curry Red, Antimony Zhu, Permanent Red 4R, Para Red, Phiseley Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B , Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oy Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and litbon. These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass.
The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, styrene copolymer, polymethyl methacrylate resin, polybutyl Methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polypropylene resin, polyester resin, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral resin, polyacrylic acid resin, rosin, modified rosin, terpene Examples thereof include resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffins. These may be used individually by 1 type and may use 2 or more types together.

<Charge control agent>
There is no restriction | limiting in particular as said charge control agent, According to the positive / negative of the electric charge charged to a photoreceptor, it can select and use a positive or negative charge control agent suitably.
-Negative charge control agent-
As the negative charge control agent, for example, a resin or compound having an electron donating functional group, an azo dye, a metal complex of an organic acid, or the like can be used.
Specifically, Bontron (product numbers: S-31, S-32, S-34, S-36, S-37, S-39, S-40, S-44, E-81, E-82, E -84, E-86, E-88, A, 1-A, 2-A, 3-A) (all manufactured by Orient Chemical Co., Ltd.), Kaya Charge (product numbers: N-1, N-2) Kaya Set Black (Part No .: T-2, 004) (all manufactured by Nippon Kayaku Co., Ltd.); Eisenspiron Black (T-37, T-77, T-95, TRH, TNS-2) (all Are also manufactured by Hodogaya Chemical Co., Ltd.); FCA-1001-N, FCA-1001-NB, FCA-1001-NZ (all manufactured by Fujikura Kasei Co., Ltd.), and the like. These may be used individually by 1 type and may use 2 or more types together.

-Positive charge control agent-
Examples of the positive charge control agent include basic compounds such as nigrosine dyes; cationic compounds such as quaternary ammonium salts; and metal salts of higher fatty acids.
Specifically, Bontron (part numbers: N-01, N-02, N-03, N-04, N-05, N-07, N-09, N-10, N-11, N-13, P -51, P-52, AFP-B) (all manufactured by Orient Chemical Co., Ltd.); TP-302, TP-415, TP-4040 (all manufactured by Hodogaya Chemical Co., Ltd.); Copy Blue PR , Copy charge (part numbers: PX-VP-435, NX-VP-434) (both manufactured by Hoechst); FCA (part numbers: 201, 201-B-1, 201-B-2, 201-B-3) , 201-PB, 201-PZ, 301) (all manufactured by Fujikura Kasei Co., Ltd.); PLZ (product numbers: 1001, 2001, 6001, 7001) (all manufactured by Shikoku Kasei Kogyo Co., Ltd.), and the like. . These may be used individually by 1 type and may use 2 or more types together.

  The addition amount of the charge control agent is not particularly limited and can be appropriately selected according to the kind of the binder resin, the toner production method including the dispersion method, and the like. 1 mass part-10 mass parts are preferable, and 0.2 mass part-5 mass parts are more preferable. When the added amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, and the fluidity of the electrophotographic developer is lowered. If the amount is less than 0.1 part by mass, the charge rise and charge amount may be insufficient, and the toner image may be easily affected.

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, an inorganic fine particle, a fluid improvement agent, a mold release agent, a magnetic body etc. are mentioned.

-Inorganic fine particles-
Examples of the inorganic fine particles include silica, titania, alumina, cerium oxide, strontium titanate, calcium carbonate, magnesium carbonate, calcium phosphate, etc., and silica fine particles hydrophobized with silicone oil, hexamethyldisilazane, or the like. It is more preferable to use titanium oxide subjected to a specific surface treatment.
Examples of the silica fine particles include Aerosil (Product Nos .: 130, 200 V, 200 CF, 300, 300 CF, 380, OX50, TT600, MOX80, MOX170, COK84, RX200, RY200, R972, R974, R976, R805, R811, R812, T805. , R202, VT222, RX170, RXC, RA200, RA200H, RA200HS, RM50, RY200, REA200) (all manufactured by Nippon Aerosil Co., Ltd.), HDK (part numbers: H20, H2000, H3004, H2000 / 4, H2050EP, H2015EP, H3050EP, KHD50), HVK2150 (all manufactured by Wacker Chemical Co., Ltd.), Cabozil (Part No .: L-90, LM-130, LM-150, M-5, PTG, S-55, H-5, HS-5, EH-5, LM-150D, M-7D, MS-75D, TS-720, TS-610, TS-530) (all manufactured by Cabot) Can be used. These may be used alone or in combination of two or more.
The addition amount of the inorganic fine particles is preferably 0.1 parts by mass to 5.0 parts by mass, and more preferably 0.8 parts by mass to 3.2 parts by mass with respect to 100 parts by mass of the toner base particles.

-Release agent-
As the mold release agent, for example, a carbonyl group-containing wax, a polyolefin wax, a long chain hydrocarbon, or the like may be used, but it is preferable not to use a mold release agent. Toner used in the conventional heat and pressure fixing system is a toner material that is melted during heat roller fixing, called a release agent, for the purpose of preventing hot offset at the time of fixing. A substance (such as a low molecular weight polyolefin wax) having an effect of preventing adhesion between the toner and the toner on the fixing material has been used. However, it is difficult for these release agents to uniformly disperse the toner in a binder resin. This may also cause problems such as mingling, spenting, and contamination of members over time.
Since the toner used in the method of fixing the toner to the recording medium using a fixing liquid containing a plasticizer that softens the toner is used in a non-heating fixing method, the toner melts when performing heat roller fixing, It is not necessary to have a substance having an effect of preventing adhesion between the roller and the toner on the fixing material, and a release agent may not be used.

-Magnetic material-
Examples of the magnetic material include (1) magnetic iron oxide such as magnetite, maghemite, and ferrite, or iron oxide containing other metal oxides, (2) metals such as iron, cobalt, and nickel, or these metals. And alloys of aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, etc. (3) or mixtures thereof, etc. Is used.

Examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , and PbFe _12. Examples thereof include O, NiFe ₂ O ₄ , NdFe ₂ O, BaFe ₁₂ O ₁₉ , MgFe ₂ O ₄ , MnFe ₂ O ₄ , LaFeO ₃ , iron powder, cobalt powder, and nickel powder. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of iron trioxide and γ-iron trioxide are particularly preferable.

  Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Is preferably contained as an oxide.

The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grains production | generation, or adding salt of each element and adjusting pH.
As the usage-amount of the said magnetic body, 10 mass parts-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of said binder resin, and 20 mass parts-150 mass parts are more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 μm to 2 μm, and more preferably 0.1 μm to 0.5 μm.
The number average particle diameter can be obtained, for example, by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.

Further, as the magnetic properties of the magnetic material, those having a coercive force of 20 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g are preferable.
The magnetic material can also be used as a colorant.

<Toner production method>
The method for producing the toner base particles constituting the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a pulverization method, a monomer composition containing a specific polymerizable monomer Polymerization method (suspension polymerization method, emulsion polymerization method) in which water is directly polymerized in water phase, a method of emulsifying or dispersing a specific binder resin solution in an aqueous medium, dissolving in a solvent, removing the solvent and grinding And a melt spray method. Among these, since the selectivity of the resin is high, the granulation property is excellent, and the particle size, the particle size distribution, and the shape are easily controlled, the production method for emulsifying or dispersing a specific binder resin solution in an aqueous medium. Is preferred.

-Grinding method-
The pulverization method is, for example, a method of obtaining the toner base particles by melting, kneading, pulverizing, and classifying the toner material.
In the case of the pulverization method, for the purpose of increasing the average circularity of the toner, the shape may be controlled by applying a mechanical impact force to the obtained toner base particles. In this case, the mechanical impact force can be applied to the toner base particles using a device such as a hybridizer or mechanofusion.
The toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial continuous kneader, a biaxial continuous kneader, or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel Co., Ltd., TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikegai Iron Works, Inc. A manufactured kneader or the like is preferably used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature is performed with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. In this case, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing in a narrow gap between a mechanically rotating rotor and a stator is preferably used. .
In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion by a cyclone, a decanter, centrifugation, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like to produce a toner having a predetermined particle size.

-Suspension polymerization method-
The suspension polymerization method will be described later in an aqueous medium in which a colorant, a release agent, and the like are dispersed in an oil-soluble polymerization initiator and a polymerizable monomer, and a surfactant and other solid dispersant are contained. Emulsified and dispersed by an emulsification method. Thereafter, a polymerization reaction is performed to form particles, and then wet processing for attaching inorganic fine particles to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.
Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and other acids, acrylamide, methacrylic acid, and the like. Functional groups on the surface of toner particles by partially using amide, diacetone acrylamide or their methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, acrylates with methacrylates such as dimethylaminoethyl methacrylate, methacrylates, etc. Can be introduced.
Further, by selecting a dispersant having an acid group and a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

-Emulsion polymerization method-
As the emulsion polymerization method, a water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by a usual emulsion polymerization method. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, wet processing of inorganic fine particles described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer used in the suspension polymerization method.

-Method of emulsifying or dispersing a specific binder resin solution in an aqueous medium-
As a method for emulsifying or dispersing a specific binder resin solution in the aqueous medium, a solution or dispersion of a toner material having at least a binder resin is emulsified or dispersed in an aqueous medium, and the emulsion or dispersion is obtained. After the toner is prepared, the toner is granulated (aqueous granulation). As this method, for example, the following steps [1] to [4] are included.

<< Step [1]: Preparation of Solution or Dispersion of Toner Material >>
The solution or dispersion of the toner material is prepared by dissolving or dispersing a toner material such as a colorant and a binder resin in an organic solvent. The organic solvent is removed during or after the toner granulation.

<<< Step [2]: Preparation of aqueous medium >>>
The aqueous medium is not particularly limited and may be appropriately selected from known ones. For example, water, alcohol miscible with water, dimethylformamide, tetrahydrofuran, cellosolves, solvents such as lower ketones, or the like Examples thereof include a mixture thereof. Among these, water is particularly preferable.
The aqueous medium can be prepared, for example, by dispersing a dispersion stabilizer such as resin fine particles in the aqueous medium. The amount of the resin fine particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 0.5 mass% to 10 mass% is preferable.
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. , Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferably formed of at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin because an aqueous dispersion of fine spherical resin fine particles can be easily obtained.
In addition, in the aqueous medium, if necessary, from the viewpoint of stabilizing the oil droplets of the solution or dispersion at the time of emulsification or dispersion described later, and sharpening the particle size distribution while obtaining a desired shape, It is preferable to use a dispersant. There is no restriction | limiting in particular as a dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are particularly preferable.

<<< Step [3]: Emulsification or Dispersion >>>
When the solution or dispersion containing the toner material is emulsified or dispersed in the aqueous medium, the solution or dispersion containing the toner material is preferably dispersed while stirring in the aqueous medium. The dispersion method is not particularly limited, but a batch type emulsifier such as a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Aihara Seisakusho), TK Fillmix, TK Pipeline Homomixer (made by Tokushu Kika Kogyo Co., Ltd.), Colloid Mill (made by Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Fine Crusher (Mitsui Miike Chemical Industries) Co., Ltd.), Capitoron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Kiko Co., Ltd.) and other continuous emulsifiers, Microfluidizer (Mizuho Kogyo Co., Ltd.), Nanomizer (Nanomizer Co., Ltd.), APV Gaulin High-pressure emulsifiers (made by Gaulin), membrane emulsifiers such as membrane emulsifiers (made by Chilling Industries Co., Ltd.), Bro mixer (Hiyaka Kogyo Co., Ltd.) vibration type emulsifying machine such as, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.), and the like. Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer are particularly preferable from the viewpoint of uniform particle size.
In the case where a modified polyester (prepolymer) capable of reacting with an active hydrogen group-containing compound is included as the binder resin contained in the solution or dispersion, the reaction proceeds during emulsification or dispersion. The reaction conditions are not particularly limited and can be appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is 10 minutes to 40 hours is preferable, and 2 hours to 24 hours is more preferable.

<< Step [4]: Removal of solvent >>
Next, the organic solvent is removed from the emulsified slurry obtained by the emulsification or dispersion. The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed in a dry atmosphere, Examples thereof include a method in which the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation.

<Additional mixing of inorganic fine particles>
Further, in order to improve the fluidity, storage stability, developability, and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added and mixed with the toner base particles produced as described above. .
For mixing the additive, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. First, a strong load may be given first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

-Average particle diameter and average circularity of toner-
The shape, size, etc. of the toner are not particularly limited and can be appropriately selected according to the purpose. The average circularity, volume average particle size, volume average particle size and number are as follows. It is preferable to have a ratio to the average particle size (volume average particle size / number average particle size).

The average circularity of the toner is a value obtained by dividing the circumference of an equivalent circle having the same projected area as the shape of the toner by the circumference of the actual particles, and is preferably 0.90 to 0.98, for example, 0.95. -0.975 is more preferable. Note that particles having an average circularity of less than 0.94 are preferably 15% or less.
When the average circularity is less than 0.90, satisfactory transferability and a high quality image without dust may not be obtained. When the average circularity exceeds 0.98, image formation employing blade cleaning or the like is employed. In the system, defective cleaning of the photoconductor and transfer belt occurred, and in the case of image formation with a high image area ratio such as a photographic image, an untransferred image was formed due to poor paper feed, etc. The toner accumulated on the photoconductor as a transfer residual toner may cause background smearing, or it may contaminate the charging roller etc. that charges the photoconductor in contact with it, and demonstrates its original charging ability. It may not be possible.
The average circularity is measured, for example, using a flow particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation), and using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). Analysis can be performed.
Specifically, 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a glass 100 mL beaker, and each toner 0 Add 1 g to 0.5 g, stir with microspatel, then add 80 mL of ion exchanged water. The obtained dispersion is subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). Using the FPIA-2100, the dispersion is measured for toner shape and distribution until a density of 5,000 / μL to 15,000 / μL is obtained. In this measurement method, it is important that the concentration of the dispersion is 5,000 / μL to 15,000 / μL from the viewpoint of measurement reproducibility of the average circularity.
In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner.
Similar to the measurement of the toner particle size described above, the amount of the surfactant varies depending on the hydrophobicity of the toner, and if it is added in a large amount, noise due to bubbles is generated. Dispersion is insufficient. The amount of toner added varies depending on the particle size, and is small when the particle size is small, and needs to be increased when the particle size is large. When the volume average particle size of the toner is 3 μm to 10 μm, the toner amount is reduced to 0.1%. By adding 1 g to 0.5 g, the dispersion concentration can be adjusted to 5,000 / μL to 15,000 / μL.

There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, 3 micrometers-10 micrometers are preferable, and 3 micrometers-8 micrometers are more preferable. When the volume average particle size is less than 3 μm, in the electrophotographic developer, the toner is fused to the surface of the electrophotographic carrier during a long period of stirring in the developing device, and the charging ability of the electrophotographic carrier is reduced. If it exceeds 10 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the electrophotographic developer is carried out, the fluctuation of the toner particle size may increase. is there.
The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, more preferably 1.10 to 1.25. .
The volume average particle diameter and the ratio between the volume average particle diameter and the number average particle diameter (volume average particle diameter / number average particle diameter) are measured using a particle size measuring device (“Multisizer III” manufactured by Beckman Coulter, Inc.). Measurement can be performed with an aperture diameter of 100 μm, and analysis can be performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51).
Specifically, 0.5 mL of 10 mass% surfactant (alkylbenzene sulfonate Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 mL glass beaker, and 0.5 g of each toner is added. Stir with microspatel, then add 80 mL of ion exchanged water. The obtained dispersion is subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion is measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion is dropped so that the concentration indicated by the apparatus is 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

  The toner of the present invention can be fixed on a recording medium using a fixing solution containing at least a plasticizer that softens or swells at least a part of the toner, and can be used for various applications. The fixing method of the present invention described below. And a fixing device.

<Fixing solution>
The fixing solution contains a plasticizer that softens or swells at least a part of the toner and a diluent, and further contains other components as necessary. When the fixing solution is used as a foamy fixing solution, the fixing solution is used in the form of foam. The foam-like fixing solution contains a diluent, a foaming agent that makes the fixing solution foam, and a plasticizer that softens or swells at least a part of the toner, and further contains other components as necessary. Do it. In the fixing method of the present invention, it is preferable to use this foamy fixing solution.

<< Plasticizer >>
Examples of the plasticizer include liquid plasticizers and solid plasticizers.

-Solid plasticizer-
The solid plasticizer is not particularly limited as long as it is solid at normal temperature and is soluble in a diluent described later and can soften the toner in a state dissolved in the diluent. Here, “normal temperature” refers to a temperature achieved without heating or cooling, and for example, 5 ° C. to 35 ° C. defined in JIS Z8703 is preferable. If it is within this normal temperature range, the solid plasticizer is in a solid state. That is, in the foam-type fixing solution, the solid plasticizer is in a molten state because it contains water, but is applied to the unfixed toner, penetrates into the toner, and further penetrates into the toner. When the amount decreases due to vaporization or the like, the solid plasticizer changes to a solid state. In the present invention, attention is paid to the fact that the solid plasticizer changes to a solid state as described above, and by utilizing this characteristic, the toner hardness after application of the fixing solution is increased and the problem relating to tack is solved. In addition, the solid plasticizer exerts its plastic ability with respect to the toner under appropriate conditions at room temperature, and when it loses its plastic ability and becomes a solid state, it hardens itself and contributes to prevention of tack. preferable.

The solid plasticizer preferably has, for example, a functional group having an affinity such as having a certain compatibility with the toner that is a fixing target. The functional group having affinity here is preferably a case where the functional group contained in the molecule constituting the toner is the same as the functional group contained in the solid plasticizer, and between these functional groups. It means having a functional group capable of a certain interaction. If the functional group contained in the solid plasticizer has a functional group that can have a certain interaction with the molecules constituting the toner, the interaction between these functional groups will cause the solid plasticizer to enter between the molecules constituting the toner. As a result, a so-called polymer blend state is formed between the solid plasticizer and the toner, and the solid plasticizer is effective in softening or swelling at least a part of the toner. As a specific example, the solid plasticizer is a polyethylene glycol compound, and the polyethylene glycol contains an ethylene oxide group. The corresponding toner corresponds to a combination containing an ethylene oxide group in the resin molecule. In such a case, an ethylene oxide group is contained in both the solid plasticizer and the toner, thereby improving the compatibility, thereby producing an effect of increasing the compatibility between the two. On the other hand, this concept is based on having a functional group having an affinity for both the solid plasticizer and the toner, and thus is not limited to the ethylene oxide group. As another example, a propylene oxide group is used. Further, it also works effectively when a functional group contained in a known toner is contained in the solid plasticizer.

  Examples of the solid plasticizer include those that exhibit plastic ability under certain conditions in addition to the above-mentioned requirements. Examples include the following.

(1) Plastic ability is exhibited by dissolving in a diluent described later Part having an ethylene oxide group: Among polyethylene glycols, those having a peak molecular weight of 1,000 to 2,000 (2) In the diluent Even if dissolved, the plastic ability is not exhibited, but the plastic ability is exhibited when a small amount of the liquid plasticizer described below is present. Part having an ethylene oxide group: Among polyethylene glycols, the peak molecular weight is 2,000 to 10,000. (3) Plastic ability is not exhibited even when dissolved in a diluent, but plastic ability is exhibited by slight heating (for example, about 50 ° C. to 100 ° C.) Part having an ethylene oxide group: polyethylene glycol Among them, the peak molecular weight is 2,000 to 10,000.
Polyoxyethylene monoalkyl ethers: polyoxyethylene monolauryl ether, polyoxyethylene monocetyl ether, etc.

  When the peak molecular weight of the polyethylene glycol exemplified in the above (1) is less than 1,000, the fixed image may be melted depending on the surrounding environment, and when it exceeds 2,000, the solid state is no longer in the normal temperature state. In a fixing liquid system that does not share the liquid plasticizer described later, sufficient plasticizing ability may not be exhibited. Based on such technical significance, the peak molecular weight is preferably 1,000 to 2,000.

  When the peak molecular weight of the polyethylene glycol exemplified in the above (2) exceeds 10,000, it is clearly not in a solid state at room temperature, and thus a grain boundary may occur between toners to be fixed. From such a viewpoint, in the system of the fixing solution that does not share the liquid plasticizer, it is clarified that it is difficult to use when the peak molecular weight is 10,000 or more, and the fixing solution contains water. Is used, the peak molecular weight is 1,000 to 10,000.

  The heating temperature of the solid plasticizer exemplified in the above (3) is not particularly limited as long as the plastic ability can be exhibited, but is preferably 50 ° C to 100 ° C. If the heating temperature is less than 50 ° C., fixing may be insufficient, and if it exceeds 100 ° C., it is uneconomical in terms of energy consumption.

  There is no restriction | limiting in particular as content of the said solid plasticizer, Although it can select suitably according to the objective, 5 mass%-30 mass% are preferable with respect to the mass of a fixing solution. When the content is less than 5% by mass, fixing becomes difficult. When the content exceeds 30% by mass, the viscosity of the fixing solution and the foamy fixing solution increases, and in addition, poor foaming and foam As a result, there is a problem in quality.

-Liquid plasticizer-
The fixing solution may contain a liquid plasticizer as a plasticizer. The liquid plasticizer is not particularly limited as long as it is soluble in a diluent described later and exhibits a plastic ability under a certain condition. The toner may be softened by dissolving or swelling a part thereof, but may be one that exhibits plastic ability when combined with the solid plasticizer. Examples of liquid plasticizers include ester compounds in that they are excellent in solubility or swelling under certain conditions. Among these ester compounds, an aliphatic ester or a carbonate ester is more preferable from the viewpoint that the softening ability of the resin is excellent or the degree of foaming inhibition by the diluent described later is low.

The liquid plasticizer, from the viewpoint of safety for human bodies, it is preferable that the acute oral toxicity _{LD 50} is greater than 3 g / kg, more 5 g / kg is more preferable. As the liquid plasticizer, the aliphatic ester is particularly preferable because it has high safety to the human body, as it is frequently used as a cosmetic raw material.

  In addition, the toner is fixed to the recording medium by a device that is frequently used in a sealed environment, and the liquid plasticizer remains in the toner even after the toner is fixed to the recording medium. It is preferable that the fixing of the ink does not involve generation of a volatile organic compound (VOC) and an unpleasant odor. In this respect, it is preferable that the liquid plasticizer does not contain a volatile organic compound (VOC) and a substance that causes an unpleasant odor. The aliphatic ester is more preferable in that it has a high boiling point, low volatility, and no irritating odor as compared to generally used organic solvents (toluene, xylene, methyl ethyl ketone, ethyl acetate, etc.).

  In addition, as a practical odor measurement scale that can measure odors in office environments with high accuracy, the odor index [10 × log (substance odor is felt by sensory measurement) The dilution factor of the substance until it disappears)] may be used as an indicator of odor. The odor index of the aliphatic ester contained in the liquid plasticizer is preferably 10 or less. In this case, an unpleasant odor is not felt in a normal office environment. Furthermore, it is preferable that not only the liquid plasticizer but also other liquids contained in the fixing solution have no unpleasant odor and irritating odor, as with the liquid plasticizer.

-Aliphatic ester-
The aliphatic ester is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include saturated aliphatic esters, aliphatic monocarboxylic acid esters, aliphatic dicarboxylic acid esters, and aliphatic dicarboxylic acid dicarboxylic acids. Alkoxyalkyl may also be used.

--Saturated aliphatic ester--
When the aliphatic ester is a saturated aliphatic ester, the storage stability (resistance to oxidation, hydrolysis, etc.) of the liquid plasticizer can be improved. Further, the saturated aliphatic ester has high safety to the human body, and many saturated aliphatic esters can dissolve or swell the resin contained in the toner in a short time such as within 1 second. Furthermore, saturated aliphatic esters can reduce the tackiness of the toner provided on the recording medium. This is presumably because the saturated aliphatic ester forms an oil film on the surface of the dissolved or swollen toner.

In the fixing solution according to the present invention, preferably, the general formula of the saturated aliphatic ester may be a compound represented by R ¹ COOR ² , wherein R ¹ has 11 to 14 carbon atoms. An alkyl group, and R ² is a linear or branched alkyl group having 1 to 6 carbon atoms. If the number of carbon atoms of R ¹ and R ² is less than the desired range, odor is generated, and if it is greater than the desired range, the resin softening ability is lowered. That is, the saturated aliphatic ester is a compound represented by the general formula R ¹ COOR ² , R ¹ is an alkyl group having 11 to 14 carbon atoms, and R ² is 1 or more carbon atoms. In the case of 6 or less linear or branched alkyl group, the solubility or swelling property with respect to the resin contained in the toner can be improved. Further, the odor index of the compound represented by the general formula R ¹ COOR ² is preferably 10 or less from the viewpoint of having no unpleasant odor and irritating odor.

-Aliphatic monocarboxylic acid ester-
Examples of the aliphatic monocarboxylic acid ester include ethyl laurate, hexyl laurate, ethyl tridecylate, isopropyl tridecylate, ethyl myristate, and isopropyl myristate. Many of these aliphatic monocarboxylic acid esters are soluble in oily solvents but not in water. Therefore, when an aliphatic monocarboxylic acid ester is used to form a fixing solution composed of an aqueous solvent, glycols may be contained in the fixing solution as a solubilizing agent described later, and the solution may be dissolved or in the form of a microemulsion.

-Aliphatic dicarboxylic acid ester-
The aliphatic ester may be an aliphatic dicarboxylic acid ester. When the aliphatic ester is an aliphatic dicarboxylic acid ester, the toner can be dissolved or swollen in a shorter time. For example, in high-speed printing of about 60 ppm, it is preferable that the time required for applying the fixing liquid to the unfixed toner on the recording medium and fixing the toner on the recording medium is within 1 second. When the aliphatic ester is an aliphatic dicarboxylic acid ester, the time required for fixing the toner to the recording medium by applying a fixing solution to the unfixed toner on the recording medium is within 0.1 seconds. It becomes possible to. Furthermore, since the toner can be dissolved or swollen by adding a smaller amount of the liquid plasticizer, the content of the liquid plasticizer contained in the fixing liquid can be reduced.

In the fixing solution according to the present invention, preferably, the general formula of the aliphatic dicarboxylic acid ester is a compound represented by R ³ (COOR ⁴ ) ₂ , wherein R ³ is an alkylene having 3 to 8 carbon atoms. R ⁴ may be a linear or branched alkyl group having 3 to 5 carbon atoms. If the number of carbon atoms in R ³ and R ⁴ is less than the desired range, odor is generated, and if it is greater than the desired range, the resin softening ability decreases.

The aliphatic dicarboxylic acid ester is a compound represented by the general formula R ³ (COOR ⁴ ) ₂ , wherein R ³ is an alkylene group having 3 to 8 carbon atoms, and R ⁴ has 3 carbon atoms. When the linear or branched alkyl group is 5 or less, the solubility or swelling property with respect to the toner can be improved. Moreover, the odor index of the compound represented by the general formula R ³ (COOR ⁴ ) ₂ is preferably 10 or less in that it does not have an unpleasant odor or an irritating odor.

  Examples of the aliphatic dicarboxylic acid ester include 2-ethylhexyl succinate, dibutyl adipate, diisobutyl adipate, diisopropyl adipate, diisodecyl adipate, diethyl sebacate, and dibutyl sebacate. Many of these aliphatic dicarboxylic acid esters are soluble in oily solvents but not in water. For this reason, when an aliphatic dicarboxylic acid ester is used to form a fixing solution composed of an aqueous solvent, glycols may be contained in the fixing solution as a solubilizing agent described later, and the solution may be in the form of a solution or a microemulsion.

-Dialkoxyalkyl aliphatic dicarboxylate-
Furthermore, in the fixing solution according to the present invention, the aliphatic ester improves the fixability of the toner to the recording medium when the aliphatic dicarboxylic acid dialkoxyalkyl aliphatic ester is an aliphatic dicarboxylic acid dialkoxyalkyl. be able to.

In the liquid plasticizer contained in the fixing solution according to the present invention, the dialkoxyalkyl aliphatic dicarboxylate is a compound represented by the general formula R ⁵ (COOR ⁶ —O—R ⁷ ) ₂ , wherein R ⁵ is the number of carbon atoms. Is an alkylene group having 2 to 8 carbon atoms, R ⁶ is an alkylene group having 2 to 4 carbon atoms, and R ⁷ may be an alkyl group having 1 to 4 carbon atoms. If the number of carbon atoms of R ⁵ , R ⁶ and R ⁷ is less than the desired range, odor is generated, and if it is greater than the desired range, the resin softening ability is lowered.

The aliphatic dicarboxylic acid dialkoxyalkyl is a compound represented by the general formula R ⁵ (COOR ⁶ —O—R ⁷ ) ₂ , wherein R ⁵ is an alkylene group having 2 to 8 carbon atoms, and R ⁶ Is an alkylene group having 2 to 4 carbon atoms, and R ⁷ is an alkyl group having 1 to 4 carbon atoms, which can improve the solubility or swelling of the resin contained in the toner. . In addition, the odor index of the compound represented by the general formula R ⁵ (COOR ⁶ —O—R ⁷ ) ₂ is preferably 10 or less because it does not have an unpleasant odor or an irritating odor.

Examples of the aliphatic dicarboxylic acid dialkoxyalkyl include diethoxyethyl succinate, dibutoxyethyl succinate, dimethoxyethyl adipate, diethoxyethyl adipate, dibutoxyethyl adipate, diethoxyethyl sebacate and the like. When these aliphatic dicarboxylic acid dialkoxyalkyls are used in an aqueous solvent, glycols are included in the fixing solution as a dissolution aid, if necessary, to form a solution or microemulsion.
Furthermore, as a similar structure of an aliphatic dicarboxylic acid dialkoxyalkyl, the compound represented by the general formula (5) has a high ratio in the molecule of the ether group, and therefore has very high solubility in water as a diluent. The fixing solution becomes high and contains a high concentration liquid plasticizer.
^{R 8 (COO- (R 9 -O} ) n-R 10) 2 General Formula (5)
However, n in the general formula (5) is 1 or more and 3 or less, R ⁸ is an alkylene group having 2 to 8 carbon atoms, and R ⁹ is an alkylene group having 1 to 3 carbon atoms. , R ¹⁰ is an alkyl group having 1 to 4 carbon atoms.
Examples of the compound represented by the general formula (5) include diethoxyethoxyethyl succinate, diethoxyethoxyethyl adipate, dimethoxyethoxyethyl succinate, dimethoxymethoxypropyl succinate and the like.

-Carbonate ester-
Examples of the carbonate ester which is an example of the liquid plasticizer include cyclic esters such as ethylene carbonate and propylene carbonate (propylene carbonate), glycerol 1,2-carbonate, 4-methoxymethyl-1,3-dioxolan-2-one and the like. Is mentioned.

  Examples of ester compounds other than the above include citric acid esters such as triethyl citrate, acetyl triethyl citrate, tributyl citrate, and tributyl acetyl citrate; ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate And compounds obtained by esterifying glycols such as monoacetin; compounds obtained by esterifying glycerol such as monoacetin, diacetin, and triacetin.

  The content of the liquid plasticizer is preferably 0.5% by mass to 50% by mass and more preferably 5% by mass to 40% by mass with respect to the mass of the fixing solution. If the content is less than 0.5% by mass, the effect of dissolving or swelling the toner may be insufficient. If the content exceeds 50% by mass, the fluidity of the resin contained in the toner over a long period of time may be obtained. The fixing toner layer may have adhesiveness.

<Foaming agent>
The foaming agent contained in the fixing solution according to the present invention is not particularly limited as long as it can foam the fixing solution, and can achieve excellent foaming properties and foam stability. Examples of foaming agents include saturated or unsaturated fatty acid salts, monoalkyl sulfates, sulfonates such as alkyl polyoxyethylene sulfates, alkyl polyoxyethylene sulfates or alkylbenzene sulfonates, or monoalkyl phosphates. Anionic surfactants such as phosphates.

-Fatty acid salt-
Among the foaming agents, fatty acid salts are most excellent in foam stability and are most suitable as foaming agents for fixing solutions.

  The fatty acid salt is preferably a fatty acid sodium salt, a fatty acid potassium salt or a fatty acid amine salt, more preferably a fatty acid amine salt. The method for producing these fatty acid salts is not particularly limited. For example, by heating water, adding a fatty acid, then adding triethanolamine, and heating the mixture with stirring for a certain period of time to cause a saponification reaction. It may be manufactured. At this time, by increasing the molar ratio of fatty acid to triethanolamine within the range of 1: 0.5 to 1: 0.9 and the fatty acid ratio, unreacted fatty acid remains after saponification, and the fixing solution Fatty acid and fatty acid amine salt can be mixed therein. The same is possible with sodium and potassium salts.

  The unsaturated fatty acid salt that can be used as the foaming agent is not particularly limited, but an unsaturated fatty acid salt having 18 carbon atoms and 1 to 3 double bonds is preferred. Specific examples include oleate, linoleate and linolenate. Since the reactivity is strong when the double bond is 4 or more, the stability of the fixing solution is poor. You may use the unsaturated fatty acid salt by these unsaturated saturated fatty acids individually by 1 type or in mixture of 2 or more types as a foaming agent. Further, the above saturated fatty acid salt and unsaturated fatty acid salt may be mixed and used as a foaming agent.

  The liquid plasticizer has a strong antifoaming effect, and as the concentration of the liquid plasticizer increases in the fixing solution, the foaming property and foam stability of the fixing solution deteriorates, so it is difficult to foam and the foam breaks immediately. In some cases, it is impossible to obtain a foam-like fixing solution having a low foam density.

  Therefore, in order to eliminate the deterioration of foaming properties when the concentration of the liquid plasticizer in the fixer is increased, various prototypes were made using the types and concentrations of anionic surfactants as factors. By using a fatty acid salt having 12 to 18 carbon atoms as a foaming agent and further containing a fatty acid having 12 to 18 carbon atoms in the fixing solution, the foaming property of the fixing solution can be improved even when the concentration of the liquid plasticizer increases. Does not deteriorate. Thereby, a stable foamy fixing solution can be provided.

  Here, in the foaming agent contained in the fixing solution, the number of carbon atoms of the fatty acid salt is preferably 12 to 18 in that the foaming property is superior to the case of simply foaming water. Specifically, laurate (12 carbon atoms), myristic acid salt (14 carbon atoms), pentadecyl acid (15 carbon atoms), palmitate (16 carbon atoms), margaric acid (17 carbon atoms), stearic acid And a salt (carbon number 18).

  The effect | action of the fatty acid used with the fatty acid salt used as a foaming agent and a liquid plasticizer is demonstrated. When an ester compound is used as the liquid plasticizer, the ester compound has an ester group in the chemical structure, and the fatty acid has a carbonyl group in the chemical structure. From this point, the ester group of the liquid plasticizer and the carbonyl group of the fatty acid show an electrical action in the fixing solution system, and this causes a binding action between molecules, and foams as a characteristic of the fixing solution. It is thought to improve the property and foam stability.

  In the fatty acid salt having 12 to 18 carbon atoms that can be used as a foaming agent, the foaming stability is low, but the foaming stability is poor, but the foaming stability is poor, and the foaming stability is high. It is extremely superior. Therefore, a single fatty acid salt may be used as the fatty acid salt, but it is more preferable to mix a plurality of fatty acid salts having 12 to 18 carbon atoms and having different carbon numbers. As a mixing ratio, it is preferable to contain the most myristate (carbon number 14) and to lower the ratio of laurate (carbon number 12) and stearate. More specific fatty acid salt ratios are 0: 6: 3: 1, 0: 5: 4: 1, 1: 5 in terms of mass ratio of laurate: myristate: palmitate: stearate. : 3: 1, 1: 4: 4: 1, etc. are suitable.

  The content of the foaming agent is preferably 0.1% by mass to 20% by mass and more preferably 0.5% by mass to 10% by mass with respect to the mass of the fixing solution. When the content is less than 0.1% by mass, the foamability may be insufficient. When the content is more than 20% by mass, the viscosity of the fixing solution may be increased and the foamability may be reduced. There is.

  By containing a fatty acid having the same carbon number as the foaming agent fatty acid salt in the fixing solution, foamability and foam stability can be maintained even when the concentration of the liquid plasticizer increases. If the concentration of the liquid plasticizer is less than 10% by mass, there is no problem in foaming properties even if no fatty acid is contained. However, when the concentration of the liquid plasticizer is 10% by mass or more, particularly when the concentration of the liquid plasticizer is 30% by mass or more, the fatty acid salt hardly foams and the foamability may deteriorate. Even when the foamability is deteriorated, the foamability can be maintained by containing a fatty acid having the same carbon number as that of the fatty acid salt.

  However, if the fatty acid content is too high, the ratio of the fatty acid salt, which is a foaming agent, decreases, and foamability may deteriorate again. In such a case, the number of moles of the fatty acid salt may be equal to or greater than the number of moles of the fatty acid, and the ratio of the fatty acid to the fatty acid salt is 5: 5 to 1: 9. It is good also as a range.

  Not only a combination of a fatty acid having the same number of carbon atoms and a fatty acid salt, but also, for example, a combination in which the fatty acid salt is amine myristate and the fatty acid is stearic acid, a combination in which the fatty acid salt is potassium palmitate and the fatty acid is stearic acid As such, a combination of different fatty acid salts and fatty acids in the range of 12 to 18 carbon atoms may be used. By containing a fatty acid having a carbon number in the range of 12 to 18 in the fixing solution, even if a high concentration liquid plasticizer is contained, the foamability is not deteriorated, the foam stability is excellent, and the foaming is extremely low in density. Is possible.

  In addition, in order to prevent deterioration of foaming properties, other anionic surfactants (for example, alkyl ether sulfate (AES)) are used as foaming agents, and further contain a fatty acid having 12 to 18 carbon atoms. May be.

<Diluent>
The diluent contained in the fixing solution according to the present invention is not particularly limited as long as it contains water. For example, water, an aqueous solvent obtained by adding an alcohol or the like to water, and the like are preferable. As water, for example, pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water, or ultrapure water can be used.

  When an aqueous solvent is used as a diluent, a surfactant may be added. In particular, the surface tension of the fixing solution is preferably 20 mN / m to 30 mN / m. Examples of the alcohols include unitary alcohols such as cetanol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, diethylene glycol, and the like in terms of enhancing the stability of bubbles in the foam-like fixing solution and making it difficult to break bubbles. Polyhydric alcohols such as propylene glycol, tripropylene glycol, 1,3-butylene glycol and glycerin are preferred. By containing these unit prices or polyhydric alcohols, it is effective in preventing curling of media such as paper.

  The diluent preferably contains an oil component to form an O / W emulsion or a W / O emulsion for the purpose of improving permeability and preventing curling of a medium such as paper. As this oil component, various known materials can be used. In the case of a diluent containing an oil component, an emulsion may be formed by using a dispersant, and various known materials can be used as the dispersant used to form this emulsion, but sorbitan monooleate Sorbitan fatty acid esters such as sorbitan monosterate and sorbitan sesquiolate; sucrose esters such as sucrose laurate and sucrose stearate are preferred.

  There is no particular limitation on the method for dispersing the fixing solution in the form of an emulsion using a dispersant, and various known methods may be used. Examples thereof include a mechanical mixer such as a homomixer using rotating blades and a homogenizer, and a means for applying vibration such as an ultrasonic homogenizer. Among these, a method of applying a strong shear stress to the plasticizer in the fixing solution is preferable.

<Recording medium>
The recording medium is not particularly limited as long as it can fix toner. Among them, the recording medium is preferably a medium having permeability to the fixing solution. If the medium substrate does not have liquid permeability, a medium having a liquid-permeable layer on the substrate is preferable. There is no restriction | limiting in particular as a form of the said recording medium, Although it can select suitably according to the objective, In addition to a sheet form, the solid thing which has a plane and a curved surface may be sufficient. For example, it may be one in which transparent toner is uniformly fixed on a medium such as paper to protect the paper surface (so-called varnish coat). The material of the recording medium is not particularly limited and can be appropriately selected according to the purpose. For example, a plastic film such as a sheet for OHP having a general fiber constituting a paper, a cloth, a liquid permeable layer, or the like. , Metals, resins, and ceramics.

<Other ingredients>
<< Solution aid >>
The fixing solution may contain a dissolution aid for the purpose of dissolving the liquid plasticizer in the fixing solution. The dissolution aid is not particularly limited as long as it can dissolve the liquid plasticizer, and examples thereof include polyhydric alcohols. Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butylene glycol, and glycerin. Of these, propylene glycol and dipropylene glycol are preferable in that the liquid plasticizer can be dissolved even at a high concentration and does not deteriorate the foamability of the foaming agent. The content of the polyhydric alcohol is preferably 1% by mass to 30% by mass with respect to the mass of the fixing solution. If the content exceeds 30% by mass, the foaming property is rather deteriorated, which is not suitable. If the content is less than 1% by mass, the liquid plasticizer is diluted with water as a diluted solution when the concentration of the liquid plasticizer in the fixing solution increases. The agent may become difficult to dissolve.

<< Foaming agent >>
The fixing solution is foamed and used as a later-described foam fixing solution for fixing toner. When the foam fixing solution is pressed into the toner layer at the coating contact nip portion, the bubbles break. If it foams, it will inhibit penetration. Therefore, the fixing solution according to the present invention may further include a foaming agent for the purpose of suppressing such a phenomenon and improving foam stability. Although there is no restriction | limiting in particular as a foaming agent, Fatty acid alkanolamide is preferable and a fatty acid alkanolamide (1: 1) type is more preferable at the point of foam stability. The content of the foam increasing agent is preferably 0.01% by mass to 3% by mass with respect to the mass of the fixing solution.

(Fixing method)
The fixing method of the present invention includes a foamy fixing solution generation step, a film thickness adjustment step, and a foamy fixing solution application step, and further includes other steps as necessary.
The fixing device used in the present invention includes a foamy fixing solution generating unit, a foaming fixing solution applying unit, and a film thickness adjusting unit, and further includes other units as necessary.

  The fixing method of the present invention can be preferably carried out by the fixing device used in the present invention, the foamy fixer generating step can be performed by a foamy fixer generating means, and the film thickness adjusting step It can be performed by the thickness adjusting means, the foam-like fixing liquid application step can be performed by the foam-type fixing liquid application means, and the other steps can be performed by the other means.

<Foam Fixer Generation Step and Foam Fixer Generation Unit>
The foamy fixing solution generation step is a step of generating a foamy fixing solution by foaming the fixing solution, and is performed by a foaming fixing solution generating means.

  As shown in FIG. 1, by using the foam-like fixing liquid generating means as the foam-like fixing liquid 114 composed of foam, the bulk density of the fixing liquid can be lowered and the fixing liquid layer on the coating roller 111 can be formed. Since the thickness can be increased and the influence of the surface tension of the fixing liquid can be suppressed, the foamy fixing liquid 114 is uniformly applied to the toner layer on the recording medium 112 while preventing the resin fine particles from being offset to the application roller 111. It can be attached.

  FIG. 2 is a schematic diagram showing an example of the layer structure of the foamy fixing solution at the time of application. The liquid 121 shown in FIG. 2 contains a plasticizer and has a foam-like configuration in which bubbles 122 are contained in the liquid. Thus, the bulk density of the fixing liquid 120 can be made extremely low by containing a large amount of the bubbles 122. By adopting this configuration, even when the fixing solution is applied in a large volume state, the bulk density is low and the application mass is small. Can be very low. In addition, the bubble shape in this invention shows the state which the bubble disperse | distributed in the liquid and the liquid was tinged with compressibility.

  There are no particular limitations on the foam fixing solution generation step and the foam fixing solution generation means as long as the fixing solution according to the present invention can be foamed to generate a foam fixing solution. One mode thereof will be described with reference to FIG.

  FIG. 3 is a schematic view showing the configuration of the foamy fixing solution generating means in the fixing device according to the present invention. 3 includes a fixing liquid container 131 for storing the liquid fixing liquid 132 such as the fixing liquid according to the present invention, a liquid transport pipe 134 for transporting the liquid fixing liquid 132, and a liquid. A transport pump 133 that obtains driving for transport, a gas / liquid mixing unit 135 that mixes gas and liquid, and a foam generation unit 138 that foams the liquid fixer 132 to obtain a desired foamy fixer. Have.

  The liquid fixing liquid 132 stored in the fixing liquid container 131 is transported through the liquid transport pipe 134 by the driving force of the transport pump 133 and is sent to the gas / liquid mixing unit 135. The transport pump is not particularly limited as long as it can transport the liquid fixing solution, and can be appropriately selected according to the purpose. For example, a gear pump, a bellows pump, and the like can be mentioned, and a tube pump is preferable. If there is a vibration mechanism or a rotation mechanism such as a gear pump, the fixer foams in the pump, and the fixer may be compressible, resulting in a decrease in conveying ability. In addition, the above-mentioned mechanical parts or the like may contaminate the fixer or conversely deteriorate the mechanical parts. On the other hand, since the tube pump is a mechanism that pushes out the liquid in the tube while deforming the tube, the only member in contact with the fixing liquid is the tube. By using a member that has liquid resistance to the fixing liquid, No contamination or deterioration of pump system parts. In addition, since the tube is only deformed, the liquid does not foam, and the conveyance capacity can be prevented from being lowered.

  The gas / liquid mixing unit 135 is provided with an air port 136, a negative pressure is generated in the air port 136 along with the flow of the liquid, and the gas is introduced from the air port 136 into the gas / liquid mixing unit 135. Are mixed. Furthermore, by passing through the microporous sheet 137, large bubbles with uniform bubble diameters can be generated. The pore diameter is preferably 30 μm to 100 μm. The porous member is not limited to the microporous sheet 137 of FIG. 3, and may be a porous member having an open cell structure, and may be a sintered ceramic plate, a nonwoven fabric, or a foamed resin sheet having a pore diameter of 30 μm to 100 μm. As another method for generating large bubbles, the liquid fixer supplied from the above-described transport pump and the air from the air port are stirred with a blade-like stirrer, and large bubbles are generated while bubbles are involved in the liquid. A configuration in which a large bubble is generated by bubbling the liquid fixer supplied from the above-described transport pump with an air supply pump or the like is also preferable.

  Next, the liquid fixing solution 132 mixed with air is sent to the foam generation unit 138 that obtains a desired foam-like fixing solution. In the foam generation unit 138, a shearing force is applied to the liquid fixing solution 132 mixed with air, and large bubbles are divided into two or more bubbles. The configuration of the bubble generation unit 138 is not particularly limited as long as it can be performed in this way, but the inner cylinder can be rotated with a closed double cylinder, which is larger than a part of the outer cylinder. A configuration may be employed in which a foam-like fixer is supplied and a shear force is received by the rotating cylinder while passing through a gap between the inner rotating cylinder and the outer cylinder (this is a flow path). Due to this shearing force, the large bubbles are changed into minute bubbles, and a foam-like fixing liquid having a desired minute bubble diameter can be obtained from the outlet of the bubbles provided in the outer cylinder. In addition, a spiral groove may be provided in the inner cylinder to increase the liquid transport capability in the cylinder.

  The fixer only needs to be foamed when applied to a toner layer on a recording medium such as paper, and need not be foamed in the fixer container. The fixing solution container is preferably a liquid that does not contain bubbles, and is provided with a means for forming bubbles in the liquid transport path until the liquid is supplied from the container until the liquid is supplied from the container. This is because the fixing liquid container is a liquid, and the foamed structure after the liquid is taken out from the container has a great advantage that the container can be downsized.

  The fixer is foamed, and the thickness of the foam-like fixer layer composed of the foamed fixer is foam-like as described later on the entire recording medium surface according to the thickness of the toner layer to be fixed. Adjustment is made in terms of the fixing solution applying means. For example, when a toner is composed and color images and black and white characters are mixed on a recording medium, if the entire surface of the recording medium is applied with a foam-type fixing liquid layer having the same thickness, a fixing failure is not obtained with a thick toner layer such as a color photographic image. In some cases, image omission may occur, or a partial defect may occur in which black and white character portions are sticky and the printed materials stick to each other. The cause of the problem will be described in detail below.

  In general, in the case of large bubbles of about 0.5 mm to 1 mm, bubbles can be generated relatively easily by simple stirring, etc., and the generation of large bubbles takes less than a few seconds (not longer than 0.1 seconds). can do. Therefore, paying attention to the fact that bubbles that are larger than the desired bubble diameter and that can be easily observed and can be quickly obtained can be obtained quickly, and from about 5 μm to 50 μm quickly from the large bubbles. As a result of diligently studying the method of generating microbubbles, dividing the large foam by applying shear force to the large foam is extremely quick compared to the method of generating microbubbles from the liquid state as described above. It has been found that microbubbles of a desired size can be generated. In this respect, the configuration of the foamy fixing solution generating unit 130 as described above is a preferable mode for realizing this.

  In this way, by combining a large bubble generating part that changes the liquid fixing solution into a liquid having a large bubble diameter and a fine bubble generating part that applies a shearing force to the large bubbles to generate minute bubbles, It is possible to generate a foamy fixing solution having a fine bubble diameter of 5 to 50 μm in a very short time.

  In particular, when the average particle diameter of the toner is about 5 μm to 10 μm, the bubble diameter of the foamed fixing liquid 114 is used to apply the foamed fixing liquid 114 to the toner layer 113 without disturbing the toner layer 113 on the recording medium 112. The range is preferably 5 μm to 50 μm. As shown in FIG. 2, the foam-like fixing liquid 120 composed of the bubbles 122 is composed of a liquid 121 that separates each of the bubbles 122.

<Film thickness adjusting step and film thickness adjusting means>
The film thickness adjusting step in the fixing method according to the present invention is a step of forming a foam-like fixing solution on the contact surface of the foam-like fixing solution applying means to a desired thickness, and is performed by the film thickness adjusting means.

  The film thickness adjusting means is not particularly limited as long as the foam fixing solution can be formed to a desired thickness on the contact surface of the foam fixing solution applying means, and can be appropriately selected according to the purpose. Examples include a blade for adjusting thickness, and a combination of a blade and a coating roller. Note that aspects of the film thickness adjusting step and the film thickness adjusting means will be described later.

<Foam Fixer Application Step and Foam Fixer Application Means>
The foamy fixing solution applying step in the fixing method according to the present invention is a step of applying the foamed fixing solution formed in a desired thickness to the toner layer on the medium, and is carried out by the foamy fixing solution applying means.

  4A and 4B are schematic configuration diagrams showing an example of a film thickness adjusting unit and a foamy fixing solution applying unit in the fixing device according to the present invention. The fixing device 140 of the present invention shown in FIG. 4A is a coating for applying the desired fine bubble foam fixing solution generated by the foam fixing solution generator 130 described above to the toner layer constituting the toner or the like. The film thickness of the desired fine bubble foam fixing solution on the roller 141 and the coating roller surface is adjusted according to the thickness of the unfixed toner layer on the recording medium, and the optimum film thickness of the foam fixing solution is adjusted. It has a film thickness adjusting blade 142 which is a film thickness adjusting means for adjusting, and a pressure roller 143 at a position facing the application roller 141.

  A recording medium having unfixed toner on the surface passes through a nip portion composed of an application roller 141 and a pressure roller 143. On the other hand, the foamed fixing solution generated by the foamed fixing solution generating means 130 is adjusted in film thickness by the film thickness adjusting blade 142 and disposed on the application roller 141 as a foamed fixing solution layer having a desired thickness. The foam-like fixing liquid layer formed on the application roller 141 in this manner is applied onto the unfixed toner in synchronization with the passage of the recording medium having unfixed toner through the nip portion.

  FIG. 4B is an enlarged schematic view of the application roller 141 and the film thickness adjusting blade 142, and a layer of foam-like fixing liquid is formed on the recording medium on the application roller 141 constituting the foam-like fixing liquid application unit. It is formed through a film thickness adjusting blade 142 which is a film thickness adjusting means according to the thickness of the upper unfixed toner layer. With the film thickness adjusting blade 142 as the film thickness adjusting means, the foam fixing solution has an unfixed toner layer corresponding to the bubble size, foam viscosity, coating pressure and unfixed toner layer thickness. The film thickness of the fixing solution layer is optimized with respect to the permeation time. As described above, the desired fine foam foam fixing solution is composed of a large foam generating section that generates large foam and a small foam generating section that separates large foam with a shearing force to generate micro foam. It is generated by the foamed fixing liquid generating means 130 that is configured to be included, and is dropped from the liquid supply port between the coating roller 141 and the film thickness adjusting blade 142 that is the film thickness adjusting means.

  As shown in FIGS. 5A and 5B, the film thickness of the foam-like fixing solution on the application roller is adjusted using a film thickness adjusting blade 142 provided with a gap as shown in FIG. 5A. When the thickness is made thinner, the gap may be narrowed, and when the film thickness is made thicker as shown in FIG. 5B, the gap may be made wider. The gap is adjusted by using a drivable rotary shaft at the end of the film thickness adjusting blade 142, the thickness of the toner layer, the environmental temperature, etc., as well as the bubble size, bubble viscosity, and application pressure of the foam-like fixer. The optimum film thickness for adjusting the permeation time of the foamy fixing solution in the unfixed toner layer according to the pressure and the layer thickness of the unfixed toner may be adjusted.

  The shape, structure, size and material of the application roller constituting the foam-like fixing liquid application means are not particularly limited as long as the foam-type fixing liquid can be applied, but have a curved surface part at least on a part of its surface. Those are preferred.

  The blade for adjusting film thickness may be a wire bar in addition to the blade for adjusting film thickness shown in FIGS. 5A and 5B. The thickness of the foam fixing solution on the application roller is adjusted by the wire bar. As described above, the foam fixing solution is a fine foam generating unit that generates large bubbles and a minute foam that separates the large bubbles with shearing force. It is produced | generated by the foam-like fixing liquid production | generation means which has a foam production | generation part, and is dripped between a film thickness adjustment wire bar and an application roller from a liquid supply port. By using the wire bar as the film thickness adjusting means, the uniformity of the foam-like fixing liquid film in the axial direction of the coating roller surface is improved as compared with the blade.

The bulk density of the foamy fixing solution ^is preferably ^{0.01g / cm 3 ~0.1g / cm 3} , from the viewpoint to prevent the occurrence of residual liquid feeling on the medium surface when the fixing liquid application, 0.01 g / cm more preferably ^{3 ~0.02g} / cm ^3, more preferably ^{0.0125g / cm 3 ~0.02g / cm 3} . This is because, like the coating roller 141 in FIGS. 4A and 4B, the foam film of the fixing liquid on the surface of the contact applying means is required to have a thickness more than the thickness of the fine particle layer on the recording medium. In general, the thickness of the foam film is preferably 50 μm to 80 μm. On the other hand, in order not to cause a residual liquid feeling (wet feeling) when the fixing liquid adheres to the recording medium surface, the amount of fixing liquid attached is preferably 0.1 mg / cm ² or less per unit area of the recording medium. .

  FIG. 6 is a schematic configuration diagram showing the configuration of the fixing device according to the embodiment of the present invention. In the fixing device 140 of the embodiment shown in FIG. 6, the pressure roller 143 may be configured using an elastic porous body (hereinafter also referred to as a sponge material) as an elastic layer. It is necessary to take a timing of the nip time so that the application roller and the toner layer are peeled off after the foamy fixing solution penetrates the toner layer and reaches the medium such as paper. In this respect, the pressure roller 43 made of a sponge material is preferable because the nip time is in the range of 50 milliseconds to 300 milliseconds and can be greatly deformed with a weak pressure.

  The nip time is calculated by nip time = nip width / paper conveyance speed. The paper transport speed can be obtained from design data of the paper transport drive mechanism. For the nip width, a colored paint that does not dry is applied thinly on the entire surface of the application roller, and the recording medium is sandwiched between the application roller 141 and the pressure roller 143 that faces the recording medium (the rollers are not rotated) to color the recording medium. It can be determined by applying paint and measuring the length in the paper conveyance direction at the colored portion (usually colored in a rectangular shape) as the nip width.

  By adjusting the nip width according to the conveyance speed of the recording medium, the nip time needs to be equal to or longer than the toner layer permeation time of the foamy fixing solution. In the example shown in FIG. 6, the pressure roller 143 is made of a sponge material with an elastic layer, so that the distance between the axes of the application roller 141 and the pressure roller 143 is changed according to the conveyance speed of the recording medium, and the nip width is increased. It becomes easy to change. Elastic rubber may be used as the material of the pressure roller 143 instead of the sponge, but the sponge can be deformed with a force weaker than that of the elastic rubber, so that the pressure applied to the application roller 141 is not excessively increased. A long nip width can be secured.

  Note that a plasticizer is contained in the fixing liquid, and if the fixing liquid should adhere to a pressure roller formed of a sponge material, there is a possibility that problems such as softening of the sponge material may occur. Therefore, the resin material of the sponge material is preferably a material that does not soften or swell with respect to the liquid plasticizer. Further, the pressure roller using a sponge material may be configured to be covered with a flexible film. Even if the sponge material is a material that deteriorates with a liquid plasticizer, the sponge roller can be prevented from being deteriorated by covering with a flexible film that does not soften or swell with the liquid plasticizer. There is no restriction | limiting in particular as a sponge material, For example, the porous body of resin, such as polyethylene, a polypropylene, polyamide, is mentioned. Moreover, as long as it has flexibility, there is no restriction | limiting in particular as a flexible film which covers sponge, For example, a polyethylene terephthalate, polyethylene, a polypropylene, a tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA) is mentioned, for example. It is done.

  In FIG. 6, when the application roller 141 and the pressure roller 143 using a sponge material are always in contact, the foamy fixing liquid on the application roller 141 is applied to the pressure roller 143 when the recording medium is not conveyed. There is a risk of adhering to and soiling. In order to prevent this, a paper leading edge detection unit (not shown) is provided upstream in the recording medium conveyance direction as viewed from the application roller 141, and the foam-like fixing liquid is applied only from the leading edge of the recording medium to the rear according to the leading edge detection signal. It is preferable to form the foam-like fixing liquid on the application roller 141 at the timing of application.

  In the fixing device 140 shown in FIG. 6, the application roller 141 and the pressure roller 143 using the sponge material are separated from each other during standby, and the leading end of the recording medium is detected only during application by a drive mechanism (not shown). A configuration in which the application roller 141 and the pressure roller 143 using a sponge material are in contact with each other is also preferable. The fixing device 140 shown in FIG. 6 also detects the trailing edge of the recording medium, and is configured to separate the application roller 141 and the pressure roller 143 using a sponge material in accordance with the trailing edge detection signal of the recording medium. It is also preferable to do.

  FIG. 7 is a schematic configuration diagram showing another configuration of the fixing device according to the embodiment of the present invention. The fixing device 140 according to the embodiment shown in FIG. 7 uses a pressure belt 144 instead of the pressure roller 143 shown in FIG. A liquid produced by a foam-like fixing liquid producing means 130 comprising a large foam producing part that produces large foams and a fine foam producing part that separates large foams with shearing force to produce fine foams. A foam-like fixing solution having a desired bubble diameter is supplied from a supply port to a supply port of a film thickness adjusting blade 142 which is a film thickness adjusting unit using a tube or the like. Then, by adjusting the gap between the film thickness adjusting blade 142 of the film thickness adjusting means and the application roller 141 to adjust the layer thickness of the foam-like fixing solution on the application roller 141, the optimum film thickness of the foam-like fixing solution is adjusted. Make adjustments. As a material of the pressure belt 144, for example, a member such as a seamless nickel belt, a seamless PET file, or the like coated with a releasable fluororesin such as PFA may be used.

  Thus, in the configuration using the belt, the nip width can be easily widened. Therefore, the configuration using the belt is not limited to the configuration shown in FIG. Further, by using at least one of the application side and the pressure side as a belt, the nip width can be easily widened, and an excessive force that causes wrinkles on the paper is not applied. Further, when the nip time and the paper transport speed are the same, the paper transport speed can be increased and high-speed fixing can be performed.

  In addition, the toner fixing device may include a pair of smoothing rollers (hard rollers) that pressurize at least a part of the softened or swollen toner after supplying the fixing liquid of the present invention to the toner. By pressurizing the above softened or swollen toner with a pair of smoothing rollers (hard rollers), the surface of the softened or swollen toner layer can be smoothed to give the toner gloss. Furthermore, by fixing the softened or swollen toner into the recording medium, the fixing property of the toner to the recording medium can be improved.

<Other processes and other means>
<< Heating process and heating means >>
The fixing method and the fixing device according to the present invention may further include a heating step and a heating means for heating the toner layer provided with the foamy fixing solution. The heating temperature in the heating step and the heating means is not particularly limited as long as sufficient fixing characteristics can be obtained, but for example, 50 ° C to 100 ° C is preferable. If the heating temperature is less than 50 ° C., fixing may be insufficient, and if it exceeds 100 ° C., it is uneconomical in terms of energy consumption.

  As a form of the heating means, a roller or the like may be appropriately selected as long as the above-described aspect can be implemented. When the heating means is constituted by a roller, for example, as shown in FIG. 8, it is constituted by a pressure roller 146 and a pressure roller 148, and a heating medium such as an infrared heater 147 is applied to the roller in contact with the fixing object. It may be provided.

(Image forming method and image forming apparatus)
The image forming method of the present invention uses the fixing method of the present invention, and the image forming apparatus of the present invention uses a fixing device that embodies the fixing method of the present invention.
The image forming method of the present invention includes a charging step for uniformly charging the surface of the latent image carrier, an exposure step for exposing the surface of the charged latent image carrier based on image data, and writing an electrostatic latent image, A developer layer having a predetermined layer thickness is formed on the developer carrier by a developer layer regulating member, and the electrostatic latent image formed on the surface of the latent image carrier is developed through the developer layer to be visualized. An electrostatic latent image forming step comprising: a developing step, a transfer step for transferring a visible image on the surface of the latent image carrier to a transfer target, and a fixing step for fixing the visible image on the transfer target. And at least a development process, a transfer process, and a fixing process, and further include other processes appropriately selected as necessary, for example, a static elimination process, a cleaning process, a recycling process, a control process, and the like. The fixing step is performed by the fixing method of the present invention.

  The image forming apparatus of the present invention includes a latent image carrier that carries a latent image, a charging unit that uniformly charges the surface of the latent image carrier, and the surface of the charged latent image carrier that is exposed based on image data. Exposure means for writing an electrostatic latent image, developing means for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier to visualize it, and a visible image on the surface of the latent image carrier. The image forming apparatus includes at least a transfer unit that transfers to a transfer body and a fixing unit that fixes a visible image on the transfer body. Further, other units appropriately selected as necessary, for example, a charge eliminating unit and a cleaning unit , Recycling means, control means, etc.

The electrostatic latent image can be formed, for example, by uniformly charging the surface of the latent image carrier with a charging unit and then exposing the surface of the latent image carrier imagewise with an exposure unit.
In the formation of a visible image by the development, a toner layer is formed on a developing roller as a developer carrying member, and the toner layer on the developing roller is conveyed so as to be in contact with a photosensitive drum as a latent image carrying member. Thus, the electrostatic latent image on the photosensitive drum is developed. The toner is stirred by the stirring means and mechanically supplied to the developer supply member. The toner supplied from the developer supply member and deposited on the developer carrier is formed into a uniform thin layer by passing through a developer layer regulating member provided to contact the surface of the developer carrier. Furthermore, it is charged. The electrostatic latent image formed on the latent image carrier is developed by attaching the toner charged by the developing means in the developing region to become a toner image.

The transfer of the visible image can be performed, for example, by charging the latent image carrier (photoconductor) using a transfer charger, and can be performed by the transfer unit.
The transferred visible image is fixed by using a fixing device to transfer the visible image transferred to the recording medium, and may be performed each time the toner of each color is transferred to the recording medium. On the other hand, it may be carried out simultaneously at the same time in a state of being laminated.
There is no restriction | limiting in particular as said fixing device, According to the objective, it can select suitably.

Next, the basic configuration of the image forming apparatus (printer) according to the embodiment of the present invention will be further described with reference to FIGS.
FIG. 9 is a schematic diagram showing the configuration of the image forming apparatus according to the embodiment of the present invention. Here, an embodiment applied to an electrophotographic image forming apparatus will be described. The image forming apparatus includes yellow (hereinafter referred to as “Y”), cyan (hereinafter referred to as “C”), magenta (hereinafter referred to as “M”), black (hereinafter referred to as “K”). The color image is formed from the four color toners.

First, a basic configuration of an image forming apparatus (a “tandem type image forming apparatus”) that includes a plurality of latent image carriers and parallels the plurality of latent image carriers in the moving direction of the surface moving member will be described.
This image forming apparatus includes four photosensitive members 1Y, 1C, 1M, and 1K as latent image carriers. Here, a drum-shaped photoconductor is taken as an example, but a belt-shaped photoconductor can also be adopted. Each of the photoconductors 1Y, 1C, 1M, and 1K is rotationally driven in the direction of the arrow in FIG. Each of the photoconductors 1Y, 1C, 1M, and 1K is rotationally driven in the direction of the arrow in FIG. Each of the photoreceptors 1Y, 1C, 1M, and 1K is obtained by forming a photosensitive layer on a relatively thin cylindrical conductive substrate and further forming a protective layer on the photosensitive layer. An intermediate layer may be provided between the protective layer.

  FIG. 10 is a schematic diagram showing a configuration of the image forming unit 2 in which the photoconductor is disposed. Since the configuration around each of the photoreceptors 1Y, 1C, 1M, and 1K in the image forming units 2Y, 2C, 2M, and 2K is the same, only one image forming unit 2 is illustrated, and a code Y for color coding is shown. , C, M, and K are omitted. Around the photosensitive member 1, along the surface movement direction, a charging device 3 as a charging unit, a developing device 5 as a developing unit, and a toner image on the photosensitive member 1 are transferred to a recording medium or an intermediate transfer belt 10. A transfer device 6 as a transfer unit and a cleaning device 7 for removing untransferred toner on the photoreceptor 1 are arranged in this order. Between the charging device 3 and the developing device 5, light is emitted from an exposure device 4 as an exposure unit that performs exposure based on image data on the surface of the charged photoconductor 1 and writes an electrostatic latent image. Space is secured so that it can pass through.

  The charging device 3 charges the surface of the photoreceptor 1 to a negative polarity. The charging device 3 according to the present embodiment includes a charging roller as a charging member that performs charging processing by a so-called contact / proximity charging method. In other words, the charging device 3 charges the surface of the photosensitive member 1 by bringing the charging roller into contact with or close to the surface of the photosensitive member 1 and applying a negative bias to the charging roller. A DC charging bias is applied to the charging roller such that the surface potential of the photoreceptor 1 is −500V.

  Note that a charging bias in which an AC bias is superimposed on a DC bias can also be used. The charging device 3 may be provided with a cleaning brush for cleaning the surface of the charging roller. As the charging device 3, a thin film may be wound around both end portions in the axial direction on the circumferential surface of the charging roller and installed so as to contact the surface of the photoreceptor 1. In this configuration, the surface of the charging roller and the surface of the photoreceptor 1 are extremely close to each other with a distance corresponding to the thickness of the film. Therefore, a discharge is generated between the surface of the charging roller and the surface of the photosensitive member 1 by the charging bias applied to the charging roller, and the surface of the photosensitive member 1 is charged by the discharge.

  An electrostatic latent image corresponding to each color is formed on the surface of the photoreceptor 1 charged in this manner by exposure by the exposure device 4. The exposure device 4 writes an electrostatic latent image corresponding to each color on the photoreceptor 1 based on image information corresponding to each color. In addition, although the exposure apparatus 4 of this embodiment is a laser system, the other system which consists of an LED array and an imaging means can also be employ | adopted.

  The toner replenished into the developing device 5 from the toner bottles 31Y, 31C, 31M, and 31K is conveyed by the supply roller 5b and carried on the developing roller 5a. The developing roller 5 a is conveyed to a developing area facing the photoreceptor 1. Here, the developing roller 5 a moves in the same direction at a linear velocity faster than the surface of the photosensitive member 1 in a region facing the photosensitive member 1 (hereinafter referred to as “developing region”). Then, the toner on the developing roller 5 a supplies the toner to the surface of the photosensitive member 1 while rubbing the surface of the photosensitive member 1. At this time, a developing bias of −300 V is applied to the developing roller 5a from a power source (not shown), thereby forming a developing electric field in the developing region. Then, between the electrostatic latent image on the photoreceptor 1 and the developing roller 5a, an electrostatic force directed toward the electrostatic latent image side acts on the toner on the developing roller 5a. As a result, the toner on the developing roller 5 a adheres to the electrostatic latent image on the photoreceptor 1. By this adhesion, the electrostatic latent image on the photoreceptor 1 is developed into a corresponding color toner image.

  The intermediate transfer belt 10 in the transfer device 6 is stretched around three support rollers 11, 12, and 13 and is configured to endlessly move in the direction of the arrow in FIG. 9. On the intermediate transfer belt 10, toner images on the photoreceptors 1Y, 1C, 1M, and 1K are transferred so as to overlap each other by an electrostatic transfer method. Although there is a configuration using a transfer charger in the electrostatic transfer system, a configuration using a transfer roller 14 that generates less transfer dust is adopted here. Specifically, primary transfer rollers 14Y, 14C, 14M, and 14K as transfer devices 6 are disposed on the back surface of the portion of the intermediate transfer belt 10 that contacts the photoreceptors 1Y, 1C, 1M, and 1K, respectively. Here, a primary transfer nip portion is formed by the portions of the intermediate transfer belt 10 pressed by the primary transfer rollers 14Y, 14C, 14M, and 14K and the photoreceptors 1Y, 1C, 1M, and 1K. When transferring the toner images on the photoreceptors 1Y, 1C, 1M, and 1K onto the intermediate transfer belt 10, a positive bias is applied to each primary transfer roller. As a result, a transfer electric field is formed in each primary transfer nip portion, and the toner images on the photoreceptors 1Y, 1C, 1M, and 1K are electrostatically attached to the intermediate transfer belt 10 and transferred.

  A belt cleaning device 115 for removing toner remaining on the surface of the intermediate transfer belt 10 is provided around the intermediate transfer belt 10. The belt cleaning device 115 is configured to collect unnecessary toner adhering to the surface of the intermediate transfer belt 10 with a fur brush and a cleaning blade. The collected unnecessary toner is transported from the belt cleaning device 115 to a waste toner tank (not shown) by a transport means (not shown).

  Further, a secondary transfer roller 16 is disposed in contact with the portion of the intermediate transfer belt 10 stretched around the support roller 13. A secondary transfer nip portion is formed between the intermediate transfer belt 10 and the secondary transfer roller 16, and transfer paper as a recording member is fed into this portion at a predetermined timing. This transfer paper is accommodated in a paper feed cassette 20 on the lower side of the exposure apparatus 4 in the drawing, and is conveyed to the secondary transfer nip portion by a paper feed roller 21, a registration roller pair 22, and the like. Then, the toner images superimposed on the intermediate transfer belt 10 are collectively transferred onto the transfer paper at the secondary transfer nip portion. At the time of the secondary transfer, a positive bias is applied to the secondary transfer roller 16, and the toner image on the intermediate transfer belt 10 is transferred onto the transfer paper by a transfer electric field formed thereby.

  Fixing is performed on the downstream side of the secondary transfer nip portion in the conveyance direction of the transfer paper by a fixing device that controls the film thickness of the foam-like fixing liquid based on image information from an exposure device (not shown). That is, for the unfixed toner image transferred to the recording member, the film thickness of the foam-like fixing liquid layer is controlled based on image information from an exposure device (not shown), for example, a color image or a solid black image. A foam-like fixing solution supplied from a toner fixing device is applied, and an unfixed toner image is formed by a plasticizer that dissolves or swells at least a part of the resin contained in the toner contained in the foam-like fixing solution. And fixing to the recording member. As a result, the toner image placed on the transfer paper is fixed on the transfer paper. Then, the fixed transfer paper is discharged by a paper discharge roller 24 onto a paper discharge tray on the upper surface of the apparatus.

-Fixing method and fixing device by spray method-
[Fixing method and fixing device]
FIG. 11 shows a main configuration of an image forming apparatus such as a copying machine, a printer, a facsimile, or a complex machine thereof. The illustrated one is an electrophotographic tandem type color image forming apparatus that directly transfers a toner image on an image carrier onto a recording medium without using an intermediate transfer belt. It is.

  Reference numeral 41 in FIG. 11 denotes an endless belt-like transport belt. In the illustrated example, the conveyor belt 41 is provided so as to be able to rotate around the support (drive) roller 12 and the support (driven) roller 13 in a counterclockwise direction in the drawing. Of course, the number of rollers around which the conveyor belt 41 is wound is not limited to two, and a roller for adjusting the deviation of the conveyor belt 41, a tension roller, and the like may be separately provided so as to be wound around three or more rollers.

  Around the conveyor belt 41, four image forming means 15K for black, magenta, cyan, and yellow are sequentially arranged along the traveling direction of the conveyor belt 41 on a horizontal stretched portion between the driving roller 12 and the driven roller 13. 15M, 15C, and 15Y are installed side by side to constitute a tandem image forming device 46. Although not shown in the figure, an exposure device and the like are further provided on the tandem image forming device 46.

  Between the transport belt 41 and the tandem image forming device 46, a paper transport path for transporting the paper 17 as a recording medium is formed from right to left in FIG. A registration roller (not shown) is disposed upstream along the sheet conveyance path, and a fixing device 18 is disposed downstream.

  FIG. 12 shows a schematic configuration of one image forming unit 15 provided in the image forming apparatus shown in FIG. The four image forming means 15K, 15M, 15C, and 15Y have the same configuration as shown in FIG.

  Reference numeral 20 in FIG. 12 denotes a photoconductor that is a drum-shaped image carrier. Around the photosensitive member 20, a developing device 22, a transfer device 23, a cleaning device 24, a static elimination device 25, and the like are arranged in order from the charging device 21 arranged at the upper left in the rotational direction indicated by the arrow in the drawing.

  Here, in the illustrated example, the charging device 21 employs a non-contact charging method that gives uniform negative charging using a charging charger, but a contact charging method using a charging roller may of course be employed. In this example, the developing device 22 uses a two-component developer composed of a positively charged carrier 26 and a negatively charged toner 27, which is carried by a developing sleeve 28 and attaches only the toner 27 to the photosensitive member 20. The electrostatic latent image on the body 20 is visualized.

  In the illustrated example, the transfer device 23 employs a non-contact plus transfer corona charger system and is disposed so as to face the photoconductor 20 with the conveying belt 41 interposed therebetween. A property brush, a transfer roller, etc. can also be used. The cleaning device 24 is provided with a cleaning brush 30 and a cleaning blade 31 as cleaning members. As a result, the toner scraped off by the cleaning brush 30 and the cleaning blade 31 can be recovered and reused in the developing device 22 by a recovery screw (not shown) and a toner recycling device. Moreover, as the static elimination apparatus 25, a static elimination lamp is used, for example.

  Then, along with the clockwise rotation of the photoconductor 20, the surface of the photoconductor 20 is uniformly charged by the charging device 21, and writing light L (Lk, Lm, Lc, Ly in FIG. 11) is emitted by an exposure device (not shown). After irradiation, an electrostatic latent image is formed on each photoconductor 20, and each color toner is attached by a developing device 22 to visualize the electrostatic latent image, and each color monochromatic toner is formed on each photoconductor 20. Form an image.

  The recording medium (paper) 17 is transported through a paper transport path, and is fed onto the transport belt 41 by registration rollers in time with each color toner image formed on the photoconductor 20. Then, as the conveyor belt 41 travels, the recording medium (paper) 17 is further conveyed, and the monochromatic toner images on the respective photoconductors 20 are sequentially transferred to the conveyed paper 17 by the transfer device 23, and onto the paper 17. A single color toner image of each color is superimposed to form a composite color image. After the toner image has been transferred, the surface of the photoconductor 20 is cleaned by the cleaning device 24, and then is neutralized by the neutralizing device 25 to be initialized, and is prepared for another image formation starting from the charging device 21 again.

  The negatively charged toner 27 on the paper 17 that forms the composite color image is only electrically attached to the paper 17 at this time, and is separated from the paper 17 when subjected to a strong impact or rubbing. The sheet 17 on which the composite color image is formed is conveyed by the conveying belt 41 and guided to the fixing device 18, and the transferred image is fixed by the fixing device 18, and then discharged to a paper discharge stack unit (not shown).

  As shown in FIG. 11, the fixing device 18 has a spray means 33 for spraying the toner fixing liquid as fixing droplets, and the fixing droplet sprayed by the spray means 33 has a negative polarity of the same polarity as the unfixed toner. A droplet charging unit 34 for applying electric charge, a medium conveying unit 35 for conveying the paper 17 on which unfixed toner is placed, through the atmosphere of the fixing droplet to which electric charge is applied by the droplet charging unit 34, and A recording medium charging unit 36 for charging the sheet 17 conveyed by the medium conveying unit 35 to a positive polarity opposite to that of the unfixed toner and the fixed droplets is provided.

FIG. 13 shows an enlarged view of the fixing device 18 shown in FIG.
As can be seen from FIG. 13, the spray means 33 is installed in the spray chamber 38 partitioned by the casing 37, and the toner fixing liquid stored in the fixing liquid storage section (not shown) has the mode value. Spraying is performed as fixing droplets having a droplet diameter of 15 μm or less, and the spray chamber 38 is filled with the fixing droplets.

  As the droplet charging unit 34, an ionizer or the like is used, air ions are sprayed into the spray chamber 38, mixed with the fixing droplet sprayed by the spraying unit 33, and the fixing droplet has the same polarity as the unfixed toner. Charge negatively. Unlike the illustrated example, when the unfixed toner is positively charged, the fixing droplet is also positively charged.

  The medium transport unit 35 includes a plurality of rollers 40 and a transport belt 41 that is wound around the rollers 40 and electrostatically attracts and transports the paper 17. Then, the sheet 17 transferred by the transfer device 23 and carrying the unfixed toner 42 having a negative residual charge as shown in the drawing is conveyed by the conveyance belt 41 and sent to the fixing device 18, and the medium conveyance of the fixing device 18 is performed. Subsequently, the toner is conveyed from the right to the left in FIG. 13 by the conveying belt 41 of the means 35 through the atmosphere of the fixing droplets to which the charge is applied by the droplet charging means 34.

  The recording medium charging unit 36 includes an electrode 44 disposed on the inner side of the conveyance belt 41 wound around the roller 40 and a power source 45 connected to the electrode 44. Then, a voltage is applied to the electrode 44 disposed inside the transport belt 41 by the power source 45, and the paper 17 transported by the transport belt 41 is charged positively with a polarity opposite to that of the unfixed toner 42 and the fixed droplets. . At this time, of course, the transport belt 41 is formed of a material that does not prevent the paper 17 from being charged. As a result, by sucking from the back side of the paper 17 by Coulomb force, the fixing droplets adhering to the paper 17 penetrate further to the back side of the paper 17, and the liquid concentration is made even more uniform on the front and back of the paper 17. Curling of the sheet 17 can be reduced.

  Note that reference numeral 46 in FIG. 13 denotes a static elimination roller as a static elimination member that neutralizes the paper 17 coming out of the fixing device 18 and, of course, is not limited to a roller and may be a brush or the like.

  As described above, according to the illustrated examples of FIGS. 11 to 13, the fixing droplet sprayed by the spraying unit 33 is given a charge having the same polarity as the unfixed toner 42 on the paper 17 by the droplet charging unit 34. The sheet 17 on which the unfixed toner 42 is mounted is conveyed by the medium conveying unit 35 through the atmosphere of the fixing droplets to which the electric charge is applied, and the conveyed sheet 17 is unfixed by the recording medium charging unit 36. 42 and the fixing droplet are charged in the opposite polarity, and are forcibly attracted by the Coulomb force, and the unfixed toner 42 and the fixing droplet 53 are adsorbed on the recording medium (paper) 17 and fixed on the recording medium (paper) 17. Is done.

  When the toner fixing liquid is sprayed by the spraying means 33 as the fixing droplet 53 having a mode droplet diameter of 15 μm or less, the sprayed fixing droplet 53 is uniformly floated in the space as a dry mist, and the paper 17 Therefore, the fixing droplet 53 can be adhered to the sheet 17 without waste, and the fixing liquid can be effectively used and the uneven fixing can be eliminated.

-Fixing method and fixing device using contact means-
[Fixing method and fixing device]
FIG. 14 shows an electrophotographic tandem color image forming apparatus, which uses an intermediate transfer belt to temporarily transfer a toner image on an image carrier to the intermediate transfer belt, and then intermediate transfer belt. This is a medium indirect transfer system in which the upper toner image is secondarily transferred to a recording medium.

  FIG. 14 is a schematic configuration diagram of a portion including a fixing device as fixing means of the image forming apparatus according to the present embodiment. In the image forming apparatus of the present embodiment, a fixing device 90 is disposed on the upstream side of the secondary transfer portion in the surface movement direction of the intermediate transfer belt 10. The fixing device 90 includes a supply roller 91 as a fixing liquid supply unit disposed so as to face the surface of the intermediate transfer belt 10 with a small gap. The fixing device 90 is configured to be movable by a driving mechanism (not shown) so that the supply roller 91 can approach or separate from the surface of the intermediate transfer belt 10. A fixing liquid 92 is accommodated in the fixing liquid tank 93 of the fixing device 90, and the supply roller 91 is disposed in the fixing liquid 92. The supply roller 91 is rotationally driven in the direction of the arrow in the drawing when the fixing liquid 92 is applied to the toner. As a result, the fixing liquid 92 is pumped up on the surface of the supply roller 91. The fixing liquid 92 pumped up in this way is regulated by the metering blade 94, and the fixing liquid adhering to the surface of the supply roller 91 is adjusted to an appropriate amount. The fixing solution on the supply roller 91 is conveyed to a position facing the surface of the intermediate transfer belt 10 as the supply roller 91 rotates, and supplies the fixing solution to the surface of the intermediate transfer belt 10.

  Further, when the supply roller 91 is used as a fixing liquid supply unit that supplies the fixing liquid to the toner on the intermediate transfer belt 10, there is a possibility that the toner image carried on the intermediate transfer belt 10 may be disturbed. Therefore, in this embodiment, a supply roller 91 in which a base made of a conductive material is covered with an insulating layer or a high resistance layer is used, and a power source 95 as an electric field forming unit is connected to the supply roller 91. Specifically, for example, a conductive rubber layer formed on a stainless steel core and the surface thereof covered with an insulating PFA tube can be used. With such a configuration, an electric field is formed between the supply roller 91 and the intermediate transfer belt 10 in a direction in which the toner is pressed toward the intermediate transfer belt. By forming such an electric field, the binding force of the toner on the intermediate transfer belt 10 toward the intermediate transfer belt 10 at the liquid supply position can be increased. As a result, the fixing liquid 92 can be supplied to the toner without disturbing the toner image carried on the intermediate transfer belt 10.

  Since the image forming method and the image forming apparatus according to the present invention use the fixing method of the present invention, the image strength immediately after fixing is high, and a high-quality image that is resistant to rubbing can be formed even in a halftone image.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Synthesis Example 1)
-Synthesis of unmodified polyester-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, 2 parts by mass of dibutyltin oxide was added and reacted at 230 ° C. under normal pressure for 8 hours. Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg to synthesize an unmodified polyester.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 5,600, and a glass transition temperature (Tg) of 55 ° C.

(Synthesis Example 2)
-Synthesis of polyalkylene glycol ester compound 1-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 1 part by mass of p-toluenesulfonic acid is added to 100 parts by mass of a mixture of both behenic acid / polyethylene glycol # 4000 having a molar ratio of 2.2. The polyalkylene glycol ester compound 1 (PAG compound 1) was synthesized by reacting at 120 ° C. under reduced pressure of 5 mmHg for 5 hours.

(Synthesis Example 3)
-Synthesis of polyalkylene glycol ester compound 2-
1 part by weight of p-toluenesulfonic acid is added to 100 parts by weight of a mixture of both behenic acid / polyethylene glycol # 6000 in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. The polyalkylene glycol ester compound 2 (PAG compound 2) was synthesized by reacting at 120 ° C. under a reduced pressure of 5 mmHg for 5 hours.

(Synthesis Example 4)
-Synthesis of polyalkylene glycol ester compound 3-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 1 part by mass of p-toluenesulfonic acid is added to 100 parts by mass of a mixture of both behenic acid / polyethylene glycol # 11000 at a molar ratio of 2.2. The polyalkylene glycol ester compound 3 (PAG compound 3) was synthesized by reacting at 120 ° C. under reduced pressure of 5 mmHg for 5 hours.

(Synthesis Example 5)
-Synthesis of polyalkylene glycol ester compound 4-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 1 part by mass of p-toluenesulfonic acid is added to 100 parts by mass of a mixture of both behenic acid / polyethylene glycol # 20000 having a molar ratio of 2.2. The polyalkylene glycol ester compound 4 (PAG compound 4) was synthesized by reacting at 120 ° C. under a reduced pressure of 5 mmHg for 5 hours.

(Synthesis Example 6)
-Synthesis of polyalkylene glycol ester compound 5-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 1 part by mass of p-toluenesulfonic acid is added to 100 parts by mass of a mixture of both of the molar ratio of montanic acid / polyethylene glycol # 20000 of 2.2. The polyalkylene glycol ester compound 5 (PAG compound 5) was synthesized by reacting at 120 ° C. under reduced pressure of 5 mmHg for 5 hours.

(Synthesis Example 7)
-Synthesis of polyalkylene glycol ester compound 6-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 1 part by mass of p-toluenesulfonic acid is added to 100 parts by mass of a mixture of stearic acid / polyethylene glycol # 4000 having a molar ratio of 2.2. The polyalkylene glycol ester compound 6 (PAG compound 6) was synthesized by reacting at 120 ° C. under reduced pressure of 5 mmHg for 5 hours.

(Synthesis Example 8)
-Synthesis of polyalkylene glycol ester compound 7-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 1 part by mass of p-toluenesulfonic acid is added to 100 parts by mass of a mixture of myristic acid / polyethylene glycol # 4000 having a molar ratio of 2.2. The polyalkylene glycol ester compound 7 (PAG compound 7) was synthesized by reacting at 120 ° C. under a reduced pressure of 5 mmHg for 5 hours.

  Next, the synthesized polyalkylene glycol ester compounds (PAG compounds) 1 to 7 were measured for weight average molecular weight and melting point as follows. The results are shown in Table 1.

<Weight average molecular weight (Mw) of polyalkylene glycol ester compound>
The weight average molecular weight (Mw) of the polyalkylene glycol ester compound was measured by the method shown below.
Gel permeation chromatography (GPC) measuring device: GPC-8220 GPC (manufactured by Tosoh Corporation)
-Column: TSKgel SuperHZM-H 15cm triple (made by Tosoh Corporation)
・ Temperature: 40 ℃
・ Solvent: Tetrahydrofuran (THF)
・ Flow rate: 0.35 ml / min
Sample: 0.4 ml of 0.15 mass% sample was injected. Sample pretreatment: 0.15 mass% of the sample was dissolved in tetrahydrofuran (THF, manufactured by Wako Pure Chemical Industries, Ltd.), and then filtered through a 0.2 μm filter. The filtrate was used as a sample solution.
100 μL of the sample solution was injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts (that is, the molecular weight calculated in terms of polystyrene) . As a standard polystyrene sample for preparing a calibration curve, Showd STANDARD Std. No. S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580 were used. An RI (refractive index) detector was used as the detector.

<Melting point of polyalkylene glycol ester compound>
It measured by the following method using the differential scanning calorimeter ("DSC-60", Shimadzu Corporation make).
First, about 5 mg of each material (sample) was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Subsequently, it heated from 20 degreeC to 150 degreeC with the temperature increase rate of 10 degrees C / min, and measured the DSC curve with the differential scanning calorimeter ("DSC-60", Shimadzu Corporation make). From the obtained DSC curve, the melting point (melting point peak temperature) was calculated from the top of the endothermic curve with respect to the baseline using the analysis system in the “DSC-60” system.

However, in the general formula (I), R ¹ and R ² are all linear or branched alkyl groups having 1 to 24 carbon atoms, and Rxm and Rym may be the same or different from each other. And represents either a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. n represents an integer of 2 or more. m represents an integer of 2 or more and 4 or less.

(Production Example 1)
-Production of polyalkylene glycol ester compound dispersion-
200 parts by mass of polyalkylene glycol ester compound 1, 400 parts by mass of unmodified polyester resin, and 1,400 parts by mass of ethyl acetate were mixed, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Corporation), The polyalkylene glycol ester compound was dispersed in 3 passes under the condition that the feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / s, and 80% by volume of 0.5 mm zirconia beads were filled. 1 "was prepared.
Similarly, “polyalkylene glycol ester compound dispersion liquid 1” to “polyalkylene glycol ester compound dispersion liquid 7” were prepared using polyalkylene glycol ester (PAG) compounds 1 to 7 shown in Table 1.

Example 1
<Preparation of Toner 1>
-Preparation of master batch-
1,000 parts by weight of water and 540 parts by weight of carbon black “trade name: Printex 35” (manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5) and 1200 parts by weight of unmodified polyester of Synthesis Example 1 Were mixed using a Henschel mixer (Mitsui Mining Co., Ltd.). The mixture was kneaded with two rolls for 30 minutes in an environment of 150 ° C., then cooled by rolling and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

-Synthesis of prepolymer-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 81 parts by mass of bisphenol A propylene oxide 2-mole adduct, 283 parts by mass of terephthalic acid, Then, 22 parts by mass of trimellitic anhydride and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined. The obtained intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,600, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl group. The value was 49 mgKOH / g.

  Next, 411 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and are heated at 100 ° C. for 5 hours. By reacting, a prepolymer (polymer capable of reacting with an active hydrogen group-containing compound) was synthesized. The free isocyanate content of the obtained prepolymer was 1.60% by mass, and the solid content concentration of the prepolymer (after standing at 150 ° C. for 45 minutes) was 50% by mass.

-Synthesis of ketimine compounds-
In a reaction vessel equipped with a stirring bar and a thermometer, 30 parts by mass of isophoronediamine and 70 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (active hydrogen group-containing compound). The amine value of the obtained ketimine compound (active hydrogen group-containing compound) was 423.

-Dissolution of toner material or preparation of dispersion-
In a beaker, 15 parts by mass of a prepolymer, 60 parts by mass of an unmodified polyester, 130 parts by mass of ethyl acetate, and 42 parts by mass of the polyalkylene glycol ester compound dispersion 1 were stirred and dissolved. Next, 10 parts by mass of the master batch was charged, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Corporation), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / s, and 80% by volume of 0.5 mm zirconia beads were filled. The raw material solution was prepared by three passes under the above conditions, and 2.7 parts by mass of ketimine was added and dissolved to prepare a toner material solution or dispersion.

-Preparation of aqueous medium phase-
Next, 306 parts by mass of ion-exchanged water, 265 parts by mass of a 10% by weight tricalcium phosphate suspension, and 0.2 parts by mass of sodium dodecylbenzenesulfonate are mixed and stirred, and uniformly dissolved to prepare an aqueous medium phase. did.

  Next, 150 parts by mass of the aqueous medium phase is put in a container, and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Was added and mixed for 10 minutes to prepare an emulsified or dispersed liquid (emulsified slurry).

  Next, 100 parts by mass of the emulsified slurry was charged into a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min.

  Next, 100 parts by mass of the dispersed slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. To the obtained filter cake, 20 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.

To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. Furthermore, 20 mass parts of 10 mass% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes) and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh having an opening of 75 μm to prepare toner base particles of Example 1.

  Next, 0.5 parts by mass of silica particles (R972, manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts by mass of the obtained toner base particles, and mixed to prepare “Toner 1”.

(Example 2)
-Production of Toner 2-
In the same manner as in Example 1 except that 42 parts by mass of “polyalkylene glycol ester compound dispersion 1” was changed to 161 parts by mass of “polyalkylene glycol ester compound dispersion 1”, “Toner 2” Was made.

(Example 3)
-Production of Toner 3-
In the same manner as in Example 1 except that 42 parts by mass of “polyalkylene glycol ester compound dispersion 1” was changed to 16 parts by mass of “polyalkylene glycol ester compound dispersion 1”, “Toner 3” Was made.

Example 4
-Production of Toner 4-
“Toner 4” was prepared in the same manner as in Example 1, except that “polyalkylene glycol ester compound dispersion liquid 1” in Example 1 was replaced with “polyalkylene glycol ester compound dispersion liquid 2”.

(Example 5)
-Production of Toner 5-
“Toner 5” was produced in the same manner as in Example 1, except that “polyalkylene glycol ester compound dispersion liquid 1” in Example 1 was replaced with “polyalkylene glycol ester compound dispersion liquid 3”.

(Example 6)
-Production of Toner 6-
“Toner 6” was produced in the same manner as in Example 1, except that “polyalkylene glycol ester compound dispersion 1” was replaced with “polyalkylene glycol ester compound dispersion 4”.

(Example 7)
-Production of Toner 7-
“Toner 7” was produced in the same manner as in Example 1, except that “polyalkylene glycol ester compound dispersion 1” was replaced with “polyalkylene glycol ester compound dispersion 5”.

(Example 8)
-Production of Toner 8-
“Toner 8” was produced in the same manner as in Example 1, except that “polyalkylene glycol ester compound dispersion liquid 1” in Example 1 was changed to “polyalkylene glycol ester compound dispersion liquid 6”.

Example 9
-Production of Toner 9-
“Toner 9” was produced in the same manner as in Example 1, except that “polyalkylene glycol ester compound dispersion liquid 1” was replaced with “polyalkylene glycol ester compound dispersion liquid 7”.

(Example 10)
-Production of Toner 10-
In the same manner as in Example 1 except that 42 parts by mass of “Polyalkylene glycol ester compound dispersion 1” was changed to 4 parts by mass of “Polyalkylene glycol ester compound dispersion 1”, “Toner 10” Was made.

(Example 11)
-Production of Toner 11-
In the same manner as in Example 1 except that 42 parts by mass of “polyalkylene glycol ester compound dispersion 1” was changed to 212 parts by mass of “polyalkylene glycol ester compound dispersion 1”, “Toner 11” Was made.

(Example 12)
-Production of Toner 12-
In the same manner as in Example 1 except that 42 parts by mass of “Polyalkylene glycol ester compound dispersion 1” was changed to 94 parts by mass of “Polyalkylene glycol ester compound dispersion 1”, “Toner 12” Was made.

(Comparative Example 1)
-Production of Toner 13-
“Toner 13” was prepared in the same manner as in Example 1, except that “polyalkylene glycol ester compound dispersion 1” was not added.

  Next, the produced toners 1 to 13 were measured for volume average particle diameter (Dv) and ratio (Dv / Dn) and average circularity as follows. The results are shown in Table 2.

<Volume average particle diameter (Dv) and ratio (Dv / Dn)>
The volume average particle diameter (Dv) and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) are determined by a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.). ) Using an analysis software (Beckman Coulter Multisizer 3 Version 3.51).
Specifically, 0.5 mL of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 mL glass beaker, and 0.5 g of each toner is added. The mixture was stirred with a microspatel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped such that the concentration indicated by the apparatus was 8% ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

<Average circularity>
The average circularity is measured using a flow type particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation) and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). went.
Specifically, 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a glass 100 mL beaker, and each toner 0 0.1 g to 0.5 g was added, and the mixture was stirred with a micropartel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). Using the FPIA-2100, the dispersion was measured for toner shape and distribution until a density of 5,000 / μL to 15,000 / μL was obtained. In this measurement method, it is important that the concentration of the dispersion is 5,000 / μL to 15,000 / μL from the viewpoint of measurement reproducibility of the average circularity.

-Production of developer-
A spherical magnetite having an average particle diameter of 50 μm is coated with a coating layer made of silicone resin (organostraight silicon): γ- (2-aminoethyl) aminopropyltrimethoxysilane: carbon black = 85: 5: 10 (mass ratio). A two-component developer was prepared by mixing 95 parts by mass of the magnetic carrier provided and 5 parts by mass of the obtained toner.

(Production Example 3)
<Fixing solution preparation>
-Liquid containing plasticizer-
・ Ion-exchanged water as dilution solvent: 53% by mass
・ Diethoxyethoxyethyl succinate as a liquid plasticizer (Higher Alcohol Industry Co., Ltd.): 10% by mass
・ Propylene carbonate as liquid plasticizer ... 20% by mass
・ Propylene glycol as thickener: 10% by mass
-Palm fatty acid diethanolamide (1: 1) type (Matsumoto Yushi Seiyaku Co., Ltd., Marpon MM) ... 0.5% by mass as a foaming agent
・ Amine palmitate as foaming agent: 2.5% by mass
・ Amyristate amine as foaming agent: 1.5% by mass
・ Amine stearate as foaming agent: 0.5% by mass
Dispersant: POE (20) lauryl sorbitan (Kao Co., Ltd., Rheodor TW-S120V) ... 1% by mass
-Polyethylene glycol monostearate as a dispersant (manufactured by Kao Corporation, Emanon 3199) ... 1% by mass
The dispersant was used to promote the solubility of the plasticizer in the diluent solvent. The fatty acid amine was synthesized from fatty acid and triethanolamine.

  First, at the above component ratio, the plasticizer was removed at a liquid temperature of 120 ° C. and mixed and stirred to prepare a solution. Next, a plasticizer was mixed, and a fixing solution (stock solution before forming) in which the plasticizer was dissolved was prepared using an ultrasonic homogenizer.

<Coating device>
-Large bubble generation part-
It produced based on FIG.
-Liquid fixer storage container: Bottle made of polyethylene terephthalate (PET) resin-Liquid transport pump: Tube pump (tube inner diameter 2mm, tube material: silicone rubber)
・ Transport flow path: Silicone rubber tube with an inner diameter of 2 mm ・ Microporous sheet for creating large bubbles: # 400 stainless steel mesh sheet (opening approx. 40 μm)

-Microbubble generator-
It produced based on FIG.
The inner cylinder of the double cylinder is fixed to the rotation shaft and is rotated by a rotation drive motor (not shown). The material of the double cylinder was polyethylene terephthalate (PET) resin.
・ Outer cylinder inner diameter: 10 mm, outer cylinder length: 120 mm
・ Outer diameter of inner cylinder: 8 mm, length of inner cylinder: 100 mm
-The rotation speed was variable in the range of 1,000 rpm to 2,000 rpm.

-Fixer application means-
It produced based on FIG. A foam-like fixing solution was prepared using the micro-bubble generating unit that generates the micro-bubbles and supplied to the liquid film thickness control blade. The gap between the liquid film thickness control blade and the application roller was 25 μm and 40 μm.

Pressure roller: A polyurethane foam material (trade name “Color Foam EMO”, manufactured by INOAC) having a diameter of 50 mm was formed by using an aluminum alloy roller (diameter 10 mm) as a core metal.
・ Coating roller: Stainless steel (SUS) roller (diameter 30mm) coated with PFA resin
・ Blade for film thickness control: A 1 mm thick parallel glass was bonded to an aluminum alloy support plate, and the gap between the coating roller and the glass surface could be controlled in the range of 10 μm to 100 μm with the glass surface facing the coating roller. .
-Paper transport speed: 150 mm / s

  Next, using each of the obtained toner and each developer, heat resistant storage stability, fixing property, and copy blocking property were evaluated as follows, and comprehensive evaluation was performed according to the following evaluation criteria. The results are shown in Table 3.

<Heat resistant storage stability (Penetration)>
Each toner is filled in a 50 mL glass container, left in a thermostatic bath at 50 ° C. for 24 hours, then cooled to 24 ° C., and the penetration (mm) is measured by a penetration test (JIS K2235-1991). The heat resistant storage stability was evaluated according to the following criteria. In addition, it means that heat resistance preservability is excellent, so that the penetration degree is large, and the penetration degree of less than 5 mm is likely to cause a problem in use.
〔Evaluation criteria〕
◎: Needle penetration is 25 mm or more ○: Needle penetration is 15 mm or more and less than 25 mm △: Needle penetration is 5 mm or more and less than 15 mm ×: Needle penetration is less than 5 mm

<Fixability>
Each developer is loaded into an electrophotographic printer (Ricoh Co., Ltd., IpsioColorCX8800) with the fixing device removed, and an unfixed toner image of halftone (setting after fixing ID = 0.25) is formed. 6 is applied to the PPC paper using the fixing device shown in FIG. 6, and the pressure roller of the sponge and the coating roller are used in the fixing device including the coating device on which the fixing solution obtained in the fixing liquid formulation example is mounted. Fixing was performed at a center distance of 15 mm (nip time 100 ms). The paper conveyance speed at this time was 150 mm / s.
After fixing for 5 seconds and 1 hour, the surface of the image was rubbed with a cotton cloth having a diameter of 1 cm, and the stain on the cotton cloth was measured with a reflection densitometer (X-Rite 939, manufactured by X-Rite), and the fixing property was evaluated according to the following criteria. did.
〔Evaluation criteria〕
A: Reflection density is less than 0.20 B: Reflection density is 0.20 or more and less than 0.30 Δ: Reflection density is 0.30 or more and less than 0.40 ×: Reflection density is 0.40 or more

<Copy blocking property>
Each developer is loaded into an electrophotographic printer (Ricoh Co., Ltd., IpsioColorCX8800) with the fixing device removed, and an unfixed toner image of halftone (setting after fixing ID = 0.25) is formed. A liquid conveying pump is driven on the PPC paper that has been prepared using the fixing device shown in FIG. 6 to draw up the liquid fixing liquid obtained in the fixing liquid prescription example from the fixing liquid container and pass through the liquid flow path. The fixing solution is passed through a large bubble generating unit that generates bubbles and a minute bubble generating unit that makes bubbles fine, and after 1 second from the liquid discharge port, a fixing solution having micro bubbles with a bubble diameter of 5 μm to 30 μm is applied by roller. Then, fixing was performed by using a fixing device composed of a mounted coating device at a distance between the axes of the sponge pressure roller and the coating roller of 15 mm (nip time 100 ms). The paper conveyance speed at this time is 150 mm / s.
Next, the two output images were overlapped so that the image portion of the output PPC paper was in contact, pressurized from the top with a weight of 1 kg, and allowed to stand for 30 minutes in an atmosphere of air temperature 25 ° C. and humidity 30% RH. . The adhesiveness between the fixed images when separating the stacked paper after being left was measured, and the copy blocking property was evaluated according to the following criteria.
〔Evaluation criteria〕
◎: The paper can be separated one by one without any problem ○: The paper is partially bonded, but when the force is applied, the paper can be separated △: The paper is partially bonded ×: The paper is completely adhered to each other

<Comprehensive evaluation>
For each evaluation item, ◎ was 3 points, ○ was 2 points, Δ was 1 point, and × was 0 point, and the evaluation was made according to the following criteria.
〔Evaluation criteria〕
◎: There is no x for each evaluation item, and the total of all evaluation item scores is 12 points. No, the total of all evaluation item scores is 4 points or more and less than 8 points ×: There is one or more × marks in any of the evaluation items

From the results of Table 3, in Examples 1 to 12, the toner material contains a polyalkylene glycol ester compound having a high affinity with the plasticizer, so that it can have a sufficient fixing strength immediately after fixing, and a halftone image. It was also found that an image having a strong fixing strength against rubbing can be obtained.
In addition, when the physical properties of the polyalkylene glycol ester compound are in an appropriate range as in Examples 4 and 5, images having good heat-resistant storage stability and good fixability and copy blocking properties can be obtained. I understood.
Further, as in Comparative Example 1, when a toner containing no polyalkylene glycol ester compound was used, sufficient fixability could not be obtained immediately after fixing.

  The toner of the present invention consumes very little energy in the fixing step of the image forming method, has high image strength immediately after fixing, and can form a high-quality image resistant to rubbing even in a halftone image. The present invention can be suitably used for an electrophotographic forming technique that employs the method.

DESCRIPTION OF SYMBOLS 1 Photoconductor 2 Image formation part 3 Charging device (charging roller)
Reference Signs List 4 exposure device 5 developing device 5a developing roller 5b developer supply roller 5c regulating blade 6 transfer device 7 cleaning device 10 intermediate transfer belt 11, 12, 13 support roller 14 primary transfer roller 16 secondary transfer roller T toner (developer)
15K, 15M, 15C, 15Y Image forming means 17 Paper (recording medium)
DESCRIPTION OF SYMBOLS 18 Fixing device 23 Transfer means 33 Spraying means 34 Droplet charging means 35 Medium conveying means 36 Recording medium charging means 38 Spraying chamber 40 Roller 41 Conveying belt 42 Unfixed toner 44 Electrode 45 Power supply 46 Tandem imaging device 50 Applying means 53 Fixing solution Droplet 111 Application roller 112 Recording medium 113 Toner layer 114 Foamed fixing liquid 115 Belt cleaning device 120 Foamed fixing liquid 121 Liquid film boundary 122 Bubble 130 Foamed fixing liquid generating means 131 Fixing liquid container 132 Liquid fixing liquid 133 Conveyance pump 134 Liquid Conveying pipe 135 Gas / liquid mixing unit 136 Air port 137 Micropore sheet 138 Foam generation unit 140 Fixing device 141 Application roller 142 Film thickness adjusting blade 143 Pressure roller 144 Pressure belt 145 Heating means 146 Pressure roller 147 Infrared heat 148 Pressure roller

JP 2006-133306 A JP 2009-008967 A JP 2008-139504 A

Claims (11)

A toner used for fixing a toner to a recording medium by applying a fixing liquid containing a diluent and a plasticizer that softens or swells at least a part of the toner to the toner on the recording medium,
A toner comprising at least a binder resin, a colorant, and a polyalkylene glycol ester compound represented by the following general formula (I):
However, the general formula (I), ^{R 1} and ^{R 2} are both represent a linear or branched alkyl group having 1 to 24 carbon atoms. Rxm and Rym may be the same as or different from each other, and represent either a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. n represents an integer of 2 or more. m represents an integer of 2 or more and 4 or less.   The toner according to claim 1, wherein the polyalkylene glycol ester compound has a weight average molecular weight of 3,600 to 20,500.   The toner according to claim 1, wherein the polyalkylene glycol ester compound has a melting point of 50 ° C. or higher.   The toner according to claim 1, wherein the content of the polyalkylene glycol ester compound is 1 to 15 parts by mass with respect to 100 parts by mass of the binder resin.   The toner according to claim 1, wherein the polyalkylene glycol ester compound contains polyethylene glycol as a structural unit. A fixing method for fixing a toner image formed on a recording medium using the toner according to claim 1,
A foamed fixing solution generating step for producing a foamed fixing solution by foaming a fixing solution containing a diluent containing water, a foaming agent, and a plasticizer;
A film thickness adjusting step for forming the foamy fixer to a desired thickness on the contact surface of the foamy fixer applying means,
A foam-like fixing solution applying step for applying the foam-like fixing solution formed in the desired thickness to the toner layer on the recording medium;
A fixing method comprising the steps of:   The fixing method according to claim 6, wherein the plasticizer is diethoxyethoxyethyl aliphatic dicarboxylate. The fixing method according to claim 6, wherein the plasticizer is a compound represented by the following general formula.
R ⁸ (COO— (R ⁹ —O) _n —R ¹⁰ ) ₂
In the general formula, n is 1 to 3, R ⁸ is an alkylene group having 2 to 8 carbon atoms, R ⁹ is an alkylene group having 1 to 3 carbon atoms, R ¹⁰ Is an alkyl group having 1 to 4 carbon atoms. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
Developing the electrostatic latent image using a developer containing toner to form a visible image;
A transfer step of transferring the visible image to a recording medium;
A fixing step of fixing the transferred image transferred to the recording medium;
An image forming method comprising:
An image forming method, wherein the fixing step is performed by the fixing method according to claim 6. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
A developer carrying member for carrying a developer to be supplied to the electrostatic latent image carrier, a developer supplying member for supplying the developer to the surface of the developer carrying member, and a developer containing a developer containing toner A developing unit that develops the electrostatic latent image using a developer containing toner and forms a visible image;
Transfer means for transferring the visible image to a recording medium;
Fixing means for fixing the transferred image transferred to the recording medium;
An image forming apparatus having
The fixing unit includes a fixing solution applying unit that applies a fixing solution to a toner layer on a recording medium,
The image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1. An electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
A developer carrying member for carrying a developer containing toner to be supplied to the electrostatic latent image carrier, a developer supplying member for supplying the developer to the surface of the developer carrying member, and a developer containing toner. A developer container for storing, and developing means for developing the electrostatic latent image with a developer containing toner to form a visible image;
Transfer means for transferring the visible image to a recording medium;
Fixing means for fixing the transferred image transferred to the recording medium;
An image forming apparatus having
A foaming fixer generating means for generating a foamy fixer by foaming a fixer containing a diluent containing water, a foaming agent, and a plasticizer;
Film thickness adjusting means for forming the foamy fixer on the contact surface of the foamy fixer applying means to a desired thickness;
A foam-like fixing solution applying means for applying the foam-like fixing solution formed in the desired thickness to the toner layer on the recording medium;
The image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1.