JP2007093637A - Electrostatic charge image developing toner and method for manufacturing the same, and electrostatic charge image developer and image forming method using the electrostatic charge image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner having satisfactory toner blocking resistance, storage property of an image, cleanability and filming resistance and a method for manufacturing the same, and an electrostatic charge image developer and image forming method using the electrostatic charge image developing toner. <P>SOLUTION: The electrostatic charge image developing toner of a core-shell structure having a core layer consisting of a toner base particle containing a binder resin and a colorant and a shell layer coating the core layer is characterized in that the shell layer contains an amorphous high polymer obtained by polymerizing 11-14C alicyclic monomer or the electrostatic charge image developing toner of the core-shell structure having a core layer consisting of a toner base particle containing a binder resin and a colorant and a shell layer coating the core layer is characterized in that the shell layer contains an acryl silicone resin, and the method for manufacturing the same, and the electrostatic charge image developer and image forming method using the electrostatic charge image developing toner are provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic image used for developing an electrostatic image in an electrophotographic apparatus utilizing an electrophotographic process such as a copying machine, a printer, and a facsimile, a manufacturing method thereof, and the electrostatic charge The present invention relates to an electrostatic charge image developer using an image developing toner and an image forming method.

Examples of the toner for developing an electrostatic image (hereinafter sometimes simply referred to as a toner) include toners obtained by a kneading and pulverization method, a suspension polymerization method, and the like. From this point of view, toner development is underway. The kneading and pulverizing method, which is a conventional manufacturing method, requires a large amount of energy to reduce the particle size, and requires a classification step to control the particle size distribution, thereby generating a by-product. Therefore, there are concerns about the impact on the environment.
On the other hand, a polymerized toner obtained by suspension polymerization or the like can obtain a uniform toner particle size when producing a small particle size, and thus can be said to be a production method suitable for the environment without requiring a classification step. . Therefore, the development of polymerized toner is now active.

  In the polymerized toner, a binder resin, a release agent, and a pigment are blended, a flocculant is added, and the toner is aggregated at a temperature lower than the Tg of the binder resin, and then united at a temperature higher than the Tg of the binder resin. A technique for producing toner is common. This method is excellent in terms of ease of production, product management, and quality assurance, and has the advantage that the energy generated during production is significantly smaller than that of the conventional kneading and pulverization method, and the environmental load is reduced. As the toner characteristics, the fixing temperature range is determined by the combination of the binder resin and the release agent, and the toner characteristics of gloss and thermal aggregation are also determined.

  In addition, the polymerized toner can easily have a core-shell structure. For example, by using a binder resin for the surface layer as the shell layer, it is possible to control the amount of the release agent to the toner surface layer, and to stably charge the toner surface without impairing the powder characteristics of the toner. Become.

  Furthermore, studies are being made to develop a toner that achieves both low-temperature fixing characteristics and toner storage by optimizing the binder resin used for the shell layer. For example, conventionally proposed core-shell type toners include, for example, a toner in which small particles are embedded and coated on the surface of base particles having an outflow start temperature of 110 ° C. or less (see, for example, Patent Document 1), molecular weight 3000 to 30000. , A toner in which a styrene acrylic core material having a glass transition point of 50 to 70 ° C. is encapsulated with a styrene shell material having a higher molecular weight and a high glass transition point (see, for example, Patent Document 2), and surface modification to core particles Toner (for example, see Patent Document 3) in which resin fine particles for use are fixed by mechanical impact force, a core substance composed of saturated fatty acid or saturated alcohol having a melting point of 40 to 100 ° C. is suspended in water, and then encapsulated with resin fine particles Layered toner (see, for example, Patent Document 4), a low-viscosity resin particle surface with a thermally stable layer and a thermoplastic resin coating layer having a Tg of 65 ° C. or higher Toner (for example, see Patent Document 5) and toner in which resin fine particles having a Tg of 60 to 110 ° C. are adhered to the surface of a toner containing a resin having a Tg of 25 to 55 ° C. (see, for example, Patent Document 6). Proposed.

  Further, although not a core-shell type, a toner using a linear polyester resin having a softening point of 90 to 120 ° C. and carnauba wax (for example, see Patent Document 7), a wax-encapsulated polymerization method toner (for example, see Patent Document 8), And a toner formed by subjecting an isocyanate group-containing prepolymer to an extension crosslinking reaction with an amine in an aqueous medium (see, for example, Patent Document 9).

On the other hand, toner having characteristics other than low-temperature fixing characteristics, gloss, and toner storage properties may be realized by the core-shell structure.
For this reason, it is considered possible to improve toner characteristics by using various resins for the shell layer.
Japanese Patent No. 2750853 Japanese Patent Laid-Open No. 5-181301 JP-A-6-342224 JP-A-8-254853 JP-A-9-258480 JP 2001-175025 A JP-A-8-220808 JP-A-5-61242 JP-A-11-149180

  The present invention has been made in view of the above problems, and has an electrostatic charge image developing toner having good toner blocking resistance, image storage stability, cleaning properties, and filming resistance, a method for producing the same, and It is an object of the present invention to provide an electrostatic image developer and an image forming method using an electrostatic image developing toner.

The above problems can be solved by the following present invention.
That is, the present invention
<1> An electrostatic charge developing toner having a core-shell structure having a core layer comprising toner base particles containing a binder resin and a colorant, and a shell layer covering the core layer, wherein the shell layer comprises: An electrostatic image developing toner comprising an amorphous polymer obtained by polymerizing an alicyclic monomer having 11 to 14 carbon atoms.
<2> The electrostatic image developing toner according to <1>, wherein the amorphous polymer has a glass transition point Tg of 150 to 180 ° C.

<3> An electrostatic charge developing toner having a core-shell structure having a core layer composed of toner base particles containing a binder resin and a colorant, and a shell layer covering the core layer, wherein the shell layer comprises an acrylic layer A toner for developing an electrostatic image characterized by containing a silicone resin.
<4> The electrostatic image developing toner according to <3>, wherein the content of the acrylic silicone resin is 4 to 70% by mass.
<5> The electrostatic charge according to <3> or <4>, wherein the acrylic silicone resin is contained only in the shell layer, and the content of the acrylic silicone resin is 4 to 40% by mass. This is an image developing toner.

<6> The electrostatic image developing toner according to any one of <1> to <5>, wherein the binder resin contains a crystalline resin.
<7> The binder resin is a crystalline polyester resin containing a dicarboxylic acid having a sulfonic acid group or a diol having a sulfonic acid group as a copolymerization component. <1> to <6> The electrostatic charge image developing toner according to any one of the above.

<8> The electrostatic image developing toner according to <6> or <7>, wherein the binder resin further contains an amorphous polymer.
<9> The electrostatic image developing toner according to any one of <1> to <8>, wherein an average value of the shape factor SF1 is in a range of 110 to 140.

<10> Any one of <1> to <9>, wherein the electrostatic charge developing toner is an electrophotographic full-color toner capable of forming a toner image composed of three colors of cyan, magenta, and yellow. The toner for developing an electrostatic image described in 1.
<11> The electrostatic charge according to any one of <1> to <10>, further comprising an electrostatic charge developing toner containing 0.5 to 40 parts by mass of a release agent. This is an image developing toner.

<12> A method for producing a toner for developing an electrostatic charge image according to any one of <1> to <11>, wherein the resin particle dispersion includes particles of a binder resin having a particle size of 1 μm or less, and An aggregating step of mixing a colorant particle dispersion containing colorant particles, adding an aggregating agent thereto to agglomerate the binder resin particles and the colorant particles to form aggregated particles, and An electrostatic charge comprising: a coalescing step for producing toner base particles by uniting at a temperature equal to or higher than a melting point of the binder resin; and an adhesion step for adhering the coating resin particles to the toner base particles. This is a method for producing a developing toner.

<13> An electrostatic charge image developer comprising a toner and a carrier, wherein the toner is the electrostatic charge developing toner according to any one of <1> to <11>. It is a developer for charge development.

<14> A latent image forming step of forming an electrostatic latent image on the surface of the electrostatic charge image carrier, and developing the electrostatic latent image formed on the surface of the developer carrier with an electrostatic charge image developer to form a toner image. A developing step for forming, a transferring step for transferring a toner image formed on the surface of the developer carrying member onto a transfer material to form a transferred image, and a fixing step for fixing the transferred image transferred on the surface of the transferring material The electrostatic charge image developer comprises the electrostatic charge developing toner according to any one of <1> to <11>. is there.

  The present invention relates to a toner for developing an electrostatic image having good toner blocking resistance, image storage, cleaning and filming resistance, a method for producing the same, and a static image using the toner for developing an electrostatic image. A charge image developer and an image forming method can be provided.

<Toner for electrostatic charge development>
The electrostatic charge developing toner of the first aspect of the invention (hereinafter sometimes referred to as “the toner of the first aspect of the invention”) comprises a core layer comprising toner base particles containing a binder resin and a colorant, An electrostatic charge developing toner having a core-shell structure having a shell layer covering the core layer, wherein the shell layer is an amorphous polymer obtained by polymerizing an alicyclic monomer having 11 to 14 carbon atoms It is characterized by containing. The toner of the first invention has a core-shell structure, the core layer is composed of toner base particles containing a binder resin and a colorant, and the shell layer contains an alicyclic polymer resin having a large number of carbon atoms. Therefore, the torsional rigidity of the shell layer is strengthened, and the destruction of the shell layer due to carrier and toner collision is suppressed, thereby preventing the generation of fine particles, toner blocking resistance, image storage stability, cleaning performance, and filming resistance. A toner having good properties can be obtained.

  The electrostatic charge developing toner of the second aspect of the invention (hereinafter sometimes referred to as “the toner of the second aspect of the invention”) includes a core layer composed of toner base particles containing a binder resin and a colorant, An electrostatic charge developing toner having a core-shell structure having a shell layer covering the core layer, wherein the shell layer contains an acrylic silicone resin. The toner of the second aspect of the present invention has a core-shell structure, the core layer is composed of toner base particles containing a binder resin and a colorant, and the shell layer contains an acrylic silicone resin, so that Si—O bonds are formed. Thus, a toner having good toner blocking resistance, image storage stability, cleaning performance, and filming resistance can be obtained.

First, the shell layers in the toners of the first and second inventions will be described.
In the first toner of the present invention, an amorphous polymer obtained by polymerizing an alicyclic monomer having 11 to 14 carbon atoms (hereinafter sometimes referred to as “amorphous polymer according to the present invention”). By using for the shell layer, the cleaning property is improved due to the unevenness of the toner surface.
In the present invention, the “amorphous polymer” refers to a polymer having a stepwise endothermic change and not having a clear endothermic peak in differential scanning mass measurement (DSC). On the other hand, “crystalline resin” refers to a resin having a clear endothermic peak rather than a change in endothermic amount in differential scanning weight measurement (DSC).

  The amorphous polymer according to the present invention preferably has a glass transition point Tg of 150 to 180 ° C. When the glass transition point Tg of the amorphous polymer according to the present invention is 150 to 180 ° C., the suppression of filming increases due to the curing of the toner surface. The glass transition point Tg is more preferably 160 to 180 ° C. The amorphous polymer according to the present invention has a glass transition point Tg of 150 to 180 ° C. by using an alicyclic monomer having 11 to 14 carbon atoms as a monomer for obtaining the polymer. Can do. Moreover, the glass transition point Tg can be adjusted by copolymerizing another monomer.

  As the alicyclic monomer, a (meth) acrylic monomer having an alicyclic structure is preferable. Since the alicyclic compound has a large number of carbon atoms and is bulky, the polymerized polymer is rigid and has a high glass transition point Tg. Furthermore, it is known that a polymer containing a large amount of an alicyclic monomer is more rigid than an aliphatic polymer or an aromatic polymer. Therefore, by using an amorphous polymer containing an alicyclic monomer (hereinafter sometimes referred to as “alicyclic polymer”) for the shell layer, the shell layer is less likely to be peeled off even when a carrier or toner collides with each other. It became possible to suppress solidification in the actual machine. Moreover, since the fine powder derived from the peeling of the shell layer is suppressed, the occurrence of filming can be suppressed. In this specification, the description of “(meth) acryl” and the like means “acryl” and “methacryl” and the like.

  As a polymer having a high glass transition point Tg (high Tg), it is generally used to use a styrene-based aromatic polymer. However, when printed and coated with an aromatic polymer, there is a possibility of yellowing. However, when the alicyclic polymer used in the present invention is used, there is no yellowing and image storability is good.

  Moreover, the contribution of the following characteristics can also be achieved by using the amorphous polymer alicyclic monomer according to the present invention as described above. The alicyclic polymer resin can produce a high Tg resin at 150 to 180 ° C. Therefore, when an alicyclic polymer having a Tg of 150 to 180 ° C. is used for the shell layer, the shell layer has a Tg equal to or higher than the toner production temperature. The toner having no irregularity on the surface is not good in cleaning property of the spherical toner, but the toner having irregularity according to the present invention has good toner cleaning property because the friction between the cleaning blade and the toner is increased even in the spherical shape. Further, since the contact area between the toners decreases, solidification due to adhesion between the toners can be suppressed. Therefore, the developer can be used without being replenished stably over a long period of time. Further, since the shell layer has a high Tg, the toner storage property is also good.

  Further, if the fixing temperature is equal to or lower than the glass transition point Tg of the amorphous polymer according to the present invention used for the shell layer, the amorphous polymer particles of the shell are pushed into the core during fixing, and the shell particles Are not fused and have a slight gap, the pressure makes it easy for the core resin to bleed out, and the core characteristics can be reflected in the fixed image. For example, a high gloss toner by using a low Tg resin or a crystalline resin for the core, an improvement in peelability due to the ease of bleeding of the release agent, and an improvement in the color gamut due to the pigment are likely to occur.

It is essential that the alicyclic monomer used in the present invention has 11 to 14 carbon atoms. When the carbon number of the alicyclic monomer is less than 11, the rigidity becomes weak, and even when used in the shell layer, a sufficiently rigid toner cannot be obtained and peeling cannot be suppressed. On the other hand, if it exceeds 14, the polymerizability of the alicyclic monomer is inferior, so that the odor derived from the residual monomer remains. For this reason, it gives an uncomfortable feeling because it smells when fixing the toner.
Examples of the alicyclic monomer used in the present invention include fan acryl 513A: dicyclopentanyl acrylate (carbon number 13: manufactured by Hitachi Chemical Co., Ltd.), acryl 513M: dicyclopentanyl methacrylate (carbon number 14). : Manufactured by Hitachi Chemical Co., Ltd.), and among them, acrylonitrile 513M having a high Tg homopolymer is preferable.

  On the other hand, in the polymerization of the amorphous polymer according to the present invention, examples of the monomer other than the alicyclic monomer include styrenes such as styrene, parachlorostyrene, and α-methylstyrene; methyl acrylate, ethyl acrylate, acrylic Has vinyl groups such as n-propyl acid, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate Esters; Vinyl nitriles such as acrylonitrile and methacrylonitrile; Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, and copolymers thereof And the like.

  In the polymerization of the amorphous polymer according to the present invention, the blending amount of the alicyclic monomer is preferably 30 to 100%, more preferably 50 to 100%. If the blending amount is less than 30%, the amorphous polymer according to the present invention may not exhibit the characteristics of the alicyclic monomer. Therefore, even when the amorphous polymer according to the present invention is used for the shell layer, the toner is not sufficiently rigid, and peeling of the shell layer may not be suppressed. On the other hand, a toner using the amorphous polymer according to the present invention polymerized only with an alicyclic monomer is preferable because sufficiently fine polymer particles can be obtained.

  In the toner according to the second aspect of the present invention, by using an acrylic silicone resin (hereinafter sometimes referred to as “acrylic silicone resin according to the present invention”) for the shell layer, the fixed image storability and the toner are obtained by Si—O bonds. Storage is improved.

The acrylic silicone resin will be described.
The acrylic silicone resin is a part of a hybrid emulsion having a core-shell structure and has particles having a silyl group in the core, and the acrylic resin is used as a shell. It may be referred to as “such an acrylic silicone emulsion”).

In the acrylic silicone emulsion according to the present invention, under water, the acrylic resin of the shell layer protects the core portion and can exist stably. However, when the emulsion is formed, the shell layer is broken and the silyl group in the core portion is deposited on the particle surface, breaking the Si—O bond and bonding the particles firmly.
In the present invention, taking advantage of this advantage, the core portion of the toner is made of a material having the characteristics of a normal toner, and the shell portion is made to contain an acrylic silicone emulsion. An acrylic silicone emulsion is attached to the outer side (shell layer) of the core part, and then the shell layer in the emulsion is destroyed by raising the temperature of Tg of the acrylic resin that is the shell layer in the emulsion. Breaking the bond, the particles are firmly bonded to each other, and the toner surface has a strong shell layer.

  Next, the effect of using an acrylic silicone emulsion for the shell layer in the toner of the second invention will be described. First, the conventional polymerized toner greatly depends on the resin Tg in the toner, and the storage stability of the toner is good in an environment below the Tg of the resin used for the shell layer. Similarly, when a fixed image is stored in a temperature environment below the resin Tg in the toner, the storage stability is improved. That is, when the fixed image is stored, if the storage environment becomes a temperature equal to or higher than the Tg temperature of the toner binder resin, the surface of the fixed image is melted and fixed. However, according to the present invention, the toner surface is protected by a structure having a Si—O bond, and when the toner is fixed, not only the bleeding from the core but also a lot of shell portions are present on the image surface. . Furthermore, since the Si—O bond existing in the shell layer is strong, the strength of the fixed image is high and the scratch is strong. Further, even if the fixed image is stored in a high temperature environment, the fused image can be prevented from being fused by Si—O bonding, so that the fixed image storability is improved.

  As the acrylic silicone emulsion according to the present invention, Aquabrid ASi-91 (manufactured by Daicel Chemical Industries, Ltd.) and Aquabrid ASi-91z3 (manufactured by Daicel Chemical Industries, Ltd.) can be used.

  In the toner of the second invention, the shell layer contains an acrylic silicone resin, but the core layer may also contain an acrylic silicone resin. In this case, the total content of the acrylic silicone resin including the shell layer and the core layer is preferably 4 to 70% by mass, more preferably 10 to 50% by mass, and more preferably 10 to 35% by mass in the toner. % Is more preferable. If the total amount of the acrylic silicone resin combined with the shell layer and the core layer is less than 4% by mass, the effect of Si—O bonding may be weakened, and the fixed image strength may be lost. Inferior properties, and fixed image unevenness is likely to occur, and the fixing characteristics may deteriorate.

  In the toner of the second invention, it is preferable that only the shell layer contains an acrylic silicone resin in that filming is difficult. The content of the acrylic silicone resin when only the shell layer contains the acrylic silicone resin is preferably 4 to 40% by mass, more preferably 8 to 35% by mass in the toner, and 15 to 35% by mass. % Is more preferable. In this case, if the total amount of the acrylic silicone resin is less than 4% by mass, the effect of the Si—O bond may be weakened, and the fixed image strength may be lost. If the total amount exceeds 40% by mass, the shell layer becomes thick, and the core Since the amount of the release agent that exudes from the toner is reduced, the releasability is inferior, the fixed image unevenness is likely to occur, and the fixing characteristics may be deteriorated.

Next, the core layer in the toner of the first invention and the toner of the second invention (hereinafter sometimes referred to as “the toner of the invention”) will be described.
In the toner of the present invention, the binder resin used for the core layer preferably contains a crystalline resin. Since the crystalline resin has sharp melt properties, the viscosity rapidly decreases at a certain temperature. Therefore, crystalline resins have been actively researched for developing toners having low-temperature fixing characteristics. Even when used in the present invention, the use of a crystalline resin for the core layer has low-temperature fixing characteristics and enables the development of a high gloss toner. Further, by blending the amorphous polymer or acrylic silicone resin according to the present invention into the shell layer, the rigidity of the toner is increased, peeling of the shell layer and generation of fine particles are suppressed, and filming is suppressed. Here, the following effects were further exhibited by using a crystalline resin for the core layer. Crystalline resins are softer than amorphous polymers. Therefore, the alicyclic particles in the shell layer are easily embedded and the peeling of the shell layer is extremely reduced. For this reason, the effect of suppressing the filming and improving the cleaning property becomes more prominent.

  The crystalline resin is not particularly limited, and examples thereof include a crystalline polyester resin, a crystalline urethane resin, a crystalline polyamide resin, and a crystalline polyacetal resin. Among these, a polyester resin is preferable, and an aliphatic resin having an appropriate melting point. The crystalline polyester resin is more preferable. Hereinafter, a crystalline polyester resin preferable as the crystalline resin will be described.

  The crystalline polyester resin is synthesized from an acid (dicarboxylic acid) component and an alcohol (diol) component. In the present invention, the “acid-derived component” refers to an acid component before synthesis of the polyester resin. The “alcohol-derived constituent component” refers to a constituent portion that was an alcohol component before the synthesis of the polyester resin.

  When the polyester resin is not crystalline, that is, amorphous, it is impossible to maintain toner blocking resistance and image storage stability while ensuring good low-temperature fixability. Therefore, in the present invention, as described above, the “crystalline polyester resin” refers to a resin having a clear endothermic peak instead of a stepwise endothermic amount change in differential scanning calorimetry (DSC). In the case of a polymer obtained by copolymerizing other components with respect to the crystalline polyester main chain, when the other components are 50% by mass or less, this copolymer is also called crystalline polyester.

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

  As the acid-derived constituent component, in addition to the above-mentioned aliphatic dicarboxylic acid-derived constituent component, constituent components such as a dicarboxylic acid-derived constituent component having a double bond and a dicarboxylic acid-derived constituent component having a sulfonic acid group are included. Is preferred.

  The component derived from a dicarboxylic acid having a double bond is derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a double bond, in addition to a component derived from a dicarboxylic acid having a double bond. Components are also included. The dicarboxylic acid-derived constituent component having a sulfonic acid group is derived from a lower alkyl ester or acid anhydride of a dicarboxylic acid having a sulfonic acid group, in addition to a constituent component derived from a dicarboxylic acid having a sulfonic acid group. Components are also included.

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

The dicarboxylic acid having a sulfonic acid group is effective in that it can favorably disperse a coloring material such as a pigment. Further, when emulsifying or suspending the entire resin in water to produce toner mother particles into fine particles, if there are sulfonic acid groups, emulsification or suspension can be performed without using a surfactant as will be described later. . Examples of such a dicarboxylic acid having a sulfone group include, but are not limited to, 2-sulfoterephthalic acid sodium salt, 5-sulfoisophthalic acid sodium salt, and sulfosuccinic acid sodium salt. Moreover, these lower alkyl esters, acid anhydrides, etc. are also mentioned. Among these, 5-sulfoisophthalic acid sodium salt is preferable in terms of cost.
In the present invention, “constituent mol%” refers to the percentage when each constituent component (acid-derived constituent component, alcohol-derived constituent component) in the polyester resin is 1 unit (mol).

-Alcohol-derived components-
The alcohol component is preferably an aliphatic diol, such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-dodecanediol, 1,12-undecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, and the like can be mentioned, but not limited thereto.

  When the alcohol-derived constituent component is an aliphatic diol-derived constituent component, the content of the aliphatic diol-derived constituent component is 80 constituent mol% or more, and other components are included as necessary. Furthermore, when the alcohol-derived constituent component is an aliphatic diol-derived constituent component, the content of the aliphatic diol-derived constituent component is preferably 90 constituent mol% or more.

  When the content of the aliphatic diol-derived constituent component is less than 80 constituent mol%, the crystallinity of the polyester resin is lowered and the melting point is lowered, so that toner blocking resistance, image storage stability, and low-temperature fixability are deteriorated. May end up.

  Other components included as necessary include diol-derived components having double bonds and diol-derived components having sulfonic acid groups.

  Examples of the diol having a double bond include 2-butene-1,4-diol, 3-butene-1,6-diol, 4-butene-1,8-diol, and the like.

  Examples of the diol having a sulfonic acid group include 1,4-dihydroxy-2-sulfonic acid benzene sodium salt, 1,3-dihydroxymethyl-5-sulfonic acid benzene sodium salt, and 2-sulfo-1,4-butanediol sodium. Examples include salts.

  The crystalline polyester resin used as the binder resin in the present invention is preferably a crystalline polyester resin containing a dicarboxylic acid having a sulfonic acid group or a diol having a sulfonic acid group as a copolymerization component.

  The method for producing the polyester resin is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. For example, direct polycondensation, transesterification method, etc. Produced separately for different types. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  The production of the polyester resin can be carried out at a polymerization temperature of 180 to 230 ° C., and the reaction system is reacted under reduced pressure as necessary to remove water and alcohol generated during condensation.

  When the monomer is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If there is a monomer with poor compatibility in the copolymerization reaction, the monomer with poor compatibility and the monomer and the acid or alcohol to be polycondensed may be condensed in advance before polycondensation with the main component. .

  Catalysts that can be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium, alkaline earth metal compounds such as magnesium and calcium, and metal compounds such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium. , Phosphorous acid compounds, phosphoric acid compounds, amine compounds, etc., specifically, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, stearic acid Zinc, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, trib Ruantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenyl Examples of the compound include phosphite, tris (2,4-di-t-butylphenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, and triphenylamine.

The melting point of the crystalline resin is preferably 50 to 120 ° C, more preferably 60 to 110 ° C. If the melting point is lower than 50 ° C., the storage stability of the toner and the storage stability of the toner image after fixing may become a problem. On the other hand, if the temperature is higher than 120 ° C., sufficient low-temperature fixing may not be obtained as compared with conventional toners.
In the present invention, the melting point of the crystalline resin is measured using a differential scanning calorimeter (DSC) when measured from a room temperature to 150 ° C. at a rate of temperature increase of 10 ° C. per minute. The melting peak temperature of the input compensation differential scanning calorimetry shown in 7121 can be obtained. The crystalline resin may show a plurality of melting peaks, but in the present invention, the maximum peak is regarded as the melting point.

  In the toner of the present invention, the binder resin may contain an amorphous polymer together with the crystalline resin. Examples of the amorphous polymer include acrylic resin, polyester resin, urethane, melamine resin, amide resin, and petroleum resin. These may be modified or copolymerized.

  The colorant used in the present invention may be a dye or a pigment, but a pigment is preferred from the viewpoint of light resistance and water resistance. Preferred pigments include carbon black, aniline black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, DuPont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black, rose bengal, Quinacridone, benzidine yellow, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 185, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 74, C.I. I. Pigment blue 15: 1, C.I. I. Known pigments such as CI Pigment Blue 15: 3 can be used. Magnetic powder can also be used as a colorant. As the magnetic powder, known magnetic materials such as ferromagnetic metals such as cobalt, iron and nickel, alloys of metals such as cobalt, iron, nickel, aluminum, lead, magnesium, zinc and manganese, and oxides can be used.

These can be used alone or in combination of two or more. The content of these colorants is preferably 0.1 to 40 parts by weight, and more preferably 1 to 30 parts by weight.
In addition, by appropriately selecting the type of the colorant, each color toner such as yellow toner, magenta toner, cyan toner, and black toner can be obtained.
By preparing yellow toner, magenta toner, and cyan toner as toners of the present invention, a full color toner for electrophotography capable of forming a toner image composed of three colors of cyan, magenta, and yellow is obtained.

  There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, well-known various additives, such as an inorganic fine particle, a charge control agent, a mold release agent, etc. are mentioned.

  If necessary, inorganic fine particles may be added to the toner of the present invention. As the inorganic fine particles, silica fine particles, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, or known inorganic fine particles such as those obtained by hydrophobizing the surface thereof can be used alone or in combination of two or more kinds. Silica fine particles having a refractive index smaller than that of the binder resin are preferable from the viewpoint that transparency such as color developability and OHP permeability is not impaired. The silica fine particles may be subjected to various surface treatments, and for example, those subjected to surface treatment with a silane coupling agent, a titanium coupling agent, silicone oil or the like are preferable.

  By adding these inorganic fine particles, the viscoelasticity of the toner can be adjusted, and the glossiness of the image and the penetration into the paper can be adjusted. The inorganic fine particles are preferably contained in an amount of 0.5 to 20% by mass, more preferably 1 to 15% by mass with respect to the raw material.

  If necessary, a charge control agent may be added to the toner of the present invention. As the charge control agent, chromium-based azo dyes, iron-based azo dyes, aluminum azo dyes, salicylic acid metal complexes, and the like can be used.

  The toner of the present invention preferably contains a release agent. By including a release agent, the releasability in the fixing process is improved. In the contact heating type fixing method, the release oil applied to the fixing roll can be reduced or eliminated. Deterioration of roll life and oil streaks can be avoided, and the cost can be reduced.

  Specific examples of the release agent include low molecular weight polyolefins such as polyethylene, polypropylene, and polybutene; silicones having a softening point by heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide Plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, etc. Minerals and petroleum waxes are listed.

The melting point of the release agent is preferably 50 to 120 ° C., more preferably below the melting point of the binder resin. If the melting point of the release agent is less than 50 ° C., the change temperature of the release agent is too low, and the blocking resistance may be inferior, or the developability may deteriorate when the temperature in the copying machine increases. On the other hand, when it exceeds 120 ° C., the change temperature of the release agent is too high, and the low-temperature fixability of the crystalline resin may be impaired.
Moreover, in this invention, these mold release agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the release agent in the toner is preferably 0.5 to 40% by mass, more preferably 1 to 20% by mass, and still more preferably 2 to 15% by mass. If the content of the release agent is less than 0.5% by mass, the effect of adding the release agent may not be obtained. If the content exceeds 40% by mass, adverse effects on the chargeability tend to appear, When the toner is easily destroyed inside the developing machine, the release agent or toner resin becomes spent on the carrier, which may cause an effect such as a tendency to decrease the charge. The surface of the image tends to be insufficiently oozed out, the release agent tends to stay in the image, and the transparency may deteriorate.

  The preferred volume average particle size of the toner of the present invention is 3.0 to 7.5 μm, more preferably 3.5 to 6.5 μm, and still more preferably 3.8 to 6.2 μm. When the volume average particle diameter of the toner of the present invention is smaller than 3.0 μm, the charging property is not sufficient, and the spread of the charge distribution due to the decrease in fluidity tends to cause fogging on the background or toner spillage from the developing device. There is a case. On the other hand, when the volume average particle diameter is larger than 7.5 μm, the resolution is lowered, and thus sufficient image quality may not be obtained.

  The volume average particle diameter can be measured, for example, by measuring with an aperture diameter of 50 μm using a Coulter counter [TA-II] type (manufactured by Coulter). At this time, the measurement is performed after the toner is dispersed in an electrolyte aqueous solution (Isoton aqueous solution) and dispersed by ultrasonic waves for 30 seconds or more.

  The value of the shape factor SF1 of the toner of the present invention is preferably 110 to 140, and more preferably 112 to 135. If the value of SF1 is less than 110, it may be difficult to produce stably, and the yield may decrease and the cost may increase. Further, if it exceeds 140, the transferability is deteriorated, the image quality is lowered, and the transfer efficiency is lowered, so that the residual toner is increased and the cost is increased, and the fluidity is also lowered. is there.

The shape factor SF1 can be measured using an image analyzer (Luzex III, manufactured by Nireco Corporation). An optical microscope image of the toner dispersed on the slide glass can be taken into an image analysis apparatus, and SF1 of each of 100 toner particles can be obtained and calculated by the average value thereof. SF1 is calculated by the following equation (1).
Formula (1)
SF1 = (maximum length of toner diameter) ² / (projection area of toner particles) × (π / 4) × 100

<Method for producing toner for developing electrostatic charge>
The toner manufacturing method of the present invention comprises mixing a resin particle dispersion containing binder resin particles having a particle size of 1 μm or less and a colorant particle dispersion containing colorant particles, and adding an aggregating agent thereto. Agglomeration step of aggregating the binder resin particles and colorant particles to form aggregated particles, and uniting the aggregated particles at a temperature equal to or higher than the melting point of the binder resin to produce toner base particles And a step of attaching the coating resin particles to the toner base particles. By this production method, the toner of the present invention described above can be obtained.

  As a method for producing the toner of the present invention, the following emulsion aggregation method is preferably exemplified. Hereinafter, the case where a preferable crystalline polyester resin is used as the binder resin in the emulsion aggregation method will be described as an example.

  The emulsion aggregation method includes an emulsification step of emulsifying the crystalline polyester resin already described in the section of “Binder resin” in the toner of the present invention to form emulsified particles (droplets), and the emulsified particles (droplets). Together with particles such as a colorant and the like, and an aggregation step of forming an aggregate, and a coalescence step of fusing the aggregate at a temperature equal to or higher than the melting point of the crystalline polyester resin and heat-merging. Further, the aggregation step and the coalescence step may be a so-called association step in which aggregation and coalescence are performed simultaneously by aggregating at a temperature equal to or higher than the melting point of the crystalline polyester resin.

  In the emulsification step, the emulsified particles (droplets) of the polyester resin are mixed into a solution obtained by mixing an aqueous medium and a sulfonated polyester resin and, if necessary, a mixed liquid (polymer liquid). It is formed by applying a shearing force.

  In that case, the viscosity of a polymer liquid can be lowered | hung by heating to the temperature beyond melting | fusing point of crystalline polyester resin, and an emulsified particle can be formed. Moreover, a dispersing agent can also be used for stabilization of emulsified particles and thickening of the aqueous medium. Hereinafter, such a dispersion of emulsified particles may be referred to as a “resin particle dispersion”.

  Examples of the dispersant include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, carboxymethyl cellulose, and sodium polyacrylate; sodium dodecylbenzenesulfonate, sodium octadecyl sulfate, sodium oleate, sodium laurate, and potassium stearate. Anionic surfactants; cationic surfactants such as laurylamine acetate and lauryltrimethylammonium chloride; zwitterionic surfactants such as lauryldimethylamine oxide; polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxy Surfactants such as nonionic surfactants such as ethylene alkylamine; tricalcium phosphate, aluminum hydroxide, calcium sulfate, calcium carbonate Include inorganic compounds such as barium carbonate.

  As the usage-amount of the said dispersing agent, 0.01-20 mass parts is preferable with respect to 100 mass parts of binder resins of the said core part.

  In the emulsification step, the polyester resin is copolymerized with a dicarboxylic acid having a sulfonic acid group (that is, a suitable amount of a dicarboxylic acid-derived component having a sulfonic acid group is included in the acid-derived component). ) And dispersion stabilizers such as surfactants can be reduced, or emulsified particles can be formed without using them.

  Examples of the emulsifier used when forming the emulsified particles include a homogenizer, a homomixer, a pressure kneader, an extruder, and a media disperser. The size of the emulsified particles (droplets) of the polyester resin is preferably 0.005 to 1 μm, more preferably 0.01 to 0.4 μm, in terms of the average particle size (volume average particle size). If the average particle size of the emulsified particles is less than 0.005 μm, it is almost dissolved in water, so that it may be difficult to produce the particles. If the average particle size exceeds 1 μm, the desired particle size is 3.0 to 7.5 μm. It may be difficult to obtain particles.

  As a method for dispersing the colorant, an arbitrary method, for example, a general dispersion method such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, or a dyno mill can be used.

  If necessary, an aqueous dispersion (colorant particle dispersion) of these colorants can also be prepared using a surfactant. As the surfactant and the dispersing agent used for dispersion, the same dispersing agents that can be used when dispersing the polyester resin can be used.

  In addition, a colorant can be mixed into the resin before forming the emulsified particles. As a method of mixing the colorant into the resin, melt dispersion using a disperser or the like can be mentioned.

  In the aggregation step, the obtained emulsified particles are aggregated by heating to a temperature near the melting point of the polyester resin or a temperature equal to or lower than the Tg of the amorphous resin polymer to form an aggregate.

  Formation of the aggregate of the emulsified particles is performed by acidifying the pH of the emulsion under stirring. As said pH, 2-6 are preferable and 2.5-5 are more preferable. At this time, it is also effective to use a flocculant.

  As the aggregating agent used in the aggregating step, a surfactant having a polarity opposite to that of the surfactant used for the dispersing agent, an inorganic metal salt, or a divalent or higher-valent metal complex can be preferably used. In particular, the use of a metal complex is particularly preferable because the amount of the surfactant used can be reduced and the charging characteristics are improved. Examples of the inorganic metal salt include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include inorganic metal salt polymers. Of these, aluminum salts and polymers thereof are particularly preferred. In order to obtain a sharper particle size distribution, the valence of the inorganic metal salt is bivalent than monovalent, trivalent than bivalent, trivalent than trivalent, and tetravalent than trivalent. The inorganic metal salt polymer is more suitable.

  Aggregated particles are formed by adding a flocculant at room temperature under stirring with a rotary shearing homogenizer to make the pH of the raw material dispersion acidic. In order to suppress rapid aggregation due to heating, it is preferable to adjust the pH at the stage of stirring and mixing at room temperature and add a dispersion stabilizer as necessary.

  In the coalescing step, under the same agitation as in the aggregation step, the aggregation suspension is stopped by setting the pH of the suspension of the aggregate to a range of 3 to 7, and the melting point of the crystalline polyester resin is higher than the melting point. The aggregates are fused and united by heating at a temperature. The heating temperature is not a problem as long as it is not lower than the melting point of the crystalline polyester resin. Further, the heating time may be performed so that the coalescence is sufficiently performed, and may be performed for about 0.2 to 10 hours. Thereafter, when the temperature is lowered to a temperature lower than the crystallization temperature of the crystalline polyester resin to solidify the particles, the particle shape and surface properties change depending on the temperature lowering rate. For example, when the temperature is lowered at a high speed, the spheroidization and the surface are easily smoothed. On the other hand, when the temperature is slowly lowered, the particle shape becomes irregular and the surface of the particles is likely to be uneven. Therefore, it is preferable to lower the temperature to a temperature equal to or lower than the crystallization temperature of the crystalline polyester resin at a rate of at least 1 ° C./min, preferably at a rate of 3 ° C./min. A toner base particle having a desired BET specific surface area of 2 to 5 and a shape factor SF1 of 110 to 140 is obtained by lowering the temperature at a rate of 1 ° C./min or more and crystallizing the binder resin. Can do.

In the present invention, the obtained toner base particles are further washed with water and filtered, and then a coating resin particle dispersion (coating resin dispersion) is blended to attach the coating resin. Have. By blending the coated resin particle dispersion and the toner base particles and stirring at a temperature of about Tg of the resin fine particle dispersion, a toner having a smooth surface can be produced.
If the coating resin is an amorphous polymer according to the present invention, the toner of the first invention is obtained, and if the coating resin is the acrylic silicone resin, the toner of the second invention is obtained. It is done. When the coating resin is the acrylic silicone resin, it is preferable that the acrylic silicone resin is attached and then heated at a temperature not higher than the glass transition point Tg of the acrylic silicone resin.

  The particles obtained by fusing can be converted into toner particles through a solid-liquid separation process such as filtration, and a washing process and a drying process as necessary. In this case, in order to ensure sufficient charging characteristics and reliability as a toner, it is preferable to sufficiently wash in the washing step.

  In the drying process, an arbitrary method such as a normal vibration type fluidized drying method, a spray drying method, a freeze drying method, or a flash jet method can be adopted. The toner particles are preferably adjusted to have a moisture content after drying of 1.5% or less, preferably 1.0% or less.

  In the coalescence step or the association step, a crosslinking reaction may be performed when the crystalline polyester resin is heated to a melting point or higher, or after the coalescence is completed. When the crosslinking reaction is performed, for example, an unsaturated sulfonated crystalline polyester resin obtained by copolymerizing a double bond component is used as the binder resin, and for example, t-butylperoxy-2-ethylhexa is added to this resin. A crosslinking reaction is introduced by causing a radical reaction using a polymerization initiator such as noate.

  The polymerization initiator may be mixed with the polymer in advance before the emulsification step, or may be incorporated into the aggregate in the aggregation step. Further, it may be introduced after the coalescence or association process, or after the coalescence or association process. In this case, a solution obtained by dissolving a polymerization initiator in an organic solvent may be added to a particle dispersion (resin particle dispersion or the like). These polymerization initiators may be added with known crosslinking agents, chain transfer agents, polymerization inhibitors and the like for the purpose of controlling the degree of polymerization.

  According to the method for producing an electrostatic charge developing toner of the present invention described above, the toner particle shape and surface smoothness can be controlled. The particle shape of the toner is preferably close to a sphere. By making it spherical, the non-electrostatic adhesive force is reduced, so that the transferability is improved, and further, the charge amount on the toner surface becomes uniform, and the charge maintenance property is also improved.

  In the toner of the present invention, an external additive such as a fluidizing agent or an auxiliary agent may be added to the surface of the toner particles. External additives include known fine particles such as silica fine particles, titanium fine particles, alumina fine particles, cerium oxide fine particles, carbon black and other inorganic fine particles, and polymer fine particles such as polycarbonate, polymethyl methacrylate and silicone resin. Of these, at least two kinds of external additives are used, and at least one of the external additives has an average primary particle diameter of 30 nm to 200 nm, more preferably 30 nm to 180 nm. preferable.

  As the toner particle size is reduced, non-electrostatic adhesion to the photoconductor increases, which causes transfer defects and image loss called hollow characters, and causes uneven transfer such as superimposed images. Therefore, it is preferable to add a large external additive having an average primary particle diameter of 30 nm to 200 nm to improve transferability. If the average primary particle diameter is less than 30 nm, the initial toner fluidity is good, but the non-electrostatic adhesion between the toner and the photoreceptor cannot be sufficiently reduced, resulting in a decrease in transfer efficiency and loss of image. If the uniformity of the image deteriorates, or the stress in the developing machine over time causes the fine particles to be embedded in the toner surface, the chargeability changes and causes problems such as a decrease in copy density and fogging on the background. There is a case. On the other hand, if the average primary particle diameter is larger than 200 nm, the particles may be easily detached from the toner surface, leading to deterioration of fluidity.

<Electrostatic image developer and carrier>
The electrostatic image developer of the present invention includes a toner and a carrier, and the toner is the toner of the present invention described above. Examples of the developer include a one-component developer composed only of a toner and a two-component developer composed of a toner and a carrier, and a two-component developer excellent in charge maintenance and stability is preferable. The carrier is preferably a carrier coated with a resin, and more preferably a carrier coated with a nitrogen-containing resin.

  Examples of the nitrogen-containing resin include acrylic resins including dimethylaminoethyl methacrylate, dimethylacrylamide, acrylonitrile, amino resins including urea, urethane, melamine, guanamine, aniline, amide resins, and urethane resins. These copolymer resins may also be used.

  Two or more of the nitrogen-containing resins may be used in combination as the carrier coating resin. Moreover, you may use combining the said nitrogen containing resin and resin which does not contain nitrogen. The nitrogen-containing resin may be used in the form of fine particles and dispersed in a resin not containing nitrogen. In particular, a urea resin, a urethane resin, a melamine resin, and an amide resin are preferable because they have high negative chargeability and high resin hardness, and can suppress a decrease in charge amount due to peeling of the coating resin.

In general, the carrier needs to have an appropriate electric resistance value, and specifically, an electric resistance value of 10 ⁹ to 10 ¹⁴ Ωcm is preferable. For example, when the electrical resistance value is as low as 10 ⁶ Ωcm as in the case of an iron powder carrier, the carrier adheres to the image portion of the photoreceptor due to charge injection from the sleeve, or the latent image charge escapes through the carrier and the latent image In some cases, problems such as disturbance of the image or loss of images may occur. On the other hand, if the insulating resin is coated thickly, the electrical resistance value becomes too high, and carrier charges may be difficult to leak, resulting in an edged image, but a large area image surface. Then, there may be a problem of an edge effect that the image density in the central portion becomes very thin. Therefore, it is preferable to disperse the conductive fine powder in the resin coating layer in order to adjust the resistance of the carrier.

  Specific examples of the conductive fine powder include metals such as gold, silver and copper; carbon black; and semiconductive oxides such as titanium oxide and zinc oxide; titanium oxide, zinc oxide, barium sulfate and boron. Examples thereof include those in which the surface of aluminum oxide, potassium titanate powder or the like is covered with tin oxide, carbon black, or metal. Among these, carbon black is preferable from the viewpoint of production stability, cost, and conductivity.

  Examples of the method for forming the resin coating layer on the surface of the carrier core material include an immersion method in which a powder of the carrier core material is immersed in the solution for forming the coating layer, and a solution for forming the coating layer on the surface of the carrier core material. Spraying method for spraying, fluidized bed method for spraying the solution for forming the coating layer in a state where the carrier core material is floated by flowing air, and a kneader for mixing the carrier core material and the coating layer forming solution in a kneader coater to remove the solvent. Examples of the coater method include a powder coat method in which a coating resin is finely divided and mixed in a carrier core material and a kneader coater at a temperature equal to or higher than the melting point of the coating resin and cooled to form a coating. The kneader coater method and the powder coating method are particularly preferably used.

  The average film thickness of the resin coating layer formed by the above method is usually in the range of 0.1 to 10 μm, preferably 0.2 to 5 μm.

  There is no restriction | limiting in particular as a core material (carrier core material) used in the carrier used for this invention, Magnetic metals, such as iron, steel, nickel, cobalt, or magnetic oxides, such as a ferrite and magnetite, glass beads, etc. From the viewpoint of using the magnetic brush method, a magnetic carrier is desirable. As an average particle diameter of a carrier core material, generally 10-100 micrometers is preferable and 20-80 micrometers is more preferable.

  The mixing ratio (mass ratio) of the toner of the present invention and the carrier in the two-component developer is in the range of toner: carrier = 1: 100 to 30: 100, and about 3: 100 to 20: 100. A range is more preferred.

<Image forming method>
The image forming method of the present invention includes a latent image forming step for forming an electrostatic latent image on the surface of the electrostatic charge image carrier, and developing the electrostatic latent image formed on the surface of the developer carrier with an electrostatic charge image developer. Development process for forming a toner image, a transfer process for transferring the toner image formed on the surface of the developer carrying member onto a transfer material to form a transfer image, and a transfer image transferred on the surface of the transfer material And a fixing step for fixing the toner, wherein the electrostatic charge image developer includes the electrostatic charge developing toner of the present invention described above.

As the electrostatic charge image carrier, for example, an electrophotographic photosensitive member and a dielectric recording member can be used.
When the electrostatic image bearing member is an electrophotographic photosensitive member, the surface of the electrophotographic photosensitive member is uniformly charged by a corotron charger, a contact charger or the like and then exposed to form an electrostatic latent image ( Latent image forming step).

  Next, the electrostatic latent image formed on the surface of the electrostatic image bearing member is developed with toner composed of colored particles containing at least a binder resin and a colorant to form a toner image. In electrophotography, an electrostatic latent image formed on the surface of a latent image carrier is formed by forming a developer layer on the surface of the electrostatic image carrier disposed opposite to the electrostatic image carrier. Develop. In the case of a two-component development system comprising a toner and a carrier, the developer layer is formed by a so-called magnetic brush in which a magnetic carrier is formed in the form of a brush on the surface of the developer carrying member, and the toner adheres to this (development process).

  The formed toner image is transferred onto the surface of a transfer medium such as paper using a corotron charger or the like. In this case, in addition to transferring the toner image obtained in the developing process to the transfer material as it is, it is possible to use an intermediate transfer member, and a means for transferring the toner image to the transfer material after being transferred to the intermediate transfer member.

  When a full color image is to be obtained, a toner image developed using toner of at least three colors of cyan, magenta and yellow and, if necessary, four colors of black in the development process is laminated and transferred. Is done. At this time, using an intermediate transfer material, once these are laminated and transferred onto the intermediate transfer body, and then transferred to the transfer body in a batch, it is preferable for obtaining an image with good color development without positional deviation. It is.

When a single color image is to be obtained, the toner mass (TMA) in the 100% area area of the transferred image transferred onto the transfer material in the transfer step is preferably 0.80 mg / cm ² or less, and 0.60 mg. / Cm ² or less is more preferable (transfer process).

  Further, the toner image transferred to the surface of the transfer medium is heat-fixed by a heating type fixing device to form a final toner image. Examples of the heating type fixing device include a contact heating type fixing method using a heating roll or the like, and a non-contact heating type fixing method using oven heating. However, a contact type fixing device should be used from the viewpoint of reliability, safety, and thermal efficiency. Is preferred. The contact-type fixing device herein refers to a fixing device of a type in which a fixing member such as a fixing roll presses a transfer material on which a transfer image is formed to fix the transfer image on the transfer material. A contact-type fixing device can be widely used. As a method of pressure contact, a transfer material on which a transfer image is formed is passed between two contacting rolls or between a contacting roll and a belt, and the transfer image is formed in a roll-roll or roll-belt nip region. And a method of fixing by pressing (fixing step).

  Examples of the transfer material (recording material) for transferring the toner image include plain paper and OHP sheet used for electrophotographic copying machines, printers, and the like.

  In order to further improve the smoothness of the image surface after fixing, it is preferable that the surface of the transfer object is as smooth as possible. For example, coated paper in which the surface of plain paper is coated with a resin or the like, art paper for printing Etc. can be used suitably.

  By using the electrostatic charge developing toner of the present invention, excellent storage stability of the formed image can also be realized. Further, since the toner has excellent fluidity and transferability, an image with excellent image quality can be formed, and charging can be stabilized. Furthermore, since the transfer efficiency is improved, the residual toner is reduced and the cost can be reduced.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these Examples. In the description of the examples below, “part” means “part by mass” and “%” means “% by mass” unless otherwise specified.
-Preparation of Amorphous Polymer Particle Dispersion (A-1)-
[Preparation of resin fine particles]
・ Fancryl 513M: 360 parts ・ Acrylic acid: 4 parts ・ Dodecanethiol: 24 parts ・ Carbon tetrabromide: 4 parts A mixture of the above was dissolved in a nonionic surfactant (Sanyo Kasei Co., Ltd.) ): Nonipol 400) 6 parts and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts are added to 560 parts of ion-exchanged water and dispersed and emulsified for 10 minutes. While slowly mixing, 50 parts of ion-exchanged water in which 4 parts of ammonium persulfate was dissolved was added to perform nitrogen substitution. Thereafter, the contents in the flask were heated with an oil bath until the contents reached 70 ° C. while stirring, and the emulsion polymerization was continued for 5 hours. Thus, an amorphous polymer dispersion liquid in which resin particles having a volume average particle diameter of 190 nm, a glass transition point Tg of 173 ° C., a weight average molecular weight Mw of 19,000, and a number average molecular weight Mn of 9,000 are dispersed ( A-1) (resin particle concentration: 40%) was prepared.

-Preparation of amorphous polymer particle dispersion (A-2)-
Amorphous polymer particles, except that in the preparation of the amorphous polymer particle dispersion (A-1), the compounding amount of vancyl 513M was changed from 360 parts to 335 parts and 25 parts of n-butyl acrylate was further compounded. Resin particles having a volume average particle diameter of 180 nm, a glass transition point Tg of 152 ° C., a weight average molecular weight Mw of 18,500, and a number average molecular weight Mn of 8,500 in the same manner as in the preparation of the dispersion (A-1). Amorphous polymer particle dispersion (A-2) (resin particle concentration: 40%) was prepared.

-Preparation of Amorphous Polymer Particle Dispersion (A-3)-
Amorphous polymer particles, except that in the preparation of the amorphous polymer particle dispersion (A-1), the compounding amount of vancyl 513M was changed from 360 parts to 305 parts, and 55 parts of n-butyl acrylate was further compounded. Resin particles having a volume average particle size of 200 nm, a glass transition point Tg of 138 ° C., a weight average molecular weight Mw of 20,000, and a number average molecular weight Mn of 9,000 as in the preparation of the dispersion (A-1). Amorphous polymer particle dispersion (A-3) (resin particle concentration: 40%) was prepared.

-Preparation of Amorphous Polymer Particle Dispersion (A-4)-
In the preparation of the amorphous polymer particle dispersion (A-1), the compounding amount of vancyl 513M was changed from 360 parts to 108 parts, and further 40 parts of n-butyl acrylate and 212 parts of methyl methacrylate were blended. The volume average particle diameter is 180 nm, the glass transition point Tg is 87 ° C., the weight average molecular weight Mw is 18,000, and the number average molecular weight Mn is the same as in the preparation of the amorphous polymer particle dispersion (A-1). An amorphous polymer particle dispersion (A-4) (resin particle concentration: 40%) obtained by dispersing 8,000 resin particles was prepared.

-Preparation of amorphous polymer particle dispersion (A-5)-
In the preparation of the amorphous polymer particle dispersion (A-1), cyclohexyl methacrylate: 108 parts, n-butyl acrylate: 40 parts, methyl methacrylate: 212 parts were blended in place of 360 parts by vancyl 513M Is the same as the preparation of the amorphous polymer particle dispersion (A-1), the volume average particle diameter is 180 nm, the glass transition point Tg is 72 ° C., the weight average molecular weight Mw is 19,000, and the number average molecular weight Mn is 9 Amorphous polymer particle dispersion (A-5) (resin particle concentration: 40%) prepared by dispersing resin particles having a molecular weight of 1,000.

-Preparation of Amorphous Polymer Particle Dispersion (A-6)-
Amorphous polymer particle dispersion liquid, except that in the preparation of the amorphous polymer particle dispersion liquid (A-1), 270 parts of styrene and 90 parts of n-butyl acrylate were blended in place of 360 parts of vancyl 513M Similarly to (A-1), resin particles having a volume average particle size of 170 nm, a glass transition point Tg of 52 ° C., a weight average molecular weight Mw of 17,000, and a number average molecular weight Mn of 7,000 are dispersed. Amorphous polymer particle dispersion (A-6) (resin particle concentration: 40%) was prepared.

-Preparation of amorphous polyester resin (B-1)-
The amorphous polyester resin (B-1) uses a known technique, and has a glass transition point Tg of 64 ° C., a weight average molecular weight Mw of 19,000, a number average molecular weight Mn of 5,000, an acid value of 16, and a volume average particle size. An amorphous polyester resin (B-1) having a diameter of 70 nm and a resin solid content of 30% was produced.

-Production of crystalline polyester resin (B-2 ')-
In a heat-dried three-necked flask, 124 parts of ethylene glycol, 22.2 parts of sodium dimethyl 5-sulfoisophthalate, 213 parts of dimethyl sebacate, and 0.3 part of dibutyltin oxide as a catalyst were put into a container by depressurization. The inside air was brought into an inert atmosphere with nitrogen gas, and stirred at 180 ° C. for 5 hours by mechanical stirring. Thereafter, the temperature was gradually raised to 220 ° C. under reduced pressure, and the mixture was stirred for 2 hours. When it became viscous, it was air-cooled, the reaction was stopped, and 220 parts of crystalline polyester resin (B-2 ′) was synthesized. did.

  The weight average molecular weight Mw of the obtained crystalline polyester resin (B-2 ′) was 9700 and the number average molecular weight Mn was 5400 by molecular weight measurement (polystyrene conversion) by gel permeation chromatography (GPC).

  Further, the melting point (Tm) of the crystalline polyester resin (B-2 ′) was measured by a differential scanning calorimeter (DSC) by the above-described measurement method. Was 69 ° C.

  The content ratio of the copolymer component (5-sulfoisophthalic acid component) and the sebacic acid component, which was measured and calculated from the NMR spectrum of the crystalline polyester resin (B-2 ′), was 7.5: 92.5.

-Preparation of crystalline polyester resin particle dispersion (B-2)-
150 parts of crystalline polyester resin (B-2 ′) is put in 850 parts of distilled water, and mixed and stirred with a homogenizer (IKA Japan Co., Ltd .: Ultra Tarax) while heating to 85 ° C. to obtain crystalline polyester resin particles Dispersion liquid (B-2) (resin particle concentration: 15%) was obtained.

-Preparation of colorant dispersion (C)-
After mixing and dissolving 250 parts of a cyan pigment (manufactured by Dainichi Seika Co., Ltd .: ECB-301), 20 parts of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) and 730 parts of ion-exchanged water, a homogenizer ( A colorant dispersion liquid (C) obtained by dispersing the colorant (cyan pigment) was prepared using IKA: Ultra Tarax.

-Preparation of release agent dispersion (D)-
350 parts of a release agent (Riken Vitamin Co., Ltd .: Riquemar B-200, melting point: 68 ° C.), 15 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) and 635 parts of ion-exchanged water are mixed. -Disperse | distributed using the homogenizer (the product made by IKA: Ultra Tarax), heating at 90 degreeC on the bath, and prepared the mold release agent dispersion liquid (D).

-Preparation of electrostatic charge developing toner (1)-
520 parts of amorphous polyester resin (B-1), 44 parts of colorant dispersion (C), 51 parts of release agent dispersion (D), 5 parts of calcium chloride (Wako Pure Chemical Industries, Ltd.), 1230 parts of ion-exchanged water Was accommodated in a round stainless steel flask and adjusted to pH 4.0, and then dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50), followed by stirring to 65 ° C. in a heating oil bath. While heating. After maintaining at 65 ° C. for 3 hours, observation with an optical microscope confirmed that aggregated particles having an average particle diameter of about 5.0 μm were formed. After maintaining heating and stirring at 65 ° C. for another hour, observation with an optical microscope confirmed that aggregated particles having an average particle diameter of about 5.5 μm were formed.

  The dispersion in which the aggregated particles were formed had a pH of 3.8. Therefore, an aqueous solution obtained by diluting sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to 0.5% was gently added to adjust the pH to 5.0. When this aggregated particle dispersion was continuously stirred, the temperature was raised to 80 ° C. and held for 30 minutes, and when observed with an optical microscope, coalesced spherical particles were observed. Thereafter, the temperature was lowered to 30 ° C. at a rate of 1 ° C./min while adding ion-exchanged water to solidify the particles.

  Thereafter, the reaction product was filtered, washed with 2000 parts of ion exchange water, and then filtered again to obtain 360 parts of a toner cake (core particle 1) having a toner solid content of 50%.

  After 3 L of the obtained toner cake 1 of core particles 1 was put in a flask, 75 parts of amorphous polymer particle dispersion (A-1) was added, and stirring was started. After 10 minutes, 170 parts of ion-exchanged water was added so that the solid content of the toner was 35%, and then the pH was adjusted to 3.0 by gradually adding a 0.3 mol / L nitric acid aqueous solution. did. After 30 minutes, 0.28 g of polyaluminum chloride was added, and 30 minutes later, the temperature was raised to 48 ° C. at a rate of 0.5 ° C./1 minute. After 2 hours at 48 ° C, the temperature was raised to 57 ° C at a rate of 0.1 ° C / 1 minute. Since the pH at this time was 7.3, the pH was adjusted to 7.5 by gradually adding a 0.5 mol / L sodium hydroxide aqueous solution, and heating was continued for 10 hours. After 10 hours, it was confirmed by electron microscope (SEM) photography that a coating layer of attached fine particles was formed on the surface of the core particles, and then the temperature was lowered to 20 ° C. in 30 minutes. The volume average particle size after cooling was 6.1 μm.

  Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and then dried using a vacuum dryer to obtain electrophotographic colored particles (1).

  The obtained electrophotographic colored particles (1) had a volume average particle size of 6.1 μm and a number average particle size of 5.3 μm. When the particles were observed with an optical microscope, the shape was spherical.

The shape factor SF1 of the electrophotographic colored particles (1) obtained by shape observation with Luzex was 121. Further, the BET specific surface area of the colored particles was 1.74 m ² / g.

  0.8% of silica fine particles (hydrophobic silica manufactured by Nippon Aerosil Co., Ltd .: RX50) having an average primary particle diameter of 40 nm, which is 98.2% of the electrophotographic colored particles (1) and surface hydrophobized, and 100 parts of metatitanic acid The reaction product treated with 40 parts of isobutyltrimethoxysilane and 10 parts of trifluoropropyltrimethoxysilane was metatitanic acid compound fine particles having an average primary particle diameter of 20 nm at a ratio of 1.0% in a Henschel mixer for 5 minutes. Added and mixed. Thereafter, the mixture was sieved with a 45 μm sieving mesh to produce an electrostatic charge developing toner (1).

-Preparation of electrostatic charge developing toner (2)-
In the preparation of the electrostatic charge developing toner (1), the electrostatic charge developing toner (1) was changed except that the amorphous polymer particle dispersion (A-1) was changed to the amorphous polymer particle dispersion (A-2). The toner (2) for developing electrostatic charge was produced in the same manner as in the production of
The electrophotographic colored particles (2) produced before the electrostatic charge developing toner (2) had a volume average particle size of 5.6 μm and a number average particle size of 4.8 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 126. Further, the BET specific surface area of the colored particles was 1.98 m ² / g.

-Preparation of electrostatic charge developing toner (3)-
To produce the electrostatic charge developing toner (1), except that the amorphous polymer particle dispersion (A-1) is changed to the amorphous polymer particle dispersion (A-3), the electrostatic charge developing toner (1 The toner for electrostatic charge development (3) was prepared in the same manner as in the preparation of
The electrophotographic colored particles (3) produced before the electrostatic charge developing toner (3) had a volume average particle size of 5.9 μm and a number average particle size of 5.1 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 122. Further, the BET specific surface area of the colored particles was 1.76 m ² / g.

-Preparation of electrostatic charge developing toner (4)-
In the production of the electrostatic charge developing toner (1), the electrostatic charge developing toner (1) was changed except that the amorphous polymer particle dispersion (A-1) was changed to the amorphous polymer particle dispersion (A-4). The toner (4) for developing an electrostatic charge was produced in the same manner as in the production of
The electrophotographic colored particles (4) produced before the electrostatic charge developing toner (4) had a volume average particle size of 6.0 μm and a number average particle size of 5.2 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 122. Further, the BET specific surface area of the colored particles was 1.80 m ² / g.

-Preparation of electrostatic charge developing toner (5)-
In the preparation of the electrostatic charge developing toner (1), 520 parts of the amorphous polyester resin (B-1) is changed to 1040 parts of the crystalline polyester resin particle dispersion (B-2), and the amount of ion-exchanged water used is changed. Except for changing from 1230 parts to 600 parts, the electrostatic charge developing toner (5) was prepared in the same manner as the electrostatic charge developing toner (1).
The electrophotographic colored particles (5) prepared before the electrostatic charge developing toner (5) had a volume average particle size of 6.2 μm and a number average particle size of 5.4 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 127. Further, the BET specific surface area of the colored particles was 2.01 m ² / g.

-Production of electrostatic charge developing toner (6)-
In the production of the electrostatic charge developing toner (4), 520 parts of the amorphous polyester resin (B-1) was changed to 1040 parts of the crystalline polyester resin particle dispersion (B-2), and the amount of ion-exchanged water used was changed. Except for changing from 1230 parts to 600 parts, the electrostatic charge developing toner (6) was prepared in the same manner as the electrostatic charge developing toner (4).
The electrophotographic colored particles (6) prepared before the electrostatic charge developing toner (6) had a volume average particle size of 5.7 μm and a number average particle size of 4.9 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 123. Further, the BET specific surface area of the colored particles was 1.68 m ² / g.

-Preparation of electrostatic charge developing toner (7)-
In the production of the electrostatic charge developing toner (2), 520 parts of the amorphous polyester resin (B-1) was changed to 360 parts, and 320 parts of the crystalline polyester resin particle dispersion (B-2) was added, followed by ion exchange. An electrostatic charge developing toner (7) was prepared in the same manner as the preparation of the electrostatic charge developing toner (2) except that the amount of water used was changed from 1230 parts to 1050 parts.
The electrophotographic colored particles (7) produced before the electrostatic charge developing toner (7) had a volume average particle size of 6.0 μm and a number average particle size of 5.2 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 125. Further, the BET specific surface area of the colored particles was 1.87 m ² / g.

-Preparation of electrostatic charge developing toner (8)-
In the preparation of the electrostatic charge developing toner (1), the electrostatic charge developing toner (1) was changed except that the amorphous polymer particle dispersion (A-1) was changed to the amorphous polymer particle dispersion (A-5). The toner (8) for developing an electrostatic charge was produced in the same manner as in the production of
The electrophotographic colored particles (8) prepared before the electrostatic charge developing toner (8) had a volume average particle size of 5.6 μm and a number average particle size of 4.8 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 122. Further, the BET specific surface area of the colored particles was 1.73 m ² / g.

-Preparation of electrostatic charge developing toner (9)-
In the preparation of the electrostatic charge developing toner (1), the electrostatic charge developing toner (1) was changed except that the amorphous polymer particle dispersion (A-1) was changed to the amorphous polymer particle dispersion (A-6). The toner (9) for developing electrostatic charge was produced in the same manner as in the production of
The electrophotographic colored particles (9) prepared before the electrostatic charge developing toner (9) had a volume average particle size of 5.8 μm and a number average particle size of 5.0 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 123. Moreover, the BET specific surface area of the colored particles was 1.82 m ² / g.

-Preparation of electrostatic charge developing toner (10)-
In the production of the electrostatic charge developing toner (8), 520 parts of the amorphous polyester resin (B-1) was changed to 1040 parts of the crystalline polyester resin particle dispersion (B-2), and the amount of ion-exchanged water used was changed. Except for changing from 1230 parts to 600 parts, the electrostatic charge developing toner (10) was prepared in the same manner as the electrostatic charge developing toner (8).
The electrophotographic colored particles (10) produced before the electrostatic charge developing toner (10) had a volume average particle size of 5.7 μm and a number average particle size of 4.9 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 124. Further, the BET specific surface area of the colored particles was 1.62 m ² / g.

-Preparation of electrostatic charge developing toner (11)-
In the production of the electrostatic charge developing toner (9), 520 parts of the amorphous polyester resin (B-1) was changed to 1040 parts of the crystalline polyester resin particle dispersion (B-2), and the amount of ion-exchanged water used was changed. Except for changing from 1230 parts to 600 parts, the electrostatic charge developing toner (11) was prepared in the same manner as the electrostatic charge developing toner (9).
The electrophotographic colored particles (11) produced before the electrostatic charge developing toner (11) had a volume average particle size of 5.9 μm and a number average particle size of 5.1 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 123. Further, the BET specific surface area of the colored particles was 1.76 m ² / g.

<Example 1>
-Measurement and evaluation of powder cohesion (toner blocking resistance) after storage at 55 ° C-
Using a powder tester (manufactured by Hosokawa Micron), place a sieve with a mesh opening of 53 μm, put 2 g of the electrostatic charge developing toner (1) accurately weighed on the 53 μm sieve, and give vibration for 90 seconds with an amplitude of 1 mm. The mass of the toner on the sieve after vibration was measured. The sample (toner for electrostatic charge development (1)) was left for about 24 hours in an environment of 55 ° C./50% RH, and the measurement was performed in an environment of 25 ° C./50% RH. The results are shown in Table 1. In the present invention, the powder cohesiveness was determined by measuring the mass of the toner on the 53 μm sieve after the vibration and determined as follows: ○: The mass of the toner on the sieve is less than 0.2 g.
Δ: The mass of toner on the sieve is 0.2 g or more and less than 0.5 g.
X: The mass of the toner on the sieve is 0.5 g or more.

-Fabrication of carrier-
Trifunctional isocyanate 80% by mass ethyl acetate in a carbon dispersion obtained by mixing 1.25 parts by mass of toluene with 0.12 parts by mass of carbon black (trade name; VXC-72, manufactured by Cabot) and stirring and dispersing in a sand mill for 20 minutes. A coating agent resin solution obtained by mixing and stirring 1.25 parts by mass of a solution (Takenate D110N: manufactured by Takeda Pharmaceutical Co., Ltd.) and mn-mg-Sr ferrite particles (average particle size: 35 μm) were put into a kneader, and at room temperature for 5 minutes. After mixing and stirring, the temperature was raised to 150 ° C. at normal pressure, and the solvent was distilled off. After further 30 minutes of mixing and stirring, the heater was turned off and the temperature was lowered to 50 ° C. The obtained coated carrier was sieved with a 75 μm mesh to prepare a carrier.

-Production of electrophotographic developer (1)-
5 parts of electrostatic charge developing toner (1) and 95 parts of carrier were placed in a V blender and stirred for 20 minutes, followed by sieving with a 105 μm mesh to prepare electrophotographic developer (1).

-Evaluation of image preservation-
Using a DocuCenter Color a450 remodeling machine (Fuji Xerox Co., Ltd.), an image was formed under the condition of a toner mass (TMA) of 0.60 mg / cm ² , and further fixed at a fixing temperature of 200 ° C. Two recording papers on which a fixed image was formed were allowed to stand for 7 days in a state where a load of 100 g / cm ² was applied in an environment of a temperature of 55 ° C. and a humidity of 85% with the image surfaces overlapped. The superimposed images were peeled off, the images were fused between the recording papers, and the presence or absence of transfer in the non-image area was visually observed and evaluated according to the following evaluation criteria. The results are shown in Table 1. The image formation includes a latent image forming process, a developing process, a transfer process, and a fixing process.

[Criteria for image preservation evaluation]
○: No problem in image storability △: Some change was observed but no problem in practical use ×: Large change was observed, and practical use was not possible

-Cleaning and filming-
2 g of the electrostatic charge developing developer (1) is uniformly coated on the photosensitive member provided with a cleaning blade and rotated twice. At that time, the cleaning property was visually evaluated from the amount of toner collected by the cleaning blade according to the following criteria. Further, filming was visually evaluated according to the following criteria from the contamination of the photoreceptor by the toner that passed through the cleaning blade and was crushed on the photoreceptor.

[Evaluation criteria for cleaning properties]
A: The amount of toner collected by the cleaning blade is 1.9 g or more.
Δ: The amount of toner collected by the cleaning blade is 0.5 g or more and less than 1.9 g.
X: The amount of toner collected by the cleaning blade is less than 0.5 g.

[Filming evaluation criteria]
A: No photoconductor contamination due to toner crushing.
○: Photoconductor contamination due to toner crushing is slight.
(Triangle | delta): Although there exists a photoreceptor contamination by toner crushing, there is no problem practically.
X: Photoconductor contamination due to obvious toner crushing.

<Example 2>
In Example 1, an electrostatic charge developing developer (2) was prepared in the same manner as in Example 1 except that the electrostatic charge developing toner (1) was replaced with the electrostatic charge developing toner (2). Evaluation similar to 1 was performed. The results are shown in Table 1.

<Example 3>
In Example 1, an electrostatic charge developing developer (3) was prepared in the same manner as in Example 1 except that the electrostatic charge developing toner (1) was replaced with the electrostatic charge developing toner (3). Evaluation similar to 1 was performed. The results are shown in Table 1.

<Example 4>
In Example 1, an electrostatic charge developing developer (4) was prepared in the same manner as in Example 1 except that the electrostatic charge developing toner (1) was replaced with the electrostatic charge developing toner (4). Evaluation similar to 1 was performed. The results are shown in Table 1.

<Example 5>
In Example 1, an electrostatic charge developing developer (5) was produced in the same manner as in Example 1 except that the electrostatic charge developing toner (1) was replaced with the electrostatic charge developing toner (5). Evaluation similar to 1 was performed. The results are shown in Table 1.

<Example 6>
In Example 1, an electrostatic charge developing developer (6) was prepared in the same manner as in Example 1 except that the electrostatic charge developing toner (1) was replaced with the electrostatic charge developing toner (6). Evaluation similar to 1 was performed. The results are shown in Table 1.

<Example 7>
In Example 1, an electrostatic charge developing developer (7) was prepared in the same manner as in Example 1 except that the electrostatic charge developing toner (1) was replaced with the electrostatic charge developing toner (7). Evaluation similar to 1 was performed. The results are shown in Table 1.

<Comparative Example 1>
In Example 1, an electrostatic charge developing developer (8) was prepared in the same manner as in Example 1 except that the electrostatic charge developing toner (1) was replaced with the electrostatic charge developing toner (8). Evaluation similar to 1 was performed. The results are shown in Table 1.

<Comparative example 2>
In Example 1, an electrostatic charge developing developer (9) was prepared in the same manner as in Example 1 except that the electrostatic charge developing toner (1) was replaced with the electrostatic charge developing toner (9). Evaluation similar to 1 was performed. The results are shown in Table 1.

<Comparative Example 3>
In Example 1, an electrostatic charge developing developer (10) was prepared in the same manner as in Example 1 except that the electrostatic charge developing toner (1) was replaced with the electrostatic charge developing toner (10). Evaluation similar to 1 was performed. The results are shown in Table 1.

<Comparative example 4>
In Example 1, an electrostatic charge developing developer (11) was prepared in the same manner as in Example 1 except that the electrostatic charge developing toner (1) was replaced with the electrostatic charge developing toner (11). Evaluation similar to 1 was performed. The results are shown in Table 1.

  From Table 1, it can be seen that Examples 1 to 7 have good toner blocking resistance, image storage stability, cleaning performance, and filming resistance.

-Preparation of acrylic resin particle dispersion (E) for comparative study-
[Preparation of resin fine particles]
-Styrene: 200 parts-Methyl methacrylate: 120 parts-N-butyl acrylate: 40 parts-Acrylic acid: 4 parts-Dodecanethiol: 24 parts-Carbon tetrabromide: 4 parts Nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) 6 parts and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 10 parts dissolved in ion-exchanged water 560 parts Then, while dispersing and emulsifying in a flask, and slowly mixing for 10 minutes, 50 parts of ion-exchanged water in which 4 parts of ammonium persulfate was dissolved was added thereto, and after replacing with nitrogen, the inside of the flask was stirred. The contents were heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. Thus, an acrylic resin particle dispersion (E) for comparison, in which resin particles having an average particle diameter of 180 nm, a glass transition point of 73 ° C., Mw of 15,000, and Mn of 7,000 are dispersed (resin particle concentration) : 40%).

-Preparation of electrostatic charge developing toner (12)-
520 parts of the amorphous polyester resin (B-1), 44 parts of the colorant dispersion (C), 51 parts of the release agent dispersion (D), 5 parts of calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.), ion-exchanged water 1230 Were accommodated in a round stainless steel flask, adjusted to pH 4.0, dispersed using a homogenizer (IKA: Ultra Turrax T50), and then stirred to 65 ° C. in a heating oil bath. While heating. After maintaining at 65 ° C. for 3 hours, observation with an optical microscope confirmed that aggregated particles having an average particle diameter of about 5.0 μm were formed. After maintaining heating and stirring at 65 ° C. for another hour, observation with an optical microscope confirmed that aggregated particles having an average particle diameter of about 5.5 μm were formed.

  The dispersion in which the aggregated particles were formed had a pH of 3.8. Therefore, an aqueous solution obtained by diluting sodium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) to 0.5% was gently added to adjust the pH to 5.0. The aggregated particle dispersion was heated to 80 ° C. and kept for 30 minutes while continuing stirring, and then observed with an optical microscope, and coalesced spherical particles were observed. Thereafter, the temperature was lowered to 30 ° C. at a rate of 1 ° C./min while adding ion-exchanged water to solidify the particles.

  Thereafter, the reaction product was filtered, washed with 2000 parts of ion-exchanged water, and then filtered again to obtain 360 parts of toner cake (core particles) having a toner solid content of 50%.

  After the obtained toner cake was put in a 3 L flask, 120 parts of an acrylic silicone emulsion (trade name: Aquabrid Asi-91, manufactured by Daicel Chemical Industries, Ltd.) was added, and stirring was started. After 10 minutes, 140 parts of ion exchange water was added so that the solid content of the toner would be 35%, and then the pH was adjusted to 3.0 by gradually adding a 0.3 mol / L nitric acid aqueous solution. did. After 30 minutes, 0.28 g of polyaluminum chloride was added, and 30 minutes later, the temperature was raised to 48 ° C. at a rate of 0.5 ° C./1 minute. After 2 hours at 48 ° C, the temperature was raised to 57 ° C at a rate of 0.1 ° C / 1 minute. Since the pH at this time was 7.3, the pH was adjusted to 7.5 by gradually adding a 0.5 mol / L sodium hydroxide aqueous solution, and heating was continued for 10 hours. After 10 hours, it was confirmed by electron microscope (SEM) photography that a coating layer of attached fine particles was formed on the surface of the core particles, and then the temperature was lowered to 20 ° C. in 30 minutes. The volume average particle size after cooling was 6.1 μm.

  Thereafter, the reaction product was filtered, sufficiently washed with ion-exchanged water, and then dried using a vacuum dryer to obtain electrophotographic colored particles (12).

The obtained electrophotographic colored particles (12) had a volume average particle size of 6.1 μm and a number average particle size of 5.3 μm. When the particles were observed with an optical microscope, the shape was spherical.
Further, the shape factor SF1 of the colored particles determined by shape observation with Luzex was 124. Further, the BET specific surface area of the colored particles was 1.88 m ² / g.

  0.8% of silica fine particles having a volume average primary particle diameter of 40 nm (hydrophobic silica manufactured by Nippon Aerosil Co., Ltd .: RX50), which is 98.2% electrophoretic colored particles (12) and surface hydrophobized, 100 parts metatitanic acid The reaction product treated with 40 parts of isobutyltrimethoxysilane and 10 parts of trifluoropropyltrimethoxysilane was metatitanic acid compound fine particles having an average primary particle diameter of 20 nm at a ratio of 1.0% in a Henschel mixer for 5 minutes. Added and mixed. Thereafter, the mixture was sieved with a 45 μm sieving mesh to produce an electrostatic charge developing toner (12).

-Preparation of electrostatic charge developing toner (13)-
In the production of the electrostatic charge developing toner (12), the amount of the amorphous polyester resin (B-1) used is changed from 520 parts to 403 parts with an acrylic silicone emulsion (trade name: Aquabrid Asi-91, Daicel Chemical Industries, Ltd.). ) Manufactured) is used in an amount of 120 parts to 230 parts, and the amount of ion-exchanged water used in the production of the aggregated particles is changed from 1230 parts to 1000 parts. In the same manner as in the preparation, an electrostatic charge developing toner (13) was prepared.
The electrophotographic colored particles (13) produced before the electrostatic charge developing toner (13) had a volume average particle size of 6.3 μm and a number average particle size of 5.5 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 128. Further, the BET specific surface area of the colored particles was 2.10 m ² / g.

-Production of electrostatic charge developing toner (14)-
In the preparation of the electrostatic charge developing toner (12), 120 parts of an acrylic silicone emulsion (trade name: Aquabrid Asi-91, manufactured by Daicel Chemical Industries, Ltd.) was added to an acrylic silicone emulsion (trade name: Aquabrid Asi-91z3, Except for changing to 120 parts (manufactured by Daicel Chemical Industries, Ltd.), an electrostatic charge developing toner (14) was prepared in the same manner as the electrostatic charge developing toner (12).
The electrophotographic colored particles (14) prepared before the electrostatic charge developing toner (14) had a volume average particle size of 5.9 μm and a number average particle size of 5.1 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 123. Further, BET specific surface area of the colored particles was 1.96m ² / g.

-Production of electrostatic charge developing toner (15)-
In the production of the electrostatic charge developing toner (12), 520 parts of the amorphous polyester resin (B-1) was changed to 1040 parts of the crystalline polyester resin (B-2 ′), and further used for producing aggregated particles. An electrostatic charge developing toner (15) was prepared in the same manner as the electrostatic charge developing toner (12) except that the amount of ion-exchanged water was changed from 1230 parts to 710 parts.
The electrophotographic colored particles (15) produced before the electrostatic charge developing toner (15) had a volume average particle size of 6.2 μm and a number average particle size of 5.3 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 127. Further, BET specific surface area of the colored particles was 1.94m ² / g.

-Preparation of electrostatic charge developing toner (16)-
In the production of the electrostatic charge developing toner (12), 520 parts of the amorphous polyester resin (B-1) was changed to 806 parts of the crystalline polyester resin (B-2 ′), and an acrylic silicone emulsion (trade name: Aquabrid Asi). -91 (manufactured by Daicel Chemical Industries, Ltd.) was changed from 120 parts to 230 parts, and the amount of ion-exchanged water used when producing the agglomerated particles was changed from 1230 parts to 600 parts. In the same manner as in the preparation of the charge developing toner (12), an electrostatic charge developing toner (16) was prepared.
The electrophotographic colored particles (16) produced before the electrostatic charge developing toner (16) had a volume average particle diameter of 6.0 μm and a number average particle diameter of 5.2 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 125. Further, the BET specific surface area of the colored particles was 1.89 m ² / g.

-Toner for electrostatic charge development (17)-
In the production of the electrostatic charge developing toner (12), the amount of the amorphous polyester resin (B-1) used was changed from 520 parts to 260 parts, and further 520 parts of the crystalline polyester resin (B-2 ′) was added. The electrostatic charge developing toner is prepared in the same manner as in the preparation of the electrostatic charge developing toner (12), except that the amount of ion-exchanged water used when preparing the aggregated particles is changed from 1230 parts to 970 parts. Toner (17) was produced.
The electrophotographic colored particles (17) prepared before the electrostatic charge developing toner (17) had a volume average particle size of 6.3 μm and a number average particle size of 5.5 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 129. Further, the BET specific surface area of the colored particles was 1.79 m ² / g.

-Toner for electrostatic charge development (18)-
In the production of the electrostatic charge developing toner (12), the amount of the amorphous polyester resin (B-1) used was changed from 520 parts to 490 parts, and an acrylic silicone emulsion (trade name: Aquabrid Asi-91 (Daicel Chemical). Toner for electrostatic charge development (12) except that 36 parts of Kogyo Co., Ltd.) were added and the aggregation process was performed to change the amount of ion-exchanged water used when producing aggregated particles from 1230 parts to 1220 parts. The electrostatic charge developing toner (18) was produced in the same manner as in the above.
The electrophotographic colored particles (18) produced before the electrostatic charge developing toner (18) had a volume average particle size of 6.1 μm and a number average particle size of 5.3 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 126. Further, the BET specific surface area of the colored particles was 2.03 m ² / g.

-Toner for electrostatic charge development (19)-
In the production of the electrostatic charge developing toner (12), the amount of the amorphous polyester resin (B-1) used was changed from 520 parts to 350 parts, and an acrylic silicone emulsion (trade name: Aquabrid Asi-91, Daicel Chemical). Toner for electrostatic charge development (12) except that the amount of ion-exchanged water used when producing aggregated particles was changed from 1230 parts to 1200 parts by adding 204 parts of Kogyo Kogyo Co., Ltd. The electrostatic charge developing toner (19) was prepared in the same manner as described above.
The electrophotographic colored particles (19) prepared before the electrostatic charge developing toner (19) had a volume average particle size of 6.2 μm and a number average particle size of 5.4 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 125. Further, the BET specific surface area of the colored particles was 2.06 m ² / g.

-Toner for electrostatic charge development (20)-
In the production of the electrostatic charge developing toner (12), 120 parts of an acrylic silicone emulsion (trade name: Aquabrid Asi-91, manufactured by Daicel Chemical Industries, Ltd.) was added to 75 parts of a comparative acrylic resin particle dispersion (E). An electrostatic charge developing toner (20) was prepared in the same manner as the preparation of the electrostatic charge developing toner (12) except that the toner was changed.
The electrophotographic colored particles (20) produced before the electrostatic charge developing toner (20) had a volume average particle size of 6.0 μm and a number average particle size of 5.2 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 123. Further, the BET specific surface area of the colored particles was 1.72 m ² / g.

-Toner for electrostatic charge development (21)-
In the preparation of the electrostatic charge developing toner (15), 120 parts of an acrylic silicone emulsion (trade name: Aquabrid Asi-91, manufactured by Daicel Chemical Industries, Ltd.) was added to 75 parts of a comparative acrylic resin particle dispersion (E). Except for the change, the electrostatic charge developing toner (21) was prepared in the same manner as the electrostatic charge developing toner (15).
The electrophotographic colored particles (21) prepared before the electrostatic charge developing toner (21) had a volume average particle size of 6.0 μm and a number average particle size of 5.2 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 122. Further, the BET specific surface area of the colored particles was 1.67 m ² / g.

-Toner for electrostatic charge development (22)-
In the production of the electrostatic charge developing toner (17), 120 parts of an acrylic silicone emulsion (trade name: Aquabrid Asi-91, manufactured by Daicel Chemical Industries, Ltd.) was added to 88 parts of a comparative acrylic resin particle dispersion (E). Except for the change, the electrostatic charge developing toner (22) was prepared in the same manner as the electrostatic charge developing toner (17).
The electrophotographic colored particles (22) prepared before the electrostatic charge developing toner (22) had a volume average particle size of 6.3 μm and a number average particle size of 5.5 μm.
The shape factor SF1 of the colored particles determined by shape observation with Luzex was 126. Further, the BET specific surface area of the colored particles was 1.81 m ² / g.

<Example 8>
In the production of the electrophotographic developer (1) in Example 1, the electrophotographic developer (1) was produced except that the electrostatic charge developing toner (1) was changed to the electrostatic charge developing toner (12). Similarly, an electrophotographic developer (12) was obtained.
Further, the same evaluation as in Example 1 was performed on the electrostatic charge developing toner (12) or the electrophotographic developer (12). The results are shown in Table 2.

<Example 9>
In Example 8, an electrostatic charge developing developer (13) was produced in the same manner as in Example 8 except that the electrostatic charge developing toner (12) was replaced with the electrostatic charge developing toner (13). Evaluation similar to 8 was performed. The results are shown in Table 2.

<Example 10>
In Example 8, an electrostatic charge developing developer (14) was prepared in the same manner as in Example 8 except that the electrostatic charge developing toner (12) was replaced with the electrostatic charge developing toner (14). Evaluation similar to 8 was performed. The results are shown in Table 2.

<Example 11>
In Example 8, an electrostatic charge developing developer (15) was prepared in the same manner as in Example 8 except that the electrostatic charge developing toner (12) was replaced with the electrostatic charge developing toner (15). Evaluation similar to 8 was performed. The results are shown in Table 2.

<Example 12>
In Example 8, an electrostatic charge developing developer (16) was prepared in the same manner as in Example 8 except that the electrostatic charge developing toner (12) was replaced with the electrostatic charge developing toner (16). Evaluation similar to 8 was performed. The results are shown in Table 2.

<Example 13>
In Example 8, an electrostatic charge developing developer (17) was prepared in the same manner as in Example 8 except that the electrostatic charge developing toner (12) was replaced with the electrostatic charge developing toner (17). Evaluation similar to 8 was performed. The results are shown in Table 2.

<Example 14>
In Example 8, an electrostatic charge developing developer (18) was produced in the same manner as in Example 8, except that the electrostatic charge developing toner (12) was replaced with the electrostatic charge developing toner (18). Evaluation similar to 8 was performed. The results are shown in Table 2.

<Example 15>
In Example 8, an electrostatic charge developing developer (19) was produced in the same manner as in Example 8, except that the electrostatic charge developing toner (12) was replaced with the electrostatic charge developing toner (19). Evaluation similar to 8 was performed. The results are shown in Table 2.

<Comparative Example 5>
In Example 8, an electrostatic charge developing developer (20) was produced in the same manner as in Example 8, except that the electrostatic charge developing toner (12) was replaced with the electrostatic charge developing toner (20). Evaluation similar to 8 was performed. The results are shown in Table 2.

<Comparative Example 6>
In Example 8, an electrostatic charge developing developer (21) was produced in the same manner as in Example 8 except that the electrostatic charge developing toner (12) was replaced with the electrostatic charge developing toner (21). Evaluation similar to 8 was performed. The results are shown in Table 2.

<Comparative Example 7>
In Example 8, an electrostatic charge developing developer (22) was prepared in the same manner as in Example 8, except that the electrostatic charge developing toner (12) was replaced with the electrostatic charge developing toner (22). Evaluation similar to 8 was performed. The results are shown in Table 2.

  From Table 2, it can be seen that Examples 8 to 15 have good toner blocking resistance, image storage stability, cleaning performance, and filming resistance.

Claims (9)

A toner for electrostatic charge development having a core-shell structure having a core layer comprising toner base particles containing a binder resin and a colorant, and a shell layer covering the core layer,
The electrostatic charge image developing toner, wherein the shell layer contains an amorphous polymer obtained by polymerizing an alicyclic monomer having 11 to 14 carbon atoms.   The toner for developing an electrostatic charge image according to claim 1, wherein the amorphous polymer has a glass transition point Tg of 150 to 180 ° C. A core-shell structure electrostatic charge developing toner having a core layer composed of toner base particles containing a binder resin and a colorant, and a shell layer covering the core layer,
The electrostatic charge image developing toner, wherein the shell layer contains an acrylic silicone resin.   The electrostatic image developing toner according to claim 3, wherein the content of the acrylic silicone resin is 4 to 70% by mass.   5. The electrostatic image developing toner according to claim 3, wherein the acrylic silicone resin is contained only in the shell layer, and the content of the acrylic silicone resin is 4 to 40% by mass.   6. The electrostatic charge image developing toner according to claim 1, wherein the binder resin contains a crystalline resin. A method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 6,
A resin particle dispersion containing particles of a binder resin having a particle size of 1 μm or less, and a colorant particle dispersion containing particles of a colorant are mixed, and an aggregating agent is added thereto to add the binder resin particles and the colorant. An aggregating step for aggregating the particles to form aggregated particles; a coalescing step for producing the toner base particles by combining the aggregated particles at a temperature equal to or higher than the melting point of the binder resin; and coating the toner base particles A method for producing an electrostatic charge developing toner, comprising: an adhesion step for adhering resin particles. An electrostatic charge image developer containing toner and carrier,
The electrostatic charge developing developer according to claim 1, wherein the toner is the electrostatic charge developing toner according to claim 1. A latent image forming step for forming an electrostatic latent image on the surface of the electrostatic charge image carrier, and development for forming a toner image by developing the electrostatic latent image formed on the surface of the developer carrier with an electrostatic charge image developer. A transfer step for transferring a toner image formed on the surface of the developer carrying member onto a transfer material to form a transfer image, and a fixing step for fixing the transfer image transferred on the surface of the transfer material. An image forming method comprising:
The image forming method according to claim 1, wherein the electrostatic charge image developer includes the electrostatic charge developing toner according to claim 1.