JP4944457B2 - Toner and image forming method using the same - Google Patents

Description

  The present invention includes a copying machine using a direct or indirect electrophotographic developing system, a laser printer, a plain paper fax machine, a full color copying machine using a direct or indirect electrophotographic multicolor developing system, a full color laser printer, a full color plain paper fax machine, etc. The present invention relates to a toner suitably used in electrophotography, electrostatic recording, and electrostatic printing, and an image forming method using the toner.

  In image formation by electrophotography or the like, generally, an electrostatic image is formed on a photoreceptor (electrostatic image carrier), and the electrostatic image is developed with a developer to form a visible image (toner image). The visible image is transferred to a recording medium such as paper and fixed to form a fixed image (see Patent Document 1). As the developer, a one-component developer using a magnetic toner or a non-magnetic toner alone and a two-component developer composed of a toner and a carrier are known.

  As the fixing method in the electrophotographic method, a heated heat roller method in which a heating roller is directly pressed against a toner image on a recording medium and fixed is widely used because of its energy efficiency. However, in the case of the heating heat roller system, there is a problem that a large amount of electric power is required for the fixing. For this reason, from the viewpoint of energy saving, various studies have been made to reduce the power consumption of the heating roller. For example, the output of the heater for the heating roller is weakened when the image is not output, and the heater is turned off when the image is output. A method of increasing the output to raise the temperature of the heating roller is generally used. However, in this case, in order to raise the temperature of the heating roller to the temperature required for fixing from the sleep time, a waiting time of about several tens of seconds is required, and this waiting time becomes a stress for the user. In addition, when the image is not output, it is desired to further reduce power consumption by completely turning off the heater. In order to achieve these demands, it is considered essential to lower the fixing temperature of the toner itself and lower the toner fixing temperature when it can be used.

In order to achieve low-temperature fixing of the toner, it is necessary to control the thermal characteristics of the resin itself. For example, a melt-miscible material that is compatible with the resin and exhibits a plastic effect (hereinafter referred to as a fixing aid) It has been practiced to reduce the glass transition temperature (Tg) of the resin by adding to the toner. However, if Tg is lowered too much, the heat-resistant storage stability is deteriorated, and if the flow tester method 1/2 temperature (F _1/2 ) is lowered too much, problems such as lowering the hot offset occurrence temperature occur. The development of a toner that can achieve both a low-temperature fixability and a heat-resistant storage stability at good levels has been a long-standing problem.

Thus, for the purpose of achieving both low-temperature fixability and heat-resistant storage stability, for example, Patent Document 2 describes a toner in which resin protrusions containing no plasticizer are present on the toner particle surface. In this case, although the protrusions are provided, the inside of the toner is mainly composed of a low Tg resin, and it is difficult to achieve both low-temperature fixability and heat-resistant storage stability at a good level.
For example, Patent Document 3 discloses a toner containing a binder that does not separate and precipitate in the wax when the wax having a melting point of 20 to 150 ° C. is dissolved in the wax as a solvent and further rapidly cooled. Are listed. According to the toner, since the wax exhibits a plastic effect on a resin having a melting point higher than the fixing temperature, it can be fixed at a low temperature, but is produced by a pulverization method including a melt-kneading step. A plasticizing effect has already been exhibited at the time of production, and the heat resistant storage stability is not sufficient.
For example, Patent Document 4 describes a toner containing two types of waxes, a compatible wax and an incompatible wax, with respect to a resin monomer. However, the toner described in Patent Document 4 is mainly intended for a toner for a one-component developer, and is intended to uniformly disperse a magnetic substance in the toner, and is a wax having compatibility with the toner. Although the plasticizing effect is mentioned, it is intended only to assist the dispersion of the magnetic material. In addition, since the toner manufacturing process includes a heating process at a temperature higher than the melting point of the compatible wax, a plasticizing effect is already manifested during the manufacturing process as in the toner described in Patent Document 3. There is a problem that heat-resistant storage stability deteriorates.
For example, Patent Document 5 describes a toner containing a polyfunctional ester compound that is compatible with a resin monomer. However, in the toner, only the melting point of the resin monomer and the melting point of the polyfunctional ester compound are just the same, and the glass transition temperature (Tg) of the toner is Since the plastic effect by the polyfunctional ester compound has already been developed, it is impossible to sufficiently achieve both low-temperature fixability and heat-resistant storage stability.

  Therefore, for the purpose of achieving both low-temperature fixability and heat-resistant storage stability, for example, a microcapsule toner having a shell portion formed of a high melting point compound and a core portion formed of a colored phase that is liquid at room temperature is provided. Proposed. As an example of this, for example, a copolymer having a microphase separation structure composed of a dispersed phase and a continuous phase and having compatibility with both phases is used as a core portion to improve the stability of an image after fixing. There is known a microcapsule toner that can be used (see Patent Document 6). However, the toner formed in such a configuration still needs to be pressurized for fixing, and also has problems such as toner stability, image disturbance, and glossiness reduction. It is difficult to develop the characteristics that are achieved.

In addition, attempts have been made to add a fixing aid having sharp melt properties at the glass transition temperature in the binder resin. For example, Patent Document 7 proposes the use of crystalline polyester as a fixing aid.
Further, in a toner having a fixing aid introduced, when the toner is heated by the fixing roller, the fixing aid, which is a material having a high affinity with the binder, bleeds (sticks out) and adheres to the roller surface. Thus, it has been found that the tack force between the toner layer and the fixing roller is increased, and sufficient low-temperature fixability cannot be obtained.

  Therefore, it has both excellent low-temperature fixability and heat-resistant storage stability, good characteristics such as fixability, good quality images can be obtained, and power saving and waiting time can be shortened. At present, the toner that can be used and the related technology using the toner are not yet provided.

US Pat. No. 2,297,691 JP-A-6-258861 JP 2002-221825 A JP 2002-202627 A JP 2001-281909 A JP-A-6-19182 JP 2003-167384 A

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. In other words, the present invention has excellent properties such as fluidity and charging characteristics when a fixing aid is introduced, enables both low-temperature fixing properties and heat-resistant storage stability, and provides high-quality images. It is an object of the present invention to provide a toner to be used and an image forming method using the toner.

Means for solving the problems are as follows. That is, <1> a toner including a toner material containing at least a resin, a colorant, and a fixing aid,
The fixing aid is a crystalline organic compound having a melting point of 50 to 150 ° C., and the endothermic amount of the melting peak derived from the fixing aid at the first temperature rise when the toner is subjected to DSC measurement is defined as Q1. The toner satisfies the following formula, 0 ≦ (Q2 / Q1) ≦ 0.30, where Q2 is the endothermic amount of the melting peak derived from the fixing assistant at the second temperature.
<2> The toner according to <1>, wherein the crystalline organic compound is an ester compound of a polyhydric alcohol.
<3> The toner according to any one of <1> to <2>, wherein the crystalline organic compound is a fatty acid having 16 to 24 carbon atoms.
<4> The toner according to any one of <1> to <3>, wherein the crystalline organic compound is an alcohol having 16 to 24 carbon atoms.
<5> The toner according to any one of <1> to <4>, wherein the crystalline organic compound is crystalline polyester.
<6> The toner according to any one of <1> to <5>, wherein the crystalline organic compound has a melting point of 60 to 100 ° C.
<7> The toner according to any one of <1> to <6>, wherein the content of the fixing aid in the toner is 5 to 30% by mass.
<8> The toner according to any one of <1> to <7>, wherein the toner contains a fixing assistant in a dispersed state, and the dispersion diameter of the fixing assistant is 10 nm to 3 μm.
<9> The toner according to any one of <1> to <8>, wherein the solubility of the fixing aid in an organic solvent at 40 ° C. or less is 1% by mass or less.
<10> When the DSC measurement of the toner including the resin is performed by setting the first peak of temperature rise of the resin as Tg1r and the second peak of temperature rise of the resin as Tg2r. In this case, the peak derived from the resin at the first temperature increase of the toner is Tg1t, and the peak derived from the resin at the second temperature increase of the toner is Tg2t, which satisfies the following formulas (1) and (2). The toner according to any one of <1> to <9>.
Tg2r> Tg2t (1)
Tg1t-Tg2t> Tg1r-Tg2r (2)
<11> The toner according to <10>, which satisfies Tg2r−Tg2t> 10 (° C.).
<12> The toner according to any one of <10> to <11>, wherein Tg1r−Tg1t <5 (° C.).
<13> The toner according to any one of <1> to <12>, wherein the toner material is granulated after the toner material is dissolved or dispersed in an aqueous medium to prepare an emulsion or dispersion. It is.
<14> The toner material includes at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound,
By granulating, by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to produce an adhesive base material, particles containing at least the adhesive base material are obtained. The toner according to <13>, which is performed.
<15> The toner according to any one of <13> to <14>, wherein a solution or dispersion of the toner material is prepared by dissolving or dispersing the toner material in an organic solvent.
<16> The toner according to any one of <1> to <15>, wherein the temperature during toner production is 20 to 60 ° C.

<17> A developer comprising the toner according to any one of <1> to <16>.
<18> A toner-containing container filled with the toner according to any one of <1> to <16>.
<19> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to <16> to be a visible image And a developing means for forming the process cartridge.
<20> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image according to <1> to <16> Developing means for developing a visible image by developing using any of the toners, Transfer means for transferring the visible image to a recording medium, Fixing means for fixing the transferred image transferred to the recording medium, The image forming apparatus is characterized by having at least.
<21> An image carrier, a toner supply unit that supplies the toner according to any one of <1> to <16> on the image carrier, and the toner brought into contact with the image carrier Visible image temporary fixing means for applying a heat corresponding to the image signal to form a visible image with the toner at the site to which the heat is applied, and temporarily fixing the visible image on the image carrier; An image forming apparatus comprising at least heat welding means for transferring and heat-welding the fixed visible image to a recording medium.
<22> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <1> to <16> An image comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is a forming method.
<23> A toner supply step of supplying the toner according to any one of <1> to <16> on the image carrier, and heat corresponding to an image signal for the toner brought into contact with the image carrier A visible image temporary fixing step of forming a visible image with the toner at the site to which the heat is applied, and temporarily fixing the visible image on the image carrier, and the temporarily fixed visible An image forming method comprising at least a heat welding step of transferring an image to a recording medium and heat-welding the image.

  The toner of the present invention comprises a toner material containing at least a resin, a colorant, and a fixing aid, and the fixing aid is a crystalline organic compound having a melting point of 50 to 150 ° C., and DSC measurement of the toner. When the endothermic amount of the melting peak derived from the fixing assistant at the first temperature increase at Q1 is Q1, and the endothermic amount of the melting peak derived from the fixing assistant at the second temperature increase is Q2, 0 ≦ Q2 / Q1 ≦ 0.30. As a result, bleeding of the fixing aid contained in the toner is suppressed during heating on the fixing roller, and adhesion of the fixing aid to the roller surface is prevented. Therefore, it is possible to prevent an increase in the tack force between the roller and the toner layer due to the fixing aid, and to sufficiently obtain the low-temperature fixability when the fixing aid is introduced. Toner having both the low-temperature fixability and the storage stability Can be provided.

  The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.

  The toner container of the present invention is filled with the toner of the present invention. Therefore, when an image is formed by electrophotography using the toner of the present invention filled in the toner-containing container, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge can be attached to and detached from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that a high-quality image with high image density and high sharpness can be formed even under low-temperature fixing conditions.

  One aspect of the image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the toner of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.

  Another aspect of the image forming apparatus of the present invention includes at least an image carrier, a toner supply unit, a visible image temporary fixing unit, and a heat welding unit. In the image forming apparatus, the toner supply unit supplies the toner of the present invention onto the image carrier. The visible image temporary fixing means applies heat according to an image signal to the toner brought into contact with the image carrier to form a visible image with the toner at a portion to which the heat is applied, A visible image is temporarily fixed on the image carrier. The thermal welding means transfers the temporarily fixed visible image to a recording medium and thermally welds it. As a result, it is not necessary to form an electrostatic latent image on the photoconductor, and a high-quality image with high image density and high sharpness can be formed at high speed.

  One aspect of the image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step. In the image forming apparatus, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.

  Another aspect of the image forming method of the present invention includes at least a toner supplying step, a visible image temporary fixing step, and a heat welding step. In the image forming method, the toner of the present invention is supplied onto the image carrier in the toner supply step. In the visible image temporary fixing step, heat corresponding to an image signal is applied to the toner brought into contact with the image carrier, and a visible image is formed by the toner of the portion to which the heat is applied, A visible image is temporarily fixed on the image carrier. In the thermal welding step, the temporarily fixed visible image is transferred to the recording medium and thermally welded. As a result, it is not necessary to form an electrostatic latent image on the photoconductor, and a high-quality image with high image density and high sharpness can be formed at high speed.

  According to the present invention, a toner that can solve various problems in the past, has good properties such as fluidity and charging properties, and has both excellent low-temperature fixability and heat-resistant storage stability, and can provide a high-quality image. In addition, it is possible to provide a developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method capable of improving image quality using the toner.

(toner)
The toner of the present invention contains at least a resin, a colorant, and a fixing aid, and a toner material containing a wax and, if necessary, other components.

<Fixing aid>
The fixing aid is a crystalline organic compound having a melting point of 50 to 150 ° C., and the melting point is preferably 60 to 100 ° C. When the melting point is less than 50 ° C., the fixing aid is likely to be melted and the heat-resistant storage stability may be inferior. For this reason, sufficient low-temperature fixability may not be obtained.

The fixing aid is preferably made compatible with the toner resin by heating and does not bleed out of the toner. When the fixing aid bleeds, the melted fixing aid adheres to the fixing surface, which increases the tack force between the toner layer and the fixing roller, and there is a possibility that sufficient low-temperature fixability cannot be obtained.
The fact that the fixing aid is compatible with the resin and does not bleed out of the toner means that the endothermic amount of the melting peak derived from the fixing aid at the first temperature rise when the DSC measurement of the toner is taken as Q1. This is realized by satisfying the following equation, 0 ≦ (Q2 / Q1) ≦ 0.30, where Q2 is the endothermic amount of the melting peak derived from the fixing assistant at the second temperature. When the fixing aid is excellent in compatibility with the resin, the endothermic amount of the melting peak derived from the fixing aid is reduced by the first heating of the temperature rise. Therefore, when the resin and the fixing assistant are easily compatible, the endothermic amount of the melting peak derived from the fixing assistant at the second temperature increase is smaller than that at the first temperature increase. Therefore, in order for the fixing aid to be sufficiently compatible with the resin and to prevent bleeding to the outside of the toner, it is necessary to satisfy 0 ≦ (Q2 / Q1) ≦ 0.30, and 0 ≦ (Q2 / Q1) ≦. It is preferable to satisfy 0.20. When the ratio (Q2 / Q1) exceeds 0.30, the compatibility between the plasticizer and the resin is insufficient during heating at the time of fixing, so that the plasticizer bleeds and adheres to the surface of the fixing roller. Therefore, since the tack force between the toner layer and the fixing roller is increased, the low-temperature fixing property may be inferior. When (Q2 / Q1) is 0 (zero), it means that the Q2 peak is not detected, and when no fixing aid is contained, both the Q1 and Q2 peaks are 0 (zero). Become.

―Measurement of melting peak endotherm of fixing aid―
The endothermic amount at the melting peak of the fixing assistant can be measured by the following method using, for example, a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation). Regarding the melting peak endotherm (hereinafter referred to as Q1) of the fixing aid at the first temperature increase, about 5.0 mg of resin or toner (sample) is first put in an aluminum sample container, and the sample container is placed in a holder unit. And set in an electric furnace. Next, the sample is heated from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere, and a DSC curve is measured with a differential scanning calorimeter (“DSC-60”, manufactured by Shimadzu Corporation). From the obtained DSC curve, using the analysis program in the DSC-60 system, the shoulder between the melting peaks of the fixing aid can be selected, and Q1 can be calculated.
With respect to the melting peak endotherm (hereinafter referred to as Q2) of the fixing aid at the second temperature increase, after the first temperature increase, the temperature is decreased from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min, and further In a nitrogen atmosphere, the sample is heated to 150 ° C. at a temperature rising rate of 10 ° C./min, and a DSC curve is measured with a differential scanning calorimeter (“DSC-60”, manufactured by Shimadzu Corporation). From the obtained DSC curve, using the analysis program in the DSC-60 system, the shoulder between the melting peak of the fixing aid can be selected, and Q2 can be calculated.

When the melting peak of the fixing aid overlaps with the melting peak of other materials (resin, wax, etc.), the same DSC measurement is performed on the other material alone and the fixing aid alone, and the melting peak derived from the fixing aid is obtained. Q1 and Q2 can be similarly calculated by identifying and subtracting melting peaks derived from other materials.
When the melting peak ratio (Q2 / Q1) of the first and second temperature increases calculated from the above is 0 or more and 0.30 or less, the fixing agent can be prevented from bleeding. Low temperature fixability can be obtained.

  The fixing aid is not particularly limited as long as it is an organic compound having a crystallinity of 50 to 150 ° C. (preferably 60 to 100 ° C.), and can be appropriately selected according to the purpose. Examples thereof include ester compounds of monohydric alcohols, long chain fatty acids, long chain alcohols, and crystalline polyesters.

-Ester compound of polyhydric alcohol-
As for the ester compound of the said polyhydric alcohol, what esterified the following alcohol components and a fatty-acid component is mentioned.
As the alcohol component, for example, it is preferable to use a monomer of a polyol such as ethylene glycol, propylene glycol, butylene glycol, tetramethylene glycol, or glycerin, or a product obtained by condensation polymerization of the polyol as necessary. When the condensation polymer is used as an alcohol component, the degree of polymerization is preferably 2 or more and less than 20. When the degree of polymerization is 20 or more, the crystallinity is lowered, so that the sharp melt property as a fixing aid is lost, and a sufficient low-temperature fixing effect may not be obtained.

As the fatty acid, it is preferable to use a simple substance having a carbon chain number of 12 to 24 or a mixture thereof. Specific examples include simple substances such as lauric acid, palmitic acid, stearic acid, arachidic acid, eicosanoic acid, behenic acid, lignoceric acid, and mixtures thereof. When the number of carbon chains is 16 or less, the crystallinity is lowered, so that the melting point of the compound itself is lowered, and sufficient heat-resistant storage stability may not be obtained. Further, the sharp melt property as a fixing aid is lost, and a sufficient low-temperature fixing effect may not be obtained.
The ester compound of the polyhydric alcohol can be obtained by appropriately selecting the fatty acid and the alcohol component according to the purpose and esterifying them. The degree of esterification of the ester compound of the polyhydric alcohol can be appropriately selected according to the purpose.

-Long chain fatty acids-
As the long chain fatty acid, those having 16 to 24 carbon chains are preferable. Specific examples thereof include simple substances such as palmitic acid, stearic acid, arachidic acid, eicosanoic acid, behenic acid, lignoceric acid, and mixtures thereof. When the number of carbon chains is 16 or less, the melting point is lowered and sufficient heat-resistant storage stability may not be obtained.

-Long chain alcohol-
As the long-chain alcohol, those having 16 to 24 carbon chains are preferable. Specific examples thereof include simple substances such as hexyl alcohol, stearyl alcohol, eicosanol, and behenyl alcohol, or a mixture thereof. When the number of carbon chains is 16 or less, the melting point is lowered and sufficient heat-resistant storage stability may not be obtained.

-Crystalline polyester resin-
The crystalline polyester resin comprises a polyvalent alcohol unit and a carboxylic acid _{unit, -OCOC-R-COO- (CH} 2) n - ( In the formula, R represents C2-20 straight-chain unsaturated An aliphatic group, and n represents an integer of 2 to 20) at least 60 mol% of all ester bonds in the entire resin. In the above formula, R preferably represents a linear unsaturated aliphatic divalent carboxylic acid residue, has 2 to 20 carbon atoms, and more preferably 2 to 4 linear unsaturated aliphatic. It is a group. n is an integer of 2-6.

  Specific examples of the linear unsaturated aliphatic group include linear unsaturated divalent carboxylic acids such as maleic acid, fumaric acid, 1,3-n-propene dicarboxylic acid, and 1,4-n-butene dicarboxylic acid. Mention may be made of linear unsaturated aliphatic groups derived from acids.

The (CH ₂ ) _n represents a linear aliphatic dihydric alcohol residue. Specific examples of the linear aliphatic dihydric alcohol residue in this case include linear aliphatic dihydric alcohols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Those derived from dihydric alcohols can be indicated. Since the crystalline polyester resin uses a linear unsaturated aliphatic dicarboxylic acid unit as a carboxylic acid unit, the crystalline polyester resin has an effect of easily forming a crystal structure as compared with the case of using an aromatic dicarboxylic acid unit. Show.

  The crystalline polyester resin is a polyvalent carboxylic acid comprising (1) a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (an acid anhydride, a lower alkyl ester acid halide having 1 to 4 carbon atoms, etc.). It can be produced by subjecting a unit and (2) a polyhydric alcohol unit comprising a linear aliphatic diol to a polycondensation reaction by a conventional method. In this case, the polyvalent carboxylic acid unit may contain a small amount of other polyvalent carboxylic acid units as necessary. In this case, the polyvalent carboxylic acid unit includes (1) an unsaturated aliphatic divalent carboxylic acid unit having a branched chain, (2) a saturated aliphatic divalent carboxylic acid, a saturated aliphatic trivalent carboxylic acid, etc. In addition to aliphatic polyvalent carboxylic acid units, (3) aromatic polyvalent carboxylic acid units such as aromatic divalent carboxylic acids and aromatic trivalent carboxylic acids are included. The content of these polyvalent carboxylic acid units is usually preferably 30 mol% or less, more preferably 10 mol% or less, based on the total carboxylic acid, and is suitably added within the range where the resulting polyester has crystallinity. The

  Specific examples of polyvalent carboxylic acid units that can be added as needed include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid Divalent carboxylic acid units such as: trimetic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid Trivalent or higher polyvalent carboxylic acid units such as acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid, etc. Can be mentioned.

If necessary, the polyhydric alcohol unit may contain a trivalent or higher polyhydric alcohol unit in addition to a small amount of an aliphatic branched dihydric alcohol unit or cyclic dihydric alcohol unit. The content thereof is preferably 30 mol% or less, more preferably 10 mol% or less, based on the total alcohol units, and is suitably added within the range in which the resulting polyester has crystallinity.
Examples of polyhydric alcohol units added as necessary include 1,4-bis (hydroxymethyl) cyclohexane units, polyethylene glycol units, bisphenol A ethylene oxide adduct units, bisphenol A propylene oxide adduct units, glycerin units, and the like. Is mentioned.

In the crystalline polyester resin, the molecular weight distribution is preferably sharp from the viewpoint of low-temperature fixability, and the molecular weight is preferably a relatively low molecular weight. The molecular weight of the crystalline polyester resin is such that its mass average molecular weight (Mw) is 5,500 to 6,500, and its number average molecular weight (Mn) is 1, in the molecular weight distribution by GPC of the o-dichlorobenzene soluble component. It is preferable that 300-1500 and (Mw / Mn) ratio are 2-5.
The molecular weight distribution of the crystalline polyester resin is based on a molecular weight distribution diagram in which the horizontal axis is log (M: molecular weight) and the vertical axis is mass%. In the case of the crystalline polyester resin used in the present invention, in this molecular weight distribution diagram, it is preferable to have a molecular weight peak in the range of 3.5 to 4.0% by mass, and the half width of the peak is 1.5 or less. It is preferable that

  The fixing aid is preferably contained in a dispersed state in the toner, and the dispersion diameter of the fixing aid is, for example, preferably 10 nm to 3 μm, more preferably 50 nm to 1 μm, in the maximum direction. . When the dispersion diameter is less than 10 nm, the heat-resistant storage stability may be inferior due to an increase in the contact surface area between the fixing aid and the resin. When the dispersion diameter exceeds 3 μm, The compatibility is not sufficiently performed and the low-temperature fixability may be inferior.

  The method for measuring the dispersion diameter of the fixing aid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the toner is embedded in an epoxy resin to form an ultrathin slice of about 100 μm, and tetraoxide After dyeing with ruthenium, it is observed with a transmission electron microscope (TEM) at a magnification of 10,000 times, photographed, and this photograph is evaluated to observe the dispersion state of the fixing aid, and the dispersion The diameter can be measured. When it is confirmed that the fixing aid dispersion is present in the toner particles, it can be determined that the fixing aid is not contained in the toner particles in a dispersed state.

As the solubility of the fixing aid, for example, the solubility in an organic solvent at 40 ° C. or lower is preferably 1% by mass or less, and more preferably 0.1% by mass or less. If the solubility exceeds 1% by mass, the resin and the fixing aid may be miscible during production in the toner production method described later. As the solubility of the fixing aid, for example, the solubility in an organic solvent at 60 ° C. or higher is preferably 5% by mass or more, and more preferably 20% by mass or more. When the solubility is less than 5% by mass, the fixing aid is not dissolved in the organic solvent by heating, and the dispersion state in the toner may be deteriorated. Here, the solubility of the fixing aid in the organic solvent can be determined by measuring the amount (g) of the fixing aid dissolved in 100 g of the organic solvent at each measurement temperature.
The organic solvent for determining the solubility of the fixing aid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like.

  The content of the fixing aid in the toner is 5 to 30% by mass in that both low-temperature fixability and heat-resistant storage stability can be achieved, and toner characteristics such as chargeability and resolution can be maintained at a high level. Is preferable, and 10 to 20% by mass is more preferable. When the content is less than 5% by mass, the low-temperature fixability may be inferior, and when it exceeds 30% by mass, the area of the fixing aid on the toner surface may increase and the fluidity may be inferior.

<Resin>
As the resin, when the DSC measurement is performed, the first peak of the temperature rise of the resin is Tg1r, the second peak of the temperature rise of the resin is Tg2r, and the DSC measurement of the toner containing the resin is performed. In this case, the peak derived from the resin at the first temperature rise of the toner is defined as Tg1t, and the peak derived from the resin at the second temperature increase of the toner is defined as Tg2t, the following expressions (1) and (2) are satisfied. Is preferred.
Tg2r> Tg2t (1)
Tg1t-Tg2t> Tg1r-Tg2r (2)

There is no restriction | limiting in particular as said resin as long as the said Formula (1) and Formula (2) are satisfy | filled, According to the objective, it can select suitably, For example, well-known binder resin is mentioned.
Formula (1) indicates that the glass transition temperature of the toner is lower than the glass transition temperature of the resin, and Formula (2) indicates that the glass transition temperature is decreased when the toner is heated. means.
The Tg2r is preferably larger than the Tg2t, and the difference (Tg2r−Tg2t) more preferably satisfies (Tg2r−Tg2t)> 10 (° C.). As the difference (Tg2r−Tg2t) is increased, the heat characteristic value of the resin is significantly decreased by heating at the time of fixing, and the lower limit temperature of fixing of the toner can be decreased, and the difference is less than 10 ° C. The low-temperature fixability may not be sufficient.
At this time, (Tg1r−Tg1t) more preferably satisfies (Tg1r−Tg1t) <5 (° C.). When the difference (Tg1r−Tg1t) is less than 5 (° C.), the glass resin temperature of the resin alone and the toner during storage are close to each other, and the heat resistant storage stability can be maintained at a higher level.

-Wax-
There is no restriction | limiting in particular as said wax, Although it can select suitably according to the objective, The low melting point wax whose melting | fusing point is 50-120 degreeC is preferable. The low melting point wax, when dispersed with the resin, effectively acts as a release agent between the fixing roller and the toner interface, thereby preventing oilless (no release agent such as oil is applied to the fixing roller). ) But the hot offset property is good.
Examples of the wax include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin, microcrystalline, and petrolatum. Natural waxes such as In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; poly-n-stearyl methacrylate, poly-n-lauryl which are low molecular weight crystalline polymer resins A homopolymer or copolymer of a polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, or the like may be used. These may be used alone or in combination of two or more.

  The melt viscosity of the wax is preferably 5 to 1,000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

-Glass transition temperature and melting point measurement-
As a measuring method of the glass transition temperature and melting point of the resin, the fixing aid, the wax, and the toner, for example, using a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation), It can be measured by the following method.
Regarding the glass transition temperature (Tg1r and Tg1t) of the resin and toner at the first temperature increase, first, about 5.0 mg of resin or toner (sample) is placed in an aluminum sample container, and the sample container is placed on a holder unit. Set in an electric furnace. Next, the sample is heated from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere, and a DSC curve is measured with a differential scanning calorimeter (“DSC-60”, manufactured by Shimadzu Corporation). The obtained DSC curve can be calculated from the intersection of the tangent line between the curve before the inflection point of the resin (or toner) and the curve after the inflection point using an analysis program in the DSC-60 system. At the same time, by reading the bottom value of the melting peak derived from the fixing aid and the wax using an analysis program in the DSC-60 system, the melting point (Tm) of the fixing aid can be obtained. When the melting point of the fixing aid overlaps with the peak of other substances (resin, wax, etc.) in the toner, the melting point of the fixing aid is determined by performing DSC measurement on the fixing aid alone. Can be sought.
Regarding the glass transition temperatures (Tg2r and Tg2t) of the resin and toner in the second temperature increase, after the first temperature increase, the resin is cooled from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min, and further in a nitrogen atmosphere. The sample is heated to 150 ° C. at a temperature rising rate of 10 ° C./min, and the DSC curve is measured with a differential scanning calorimeter (“DSC-60”, manufactured by Shimadzu Corporation). The obtained DSC curve can be calculated from the intersection of the tangent line between the curve before the inflection point of the resin (or toner) and the curve after the inflection point using an analysis program in the DSC-60 system.

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

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.
When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

-Other ingredients-
The other components are not particularly limited and can be appropriately selected depending on the purpose. Can be mentioned.

The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. Examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, and molybdate chelate pigments. , Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine activators, salicylic acid metal salts And metal salts of salicylic acid derivatives. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include bontron 03 of a nigrosine dye, bontron P-51 of a quaternary ammonium salt, and bontron S-34 of a metal-containing azo dye. , Oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302 TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (Above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Japan) Ritto Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonate group, a carboxyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.

  The content of the charge control agent in the toner varies depending on the type of the resin, the presence or absence of an additive, a dispersion method, and the like, and cannot be generally defined. For example, with respect to 100 parts by mass of the binder resin, 0.1-10 mass parts is preferable and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

The inorganic fine particles can be used as an external additive for imparting fluidity, developability, chargeability and the like to toner particles.
The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass.

The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having an alkyl fluoride group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

The toner of the present invention can be produced using a known method such as a suspension polymerization method, an emulsion polymerization method, or a dissolution suspension method. For example, the toner material is dissolved or dispersed in an aqueous medium. It can be obtained by granulating a toner after preparing an emulsified or dispersed liquid by dispersing.
As a preferred embodiment of the toner of the present invention, a solution or dispersion of a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is emulsified or dispersed in an aqueous medium. And a toner obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium to produce particles containing at least an adhesive substrate. .
Here, the temperature for producing the toner of the present invention is more preferably 20 to 60 ° C. When the production temperature exceeds 60 ° C., the resin and the fixing aid are compatible with each other by heating, and it may be impossible to achieve both low-temperature fixability and heat-resistant storage stability.

Hereinafter, a toner according to a preferred embodiment of the present invention will be described.
-Dissolution or dispersion of toner material-
The solution or dispersion of the toner material is obtained by dissolving or dispersing the toner material in a solvent. The toner material is not particularly limited as long as the toner can be formed, and can be appropriately selected according to the purpose. Examples thereof include an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. (Prepolymer) at least, the fixing aid, the colorant, preferably the wax, and, if necessary, the above-mentioned other such as unmodified polyester resin, mold release agent, charge control agent, etc. Comprising the ingredients.

The solution or dispersion of the toner material is preferably prepared by dissolving or dispersing the toner material in the organic solvent. The organic solvent is preferably removed during or after the toner granulation.
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, methyl isobutyl ketone, and the like, and ester solvents are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.
In the method for producing a toner according to the preferred embodiment of the present invention, the dissolution or dispersion of the toner material can be reacted with the active hydrogen group-containing compound and the active hydrogen group-containing compound in the organic solvent. A toner material such as a polymer, the fixing aid, the unmodified polyester resin, the wax, the colorant, and the charge control agent can be dissolved or dispersed in the toner material. Components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound may be added and mixed in the aqueous medium in the preparation of the aqueous medium described later, or the toner material may be dissolved or dissolved. When the dispersion is added to the aqueous medium, it may be added to the aqueous medium together with the dissolved or dispersed liquid.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) are preferred in that they can be increased in molecular weight by reactions such as elongation reaction and crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). is there.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, alcoholic hydroxyl groups are particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) or those blocked (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amine groups (B) The mixing equivalent ratio of amino group [NHx] ([NCO] / [NHx]) is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, and 1/1. It is particularly preferably 5 to 1.5 / 1.
If the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may decrease. If it exceeds 3/1, the molecular weight of the urea-modified polyester resin will be low. The hot offset resistance may be deteriorated.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. However, it can be appropriately selected from known resins, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And what made the said active hydrogen group containing polyester resin react with polyisocyanate (PIC), etc. are mentioned.

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol A mixture with (TO), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycols, alkylene ether glycols, alicyclic diols, alkylene oxide adducts of alicyclic diols, bisphenols, alkylene oxide adducts of bisphenols, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

As the trivalent or higher polyol (TO), those having 3 to 8 or higher valences are preferable. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the trivalent or higher polyphenols alkylene oxide adducts include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trivalent or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-100: 10 are preferable and 100: 0.01-100: 1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tri- or higher valent polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-100: 10 are preferable and 100: 0.01-100: 1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner. In some cases, the low-temperature fixability may deteriorate.

  There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like. Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate. These can be used alone or in combination of two or more.

As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing component are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and 4/1 to 1.2 / 1. Is more preferable, and 3/1 to 1.5 / 1 is particularly preferable.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Fixability may deteriorate.

As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  The mass average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 3,000 to 40,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 4,000 to 30,000 is more preferable. When the mass average molecular weight (Mw) is less than 3,000, the heat resistant storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.

The measurement of the molecular weight distribution by the gel permeation chromatography (GPC) can be performed, for example, as follows.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or Toyo Soda Kogyo Co., Ltd. having a molecular weight of ^{6 × 10 2, 2.1 × 10} 2, 4 × 10 2, 1.75 × 10 4, 1.1 × 10 5, 3.9 × 10 5, 8.6 It is preferable to use those of × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

-Aqueous medium-
The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.

  The aqueous medium can be prepared, for example, by dispersing resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.

The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. , Etc.
These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins is preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, styrene- (meth) acrylic acid ester resin, styrene-butadiene copolymer, (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used. The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). ", Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

-Emulsification or dispersion-
In the emulsification or dispersion of the toner material in the aqueous medium, it is preferable to disperse the toner material in the aqueous medium with stirring. The dispersion method is not particularly limited and can be appropriately selected depending on the purpose. For example, the dispersion method can be performed using a known disperser, and the disperser includes the low-speed shear disperser. And the high-speed shearing disperser.

  In the method for producing a toner according to the preferable aspect of the present invention, when the emulsification or dispersion is performed, the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction. An adhesive substrate (the resin) is generated.

-Adhesive substrate-
The adhesive base material exhibits adhesiveness to a recording medium such as paper, and is formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It may contain at least a polymer and may further contain a binder resin appropriately selected from known binder resins.

There is no restriction | limiting in particular as a mass mean molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 3,000 or more are preferable and 5,000-1,000,000 are more preferable. 7,000 to 500,000 are particularly preferred.
When the mass average molecular weight is less than 3,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as a glass transition temperature (Tg) of the said adhesive base material, Although it can select suitably according to the objective, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable. In the toner, since a polyester resin subjected to a crosslinking reaction and an extension reaction coexists, the toner exhibits good storage stability even when the glass transition temperature is lower than that of a conventional polyester toner.
When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.

  The glass transition temperature can be measured by the following method using, for example, a TG-DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, the glass transition temperature (Tg) can be calculated from the contact point between the tangent line and the base line of the endothermic curve near the glass transition temperature (Tg) using the analysis system in the TG-DSC system. .

Specific examples of the adhesive substrate are not particularly limited and may be appropriately selected depending on the intended purpose. Particularly preferred examples include polyester resins.
There is no restriction | limiting in particular as said polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are mentioned especially suitably.
The urea-modified polyester resin comprises an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond, and in this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable. When the urea bond is less than 10, the hot offset resistance may be deteriorated.

  Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophorone diamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, and (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol A polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene. Mixture of oxide 2 mol adduct and polycondensate of terephthalic acid, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A A polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid (9) Bisphenol A ethylene, a mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate and uread with hexamethylene diamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and toluene diisocyanate with urea diisocyanate with hexamethylenediamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

---- Binder resin ---
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, although a polyester resin etc. are mentioned, Unmodified polyester resin (unmodified polyester resin) is especially preferable.
When the unmodified polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of a polyol (PO) and a polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure that is compatible with each other. It is preferable in terms of resistance to hot offset.

The mass average molecular weight (Mw) of the unmodified polyester resin is preferably 1,000 to 30,000, preferably 1,500 to 15, in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). 1,000 is more preferable. When the mass average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Is preferably 8 to 28% by mass. On the other hand, when the mass average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the unmodified polyester resin is preferably 35 to 70 ° C. When the glass transition temperature is less than 35 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is usually 1.0 to 30.0 mgKOH / g, and preferably 5.0 to 20.0 mgKOH / g. Generally, it becomes easy to be negatively charged by giving the toner an acid value.
When the unmodified polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the unmodified polyester resin (PE) is 5/95. -25/75 is preferable, and 10 / 90-25 / 75 is more preferable.
When the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance may be deteriorated. .

  As content of the said unmodified polyester resin in the said binder resin, 50-100 mass% is preferable, for example, and 55-95 mass% is more preferable. When the content is less than 50% by mass, low-temperature fixability, fixed image strength, glossiness, and the like may be deteriorated.

  The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). A solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium together with the active hydrogen group-containing compound (for example, the amines (B)) to form the oil droplets, and both in the aqueous medium. (2) A solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance. It may be formed by forming droplets and subjecting both to extension reaction or crosslinking reaction in the aqueous medium, or (3) dissolving or dispersing the toner material in the aqueous medium After the addition and mixing in the system medium, the active hydrogen group-containing compound is added, the oil droplets are formed, and they are produced by subjecting both to an extension reaction or a crosslinking reaction from the particle interface in the aqueous medium. Good. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive base material by the emulsification or dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours.

  Examples of a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)) in the aqueous medium include, for example, the aqueous system. In a medium, a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, the release agent, the charge control agent, and the unmodified polyester resin And the like. A method in which a solution or dispersion of the toner material prepared by dissolving or dispersing the toner material in the organic solvent is added and dispersed by shearing force.

In the emulsification or dispersion, the amount of the aqueous medium used is preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner material.
When the amount used is less than 50 parts by mass, the toner material is in a poorly dispersed state, and toner particles having a predetermined particle size may not be obtained. When the amount exceeds 2,000 parts by mass, the production cost increases. Sometimes.

In the emulsification or dispersion, if necessary, it is preferable to use a dispersant from the viewpoint of stabilizing the oil droplets and sharpening the particle size distribution while obtaining a desired shape.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and the like. Among these, those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nippon Ink Chemical Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Neos) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); Unidyne DS-202 (manufactured by Daikin Industries Ltd.), MegaFuck F-150 F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products);

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In the preparation of the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water, or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

The organic solvent is removed from the emulsified slurry obtained by the emulsification or dispersion.
The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed into a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

The toner produced by the suspension polymerization method will be described below.
As described above, the toner produced by the suspension polymerization method is prepared by emulsifying or dispersing (suspending) the toner material in an aqueous medium after preparing the emulsion or dispersion (suspension). It can be obtained by granulating toner.

-Dissolution or dispersion of toner material-
In the suspension polymerization method, the toner material is dissolved or dispersed in a polymerizable monomer, an oil-soluble polymerization initiator, the fixing aid, the colorant, and, if necessary, the wax, Components such as the charge control agent and the crosslinking agent are dissolved or dispersed. In addition, for example, in order to reduce the viscosity of the polymer produced by the polymerization reaction described later, an organic solvent, a polymer, a dispersant, and the like may be added as appropriate.

--Polymerizable monomer--
Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, and the like; acrylamide, methacrylic acid, The surface of toner particles by partially using amide, diacetone acrylamide, and their methylol compounds, acrylates and methacrylates having amino groups such as vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate, etc. Functional groups can be introduced into the. In addition, by appropriately selecting a dispersant having an acid group or a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the surface of the toner particles to introduce a functional group.
Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; methyl acrylate, ethyl acrylate Acrylic acid such as n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. Esters: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenolic methacrylate , Dimethylaminoethyl methacrylate, methacrylic acid esters such as diethylaminoethyl methacrylate; and other acrylonitrile, methacrylonitrile, acrylamide, and the like.

  In addition to the polymerizable monomer, a resin may be used. For example, since the polymerizable monomer is soluble in water and cannot be emulsified by dissolution in an aqueous suspension, an amino group, a carboxylic acid group, a hydroxyl group, a sulfone group, a glycidyl group, a nitrile When a hydrophilic functional group-containing polymerizable monomer such as a group is to be introduced into the toner, a random copolymer of these with a vinyl compound such as styrene or ethylene, a block copolymer, a graft copolymer, etc. A resin in the form of a copolymer, a polycondensate such as polyester or polyamide, or a polyaddition polymer such as polyether or polyimine can be used.

Examples of the alcohol component and the acid component that form the polyester resin include the following.
Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, Examples include 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, and the like. Polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of novolac type phenol resins may be used.
Examples of the acid component include divalent carboxylic acids such as benzene dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; succinic acid, adipic acid, sebacic acid, azelaic acid, and the like. Alkyl dicarboxylic acid or anhydride thereof; succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or anhydride thereof Thing; etc. are mentioned. Further, polycarboxylic acids such as trimellitic acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid, benzophenonetetracarboxylic acid, and anhydrides thereof may be used.
As content of the said alcohol component and the said acid component in the said polyester resin, it is preferable that the said alcohol component is 45-55 mol%, and the said acid component is 55-45 mol%.

Two or more polyester resins may be used in combination as long as the physical properties of the obtained toner particles are not adversely affected. Moreover, physical properties can be adjusted, such as modification with silicone or a fluoroalkyl group-containing compound.
Here, when using a polymer having such a polar functional group, the average molecular weight of the polymer is preferably 5,000 or more.

Furthermore, in addition to the polymerizable monomer, the following resins can be used. Examples of the resin include homopolymers of styrene such as polystyrene and polyvinyltoluene, and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid. Methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer Polymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer Coalescence, styrene-vinylmethylke Copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc .; polymethyl methacrylate, polybutyl methacrylate , Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, Aromatic petroleum resin, and the like. These may be used individually by 1 type and may use 2 or more types together.
The addition amount of the resin is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the addition amount is less than 1 part by mass, the effect of adjusting the physical properties of the toner particles due to the addition may not be exhibited, and when it exceeds 20 parts by mass, the physical property design of the toner particles may be difficult. Further, a polymer having a molecular weight different from the molecular weight range of the toner obtained by polymerizing the polymerizable monomer can be dissolved in the polymerizable monomer and polymerized.

--Oil-soluble polymerization initiator--
The oil-soluble polymerization initiator has a half-life of 0.5 to 30 hours during the polymerization reaction, and is added in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Can give a polymer having a maximum between 10,000 and 100,000 in molecular weight, and can impart desirable strength and suitable dissolution characteristics to the toner.
The oil-soluble polymerization initiator is not particularly limited as long as it is oil-soluble, and can be appropriately selected according to the purpose. For example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyro Azo or diazo polymerization initiators such as nitriles; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butyl peroxide 2- And peroxide polymerization initiators such as ethyl hexanoate.

The crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. However, a compound having two or more polymerizable double bonds can be preferably used. For example, divinyl Aromatic divinyl compounds such as benzene and divinylnaphthalene; carboxylates having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline, divinyl ether, divinyl sulfide And divinyl compounds such as divinyl sulfone; and compounds having three or more vinyl groups. These may be used individually by 1 type and may use 2 or more types together.
As addition amount of the said crosslinking agent, 0.001-15 mass parts is preferable with respect to 100 mass parts of said polymerizable monomers, for example.

-Aqueous medium-
There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water is mentioned.
The aqueous medium preferably contains a dispersion stabilizer.
As the dispersion stabilizer, for example, known surfactants, organic dispersants, inorganic dispersants and the like can be used. Among these, harmful ultrafine particles are hardly generated, and dispersion stability is improved due to steric hindrance. Therefore, an inorganic dispersant is preferable in that it maintains a stable state even when the reaction temperature is changed, is easy to wash, and does not adversely affect the toner.
Examples of the inorganic dispersant include polyvalent metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; calcium metasuccinate, calcium sulfate and barium sulfate. And inorganic oxides such as inorganic salts, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite, and alumina.

The inorganic dispersant can be used as it is, but in order to obtain finer particles, the inorganic dispersant particles may be generated and used in the aqueous medium. For example, in the case of the calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed with high-speed stirring to produce water-insoluble calcium phosphate, which enables more uniform and fine dispersion. At this time, water-soluble sodium chloride salt is by-produced at the same time. However, when the water-soluble salt is present in the aqueous medium, dissolution of the polymerizable monomer in water is suppressed, and ultrafine toner by emulsion polymerization is used. Is preferable because it is difficult to generate. However, since it becomes an obstacle when the residual polymerizable monomer is removed at the end of the polymerization reaction, it is preferable to replace the aqueous medium or desalinate with an ion exchange resin. The inorganic dispersant can be almost completely removed by dissolution with an acid or alkali after completion of the polymerization.
The inorganic dispersant is preferably used alone in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the inorganic dispersant is used, ultrafine particles are hardly generated, but it is difficult to obtain a toner having a small particle diameter.
Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

-Suspension-
The suspension is performed by emulsifying or dispersing a solution or dispersion of the toner material in which the toner material is uniformly dissolved or dispersed in the aqueous medium. At this time, if a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser is used to disperse the toner particles to a desired size at once, a toner having a sharp particle size distribution can be obtained.
The oil-soluble polymerization initiator may be added simultaneously with the addition of other additives in the polymerizable monomer, or the solution or dispersion of the toner material is suspended in the aqueous medium. You may mix just before making. Further, during the granulation of the toner, the oil-soluble polymerization initiator dissolved in the polymerizable monomer or solvent may be added immediately after the granulation of the toner and before the start of the polymerization reaction.

-Granulation-
The granulation is performed by polymerizing the polymerizable monomer.
As temperature in the said polymerization reaction, it is 40 degreeC or more, for example, and is generally 50-90 degreeC. When the polymerization is performed within the temperature range, the release agent, the wax, and the like that should be present inside the toner particles are precipitated by phase separation, and can be encapsulated. In order to consume the remaining polymerizable monomer, the reaction temperature may be set to 90 to 150 ° C. As described above, when heated above the melting point of the fixing aid, the resin and the fixing aid are used. Therefore, it is necessary to carry out the reaction at a temperature not higher than the melting point of the fixing aid.
In the granulation, a seed polymerization method may be used in which the polymerizable monomer is further adsorbed on the obtained polymer particles and then polymerized using the oil-soluble polymerization initiator. At this time, a polar compound can be dissolved or dispersed in the polymerizable monomer to be adsorbed.

After completion of the polymerization reaction, it is preferable to perform stirring using a normal stirrer at a stirring speed that maintains the particle state and prevents the particles from floating and settling.
The polymerized particles after the completion of the polymerization reaction are filtered and washed by a known method to remove excess surfactant, dried, and further mixed with inorganic fine powder to adhere to the particle surface. Thus, toner particles are obtained. At this time, it is preferable to remove coarse powder and fine powder by performing classification.

In the toner of the present invention, an inorganic fine powder having a number average primary particle size of 4 to 80 nm is preferably added as a fluidizing agent.
Examples of the inorganic fine powder include silica, alumina, titanium oxide and the like.
Examples of the silica include, for example, a so-called dry process produced by vapor phase oxidation of silicon halide as a silica fine powder, a dry silica called fumed silica, a so-called wet silica manufactured from water glass, and the like. Is mentioned. Among these, dry silica is preferable because there are few silanol groups on the surface and inside the silica fine powder, and there are few production residues such as Na ₂ O and SO ₃ ^— . In dry silica, for example, by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds, composite fine powders of the silica and other metal oxides can be obtained. Composite fine powders can also be used.

Said inorganic fine powder in order to impart good fluidity to the toner, the specific surface area measured by the BET method by nitrogen adsorption, for example, preferably 20~350m ² / g, more preferably 25~300m ² / g .
The specific surface area can be calculated according to the BET method using a specific surface area measuring device ("Autosorb 1", manufactured by Yuasa Ionics Co., Ltd.) by adsorbing nitrogen gas on the sample surface and using the BET multipoint method.

As content of the said inorganic fine powder, 0.1-3.0 mass% is preferable with respect to a toner base particle, for example. When the addition amount is less than 0.1% by mass, the fluidity may be insufficient, and when it exceeds 3.0% by mass, the fixability may be deteriorated.
The content of the inorganic fine powder can be quantified using, for example, a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

The inorganic fine powder is preferably hydrophobized in that it can maintain excellent characteristics even in a high temperature and high humidity environment.
Examples of the treating agent in the hydrophobic treatment include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds. These may be used individually by 1 type and may use 2 or more types together.
As a method for the hydrophobization treatment, for example, a silylation reaction is performed as a first-stage reaction and silanol groups are eliminated by chemical bonds, and then a hydrophobic thin film is formed on the surface with silicone oil as a second-stage reaction. The method of hydrophobizing by this is mentioned.
As a viscosity at 25 degreeC of the said silicone oil, 10-200,000 mm < ² > / s is preferable, for example, and 3,000-80,000 mm < ² > / s is more preferable.
When the viscosity is less than 10 mm ² / s, the performance of powder the inorganic fine powder becomes unstable due to thermal and mechanical stresses, it may affect the image quality, when it exceeds 200,000 mm ² / s, uniform It may be difficult to perform a hydrophobic treatment.

Preferred examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil.
As a method of using the silicone oil, for example, silica treated with a silane compound and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or a method of spraying silicone oil on silica is used. Alternatively, a method may be used in which after dissolving or dispersing silicone oil in a suitable solvent, silica fine powder is added and mixed to remove the solvent. Among these, a method using a sprayer is preferable in that the formation of the aggregate of the inorganic fine powder is relatively small.
As a processing amount of the silicone oil, for example, 1 to 40 parts by mass is preferable and 3 to 35 parts by mass is more preferable with respect to 100 parts by mass of the silica.

  The toner of the present invention is not particularly limited with respect to various physical properties such as shape and size, and can be appropriately selected according to the purpose. However, the following volume average particle diameter (Dv), volume average It is preferable to have particle diameter (Dv) / number average particle diameter (Dn), penetration, low temperature fixability, offset non-occurrence temperature, and the like.

The volume average particle diameter (Dv) of the toner is preferably 3 to 8 μm, and more preferably 4 to 6 μm, for example.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When the thickness exceeds 8 μm, the resolution is high and high. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is, for example, preferably 1.30 or less, and more preferably 1.00-1.30.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is less than 1.00, with the two-component developer, the toner is fused to the surface of the carrier during long-term stirring in the developing device, The chargeability of the carrier may be reduced, and the cleaning property may be deteriorated. In the case of a one-component developer, the filming of the toner on the developing roller and the thinning of the toner are performed. Toner fusion may occur easily, and if it exceeds 1.30, it will be difficult to obtain a high-resolution and high-quality image, and toner particles in the developer balance will be generated. Variation in diameter may be large.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.00 to 1.30, the storage stability, low-temperature fixability, and hot offset resistance are all excellent. In particular, when used in a full-color copying machine, the glossiness of the image is excellent. With two-component developers, there is little fluctuation in the toner particle diameter in the developer even if the toner balance for a long period of time is achieved, and good and stable developability can be obtained even with long-term stirring in the developing device. Even if the balance of the toner is carried out with the agent, fluctuations in the particle diameter of the toner are reduced, and there is no filming of the toner on the developing roller and no fusion of the toner to the member to the blade for thinning the toner. Even in the long-term use (stirring) of the developing device, good and stable developability can be obtained, so that a high-quality image can be obtained.

  The volume average particle diameter and the ratio (Dv / Dn) between the volume average particle diameter and the number average particle diameter are measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can do.

As the penetration, for example, the penetration measured by a penetration test (JIS K2235-1991) is preferably 15 mm or more, and more preferably 20 to 30 mm.
When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated.
The penetration can be measured according to JIS K2235-1991. Specifically, a 50 ml glass container is filled with toner and left in a thermostatic bath at 50 ° C. for 20 hours. The penetration can be measured by cooling the toner to room temperature and performing a penetration test. In addition, it has shown that the said heat-resistant preservation | save property is excellent, so that the said penetration value is large.

As the low temperature fixability, from the viewpoint of achieving both a reduction in the fixing temperature and the occurrence of no offset, it is preferable that the lower limit temperature for fixing is lower, and more preferable that the temperature at which no offset is generated is higher. As a temperature range in which both can be achieved, the minimum fixing temperature is less than 150 ° C., and the non-offset temperature is 200 ° C. or more.
The minimum fixing temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the obtained fixed image is rubbed with a pad. The roll temperature is the lower limit fixing temperature.
The offset non-occurrence temperature is set by, for example, using an image forming apparatus, setting a transfer paper, and each color of solid images of red, blue, and green as single colors of yellow, magenta, cyan, and black, and solid colors of each color. It can be determined by adjusting so that it is developed, adjusting the temperature of the fixing belt to be variable, and measuring the temperature at which no offset occurs.

  The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.

  The toner of the present invention has good properties such as fluidity and fixability, and achieves both excellent low-temperature fixability, heat-resistant storage stability and releasability. Therefore, the toner of the present invention can be suitably used in various fields, and can be more suitably used for image formation by electrophotography. The following toner-containing container, developer, and process of the present invention are described below. It can be particularly suitably used for a cartridge, an image forming apparatus, and an image forming method.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components appropriately selected such as the carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and image can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and high magnetization materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The core material has a volume average particle diameter of preferably 10 to 150 μm, more preferably 40 to 100 μm.
When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like, if necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method to use, the method using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.

Since the developer of the present invention contains the toner, it has excellent properties such as fluidity and fixability, and has both excellent low-temperature fixability, heat-resistant storage stability and releasability, and high image quality. A stable image can be formed stably.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention is formed by filling the container of the toner of the present invention or the developer.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably.
The size, shape, structure, material, etc. of the container body containing toner is not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. A spiral unevenness is formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and a part or all of the spiral part has a bellows function, etc. Is particularly preferred.
The material of the container body containing toner is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferable. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polychlorinated resin Preferred examples include vinyl resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. A developing means for forming the image forming apparatus, and further having other means such as a charging means, an exposure means, a developing means, a transfer means, a cleaning means, and a static elimination means, which are appropriately selected as necessary. .
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably provided detachably in the image forming apparatus of the present invention described later.

Here, for example, as shown in FIG. 1, the process cartridge includes a photosensitive member 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and other members as necessary. It has. In FIG. 1, reference numeral 103 denotes exposure by an exposure unit, and a light source capable of writing with high resolution is used. Reference numeral 105 denotes a recording medium.
As the photoreceptor 101, the same one as an image forming apparatus described later can be used. An arbitrary charging member is used for the charging means 102.
Next, an image forming process using the process cartridge shown in FIG. 1 will be described. The photosensitive member 101 is exposed to the surface by charging by the charging unit 102 and exposure 103 by the exposure unit (not shown) while rotating in the direction of the arrow. An electrostatic latent image corresponding to the image is formed. The electrostatic latent image is developed with toner by the developing unit 104, and the toner development is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the photoconductor after the image transfer is cleaned by the cleaning unit 107 and further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, preferably including a cleaning step, and further other steps appropriately selected as necessary. For example, it includes a static elimination process, a recycling process, a control process, and the like.
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and preferably includes a cleaning unit. In addition, other means appropriately selected as necessary, for example, static elimination means, recycling means, control means and the like are provided.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

<Electrostatic latent image forming step and electrostatic latent image forming means>
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon or the like is preferable in terms of long life.

  The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Development process and development means>
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

<Transfer process and transfer means>
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

<Fixing process and fixing means>
The fixing step is a step of fixing the visible image transferred to the recording medium using the fixing unit, and may be performed each time the toner of each color is transferred to the recording medium, or may be applied to the toner of each color. On the other hand, it may be carried out simultaneously at the same time in a state of being laminated.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose, but a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as sequencers and computers.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter also referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and the exposure. An exposure device 30 as a means, a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. A tandem image forming apparatus 100 shown in FIG. 4 is a tandem color image forming apparatus. The tandem image forming apparatus 100 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 4. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus 100, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image-corresponding image (L in FIG. 5), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image of each color toner, and the toner image is transferred to the intermediate transfer member 5. The image forming apparatus includes a transfer charger 62 for transferring the image on the surface, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta image) based on image information of each color. And cyan images) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotated by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 145, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

As the image forming method and the image forming apparatus of the present invention, those adopting the adhesive transfer method shown below can also be suitably used.
When the adhesive transfer method is employed, the toner of the present invention needs to contain at least a heat-sensitive adhesive. The heat-sensitive adhesive contains a fixing aid and a thermoplastic resin as essential components, and includes a tackifier as necessary.
The heat-sensitive adhesive does not exhibit any adhesiveness at room temperature, but develops adhesiveness by heating and external load, and maintains adhesiveness for a while after removing the heat source. First, the fixing aid is melted, and the thermoplastic resin and the tackifier are melted to develop tackiness. That is, the adhesiveness is caused by causing the fixing aid to melt and melt with the thermoplastic resin to plasticize the thermoplastic resin.

The image forming method of the present invention using the adhesive transfer method includes at least a toner supplying step, a visible image temporary fixing step, and a heat welding step, and further other steps appropriately selected as necessary, for example, toner removal Including processes.
The adhesive transfer type image forming apparatus of the present invention comprises at least an image carrier, a toner supply unit, a visible image temporary fixing unit, and a heat welding unit, and further appropriately selected as necessary. It has other means, for example, toner removing means.

  The image forming method of the present invention using the adhesive transfer method can be preferably implemented by the image forming apparatus of the present invention using the adhesive transfer method, and the toner supplying step can be performed by the toner supplying means. The visual image temporary fixing step can be performed by the visible image temporary fixing unit, the thermal welding step can be performed by the thermal welding unit, and the other steps can be performed by the other unit.

<Toner supply step and toner supply means>
The toner supply step is a step of supplying the toner of the present invention onto the image carrier. The image carrier is not particularly limited with respect to the material, shape, structure, size, etc., and can be appropriately selected from known ones. The shape is preferably an endless film. Examples of the material include light transmissive resins, and polycarbonate is preferable.

The toner supply means is not particularly limited and may be appropriately selected from known ones. For example, the toner supply unit and a container for storing the toner and the toner carrying unit are transported to the opposing portion of the image carrier. A toner supply device having at least a toner carrier, a replenishment member for replenishing the toner carrier with the toner in the container, and a layer thickness regulating member for equalizing the thickness of the toner on the toner carrier. Preferably mentioned.
The toner may be supplied by applying an electrostatic adhesive force to the toner of the present invention to replenish the toner carrier, or by applying a non-electrostatic adhesive force such as a magnetic force. The carrier may be replenished.

<Visible image temporary fixing step and visible image temporary fixing means>
In the visible image temporary fixing step, heat corresponding to an image signal is applied to the toner abutted on the image carrier to form a visible image with the toner at a portion to which the heat is applied, In this step, the visible image is temporarily fixed on the image carrier.
The visible image temporary fixing means preferably has at least viscosity imparting means for imparting viscosity to the toner.
As the viscosity imparting means, for example, a laser beam scanning device having at least a laser light source, a collimator lens, a polygon mirror, an fθ lens, and a reflecting mirror is preferably exemplified. The laser beam scanning device can apply heat according to an image signal to the toner imagewise with a laser beam. A thermal head can be used instead of the laser beam.
Viscosity can be selectively imparted to the toner present at a position corresponding to the image portion on the toner carrier by the heat from the laser beam in the viscosity imparting means. A viscous visible image is formed, and the visible image is temporarily fixed on the image carrier.
Here, the provision of the viscosity includes not only the case where the material that originally has no viscosity is made viscous, but also the case where the viscosity of the material that was originally viscous is further increased.
The adhesion force of the temporarily fixed visible image to the image carrier is weaker than the adhesion force due to electrostatic force between the toner and the toner carrier, and the residual toner on the image carrier in the toner removal step described later. Is of a size that can be easily removed.

<Thermal welding process and thermal welding means>
The thermal welding process is a process in which the temporarily fixed visible image is transferred to a recording medium and thermally welded, and can be suitably performed by a thermal welding means.
The heat welding means is not particularly limited and may be appropriately selected according to the purpose. However, it is preferable to simultaneously transfer and fix the visible image onto the recording medium, for example, a heating roller is preferable. It is mentioned in.

The toner removing step is a step of removing toner existing in a part other than the visible image on the image carrier, and can be suitably performed by a toner removing unit.
The toner removing means is not particularly limited, and may be appropriately selected from known cleaners as long as the toner remaining on the image bearing member can be removed. For example, a magnetic roller cleaner, A blade cleaner or the like is preferably used.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention adopting the adhesive transfer method will be described with reference to FIG. An image forming apparatus 500 shown in FIG. 6 includes an image carrier 510, a toner supply device 520 as the toner supply unit, a laser beam scanning device 530 as the viscosity applying unit in the visible image temporary fixing unit, A toner removing roller 540 as a toner removing unit and a heating roller 550 as the heat welding unit are provided.

  The image carrier 510 is an endless film, and is formed of polycarbonate as a light-transmitting resin film that transmits light in a predetermined wavelength range, and its thickness is 0.02 to 0.2 mm. The image carrier 510 is designed to be movable in the direction of the arrow a when one of a roller 511 and a roller 512 that are arranged inside and stretches the image carrier 510 is rotated by driving means such as a motor. A cleaning device 514 having a cleaning roller 513 that is in contact with the roller 512 via the image carrier 510 is disposed in the vicinity of the roller 512. A blade 515 is disposed in contact with the cleaning roller 513.

The toner supply device 520 includes a case 521 that accommodates the toner T, a toner carrying roller 522 that carries the toner T to a portion facing the image carrier 510, and the toner T in the case 521 to the toner carrying roller 522. A replenishing roller 523 for replenishing and a blade 524 for uniformizing the layer thickness of the toner T carried on the toner carrying roller 522 are provided in the vicinity of the image carrier 510. The toner carrying roller 522 and the replenishing roller 523 are each designed to be rotatable in the arrow direction.
In addition, a toner removing roller 540 with the leading edge of the cleaning blade 541 in contact with the toner supply device 520 is disposed.

The laser beam scanning device 530 includes a laser light source and a collimator lens (not shown), a polygon mirror 531, an fθ lens 532, and a strip-shaped reflecting mirror 534 having substantially the same length as the width of the image carrier 510. On the back side of the image carrier 510, the toner carrier roller 522 is disposed at a position where the toner T is supplied. The laser beam scanning device 530 applies heat corresponding to the image signal to the toner T on the toner carrying roller 522 via the image carrier 510 in an image-like manner. In this example, the laser beam is irradiated from the back side of the image carrier 510. However, a laser beam scanning device 530 is disposed outside the image carrier 510, and the toner is directly passed through the image carrier 510. Thermal energy may be applied by irradiating T with laser light.
The heating roller 550 is disposed so as to face and separate from the roller 511 via the image carrier 510, and when the recording medium S is sent between the heating roller 550 and the roller 511 by the registration roller pair 551, The roller 511 is in pressure contact with the image carrier 510.

In the image forming apparatus 500 employing the adhesive transfer method shown in FIG. 6, in the toner supply device 520, the toner T in the case 521 is replenished to the toner carrying roller 522 by the replenishing roller 523 and the toner carried on the toner carrying roller 522. The layer thickness of T is made uniform by the blade 524, and an appropriate amount of toner is guided to the opposing portion between the image carrier 510 and the toner carrier roller 522. At this time, the toner carrying roller 522 and the replenishing roller 523 are brought into contact with each other with a speed difference at the opposing portion so that the toner is frictionally charged (for example, negatively charged), and the toner carrying roller 522 is supplied to the replenishing roller 523. By applying a voltage having a positive potential to the toner T, an electrostatic adhesion force is applied to the toner T, and the toner T having the electrostatic adhesion force is supplied to the toner carrying roller 522.
Next, in the laser beam scanning device 530, heat corresponding to the image signal is irradiated imagewise to the toner T on the toner carrying roller 522 via the image carrier 510 by the laser beam. The toner T becomes viscous due to the thermal energy of the laser light applied to the toner T, and is temporarily fixed as a visible image on the surface of the image carrier 510. Further, after the visible image G is temporarily fixed on the image carrier 510, the toner (residual toner) existing in the portion (non-image portion) other than the visible image G on the image carrier 510 has a positive voltage. The toner is removed by the electrostatic attraction force of the applied toner removing roller 540. The toner removal roller 540 is provided for the purpose of removing toner when toner other than the toner that is originally temporarily fixed adheres to the non-image portion on the image carrier 510 and so-called scumming occurs. The suction force of the toner removing roller 540 is weaker than the temporary fixing force of the toner T to the image carrier 510. Further, when the amount of toner adhering to the non-image portion is small, the toner removing roller 540 may not be provided.

  On the downstream side of the facing portion between the image carrier 510 and the toner removing roller 540, the visible image G is transferred and fixed to the recording medium S by heat welding by the heating roller 550. Here, the recording medium S is fed from a sheet feeding device (not shown), sent to the heating roller 550 in accordance with the visible image forming area on the image carrier 510 by the registration roller pair 551, and heated from the back side. As a result, the visible image G is transferred and fixed. Note that the image carrier 510 after the transfer and fixing of the visible image is cleaned by the cleaning roller 513, and dust containing toner on the cleaning roller 513 is scraped off by the blade 515.

  In the image forming apparatus and the image forming method of the present invention, the toner of the present invention is used which has excellent properties such as fluidity and fixability and can achieve both excellent low-temperature fixability, heat-resistant storage stability and releasability. Therefore, high image quality can be obtained efficiently.

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

( Reference Example 1)
<Adhesive substrate production process>
A toner was produced as follows.
-Dissolution of toner material or preparation of dispersion-
--- Synthesis of unmodified polyester (low molecular weight polyester)-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, and dibutyltin 2 parts by mass of oxide was added and allowed to react at 230 ° C. for 8 hours under normal pressure. Next, the reaction solution was reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize an unmodified polyester.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,100, a mass average molecular weight (Mw) of 5,600, and a glass transition temperature (Tg) of 58 ° C.

-Preparation of master batch (MB)-
1000 parts by weight of water, 540 parts by weight of carbon black (“Printex35”, manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5) and 1200 parts by weight of the unmodified polyester were combined with a Henschel mixer (Mitsui Mine). Mixed). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

--- Preparation of fixing aid dispersion--
As a fixing aid, 200 parts by mass of B-DSP-60 (Matsumoto Yushi Seiyaku Co., Ltd., ethylene glycol stearic acid diester, melting point = 62 ° C.), 400 parts by mass of a polyester resin, and 800 parts by mass of ethyl acetate were mixed. “Ultra Viscomill” (manufactured by Imex) was used for 3 times under the condition that the feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / s, and 80% by volume of 0.5 mm zirconia beads were filled. Dispersion was performed to prepare a fixing aid dispersion.
In addition, it was 0 mass% when the solubility of B-DSP-60 (Matsumoto Yushi Seiyaku make, ethylene glycol stearic acid diester) as a fixing adjuvant with respect to ethyl acetate in 40 degreeC was measured.

--Synthesis of prepolymer--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,600, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.60% by mass, and the solid content concentration of the prepolymer (after standing at 150 ° C. for 45 minutes) was 50% by mass.

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

  In a beaker, 15 parts by mass of the prepolymer, 60 parts by mass of the unmodified polyester, 130 parts by mass of ethyl acetate, and 100 parts by mass of the fixing aid dispersion were stirred and dissolved. Next, 10 parts by mass of an organopolysiloxane-modified polyethylene wax (melting point = 72 ° C.) as a wax and 10 parts by mass of the masterbatch were charged, and a liquid feeding speed was obtained using a bead mill (“Ultra Visco Mill”; manufactured by Imex Corporation). A raw material solution is prepared by three passes under conditions of 1 kg / hr, disk peripheral speed 6 m / s, and 80% by volume of 0.5 mm zirconia beads, and 2.7 parts by mass of the ketimine is added and dissolved. A material dissolution or dispersion was prepared.

-Preparation of aqueous medium phase-
An aqueous medium phase was prepared by mixing and stirring 306 parts by mass of ion-exchanged water, 265 parts by mass of a 10% by mass tricalcium phosphate suspension, and 0.2 parts by mass of sodium dodecylbenzenesulfonate, and dissolving them uniformly.

-Preparation of emulsion or dispersion-
150 parts by mass of the aqueous medium phase is placed in a container, and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The mixture was added and mixed for 10 minutes to prepare an emulsified dispersion (emulsified slurry).

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

-Cleaning and drying-
After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at a rotational speed of 12,000 rpm), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. To the obtained filter cake, 20 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. Furthermore, 20 mass parts of 10 mass% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes) and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh of 75 μm to obtain toner base particles of Reference Example 1.

  The obtained toner base particles are embedded in an epoxy resin, cut into ultra-thin sections of about 100 μm, stained with ruthenium tetroxide, and then observed with a transmission electron microscope (TEM) at a magnification of 10,000 times for photography. Then, by evaluating the image of this photograph, the dispersion state of the fixing aid was observed, and the dispersion diameter was measured and found to be 0.3 μm.

( Reference Example 2)
In Reference Example 1, the same procedure as in Reference Example 1, except that the ethylene glycol stearic acid diester used in the preparation of the fixing aid dispersion was changed to 200 parts by mass of hexaglycerin stearic acid diester (melting point = 62 ° C.) The toner base particles of Reference Example 2 were produced.
The solubility of hexaglycerin stearic acid diester as a fixing aid in ethyl acetate at 40 ° C. was measured and found to be 1% by mass.
When the dispersion diameter of the fixing aid in the obtained toner base particles was measured in the same manner as in Reference Example 1, it was 0.4 μm.

( Reference Example 3)
In Reference Example 1, the same procedure as in Reference Example 1 except that the ethylene glycol stearic acid diester used in the preparation of the fixing aid dispersion was changed to 100 parts by mass of a mixture of stearic acid and behenic acid (melting point = 70 ° C.). Thus, toner base particles of Reference Example 3 were produced.
When the solubility of a mixture of stearic acid and behenic acid as a fixing aid in ethyl acetate at 40 ° C. was measured, it was 1% by mass.
When the dispersion diameter of the fixing aid in the obtained toner base particles was measured in the same manner as in Reference Example 1, it was 0.3 μm.

( Reference Example 4)
Reference Example 1, ethylene glycol monostearate diester used in the preparation of the fixing aid dispersion, was replaced by 200 parts by weight of glycerin distearate (mp = 66 ° C.), the same procedure as Reference Example 1, Reference The toner base particles of Example 4 were produced.
The solubility of glyceryl distearate as a fixing aid in ethyl acetate at 40 ° C. was measured and found to be 0% by mass.
When the dispersion diameter of the fixing aid in the obtained toner base particles was measured in the same manner as in Reference Example 1, it was 0.4 μm.

(Example 5)
In Reference Example 1, the ethylene glycol stearic acid diester used in the preparation of the fixing aid dispersion was composed of 90% fumaric acid, 5% succinic acid, 5% trimellitic anhydride (all in molar ratio), and alcohol. The same procedure as in Reference Example 1 was carried out except that 200 parts by mass of crystalline polyester (melting point: 120 ° C., mass average molecular weight (Mw) = 6,000) synthesized with 100% 1,4-butanediol as the component was used. The toner base particles of Example 5 were produced.
The solubility of the crystalline polyester as a fixing aid in ethyl acetate at 40 ° C. was measured and found to be 0% by mass.
When the dispersion diameter of the fixing aid in the obtained toner base particles was measured in the same manner as in Reference Example 1, it was 1.2 μm.

(Comparative Example 1)
Reference Example 1, except excluding the fixing aid dispersion, in the same manner as in Reference Example 1 to produce the toner base particles of Comparative Example 1.

(Comparative Example 2)
In Reference Example 1, the same procedure as in Reference Example 1 except that the stearic acid polyglycerin ester used in the preparation of the fixing aid dispersion was changed to 200 parts by mass of tetraglycerin behenic acid tetraester (melting point = 62 ° C.). Thus, toner base particles of Comparative Example 2 were produced.
The solubility of tetraglycerin behenic acid tetraester as a fixing aid for ethyl acetate at 40 ° C. was 0% by mass.
When the dispersion diameter of the fixing aid in the obtained toner base particles was measured in the same manner as in Reference Example 1, it was 0.4 μm.

(Comparative Example 3)
Comparative Example 3 was performed in the same manner as in Reference Example 1 except that the ethylene glycol stearic acid diester used in the preparation of the fixing aid dispersion in Example 1 was replaced with 400 parts by weight of behenic acid (melting point = 78 ° C.). Toner base particles were produced.
The solubility of behenic acid as a fixing aid in the organic solvent ethyl acetate at 40 ° C. was measured and found to be 0.3% by mass.
When the dispersion diameter of the fixing aid in the obtained toner base particles was measured in the same manner as in Reference Example 1, it was 0.2 μm.

(Comparative Example 4)
Reference Example 1, ethylene glycol monostearate diester used in the preparation of the fixing aid dispersion, was replaced by 200 parts by weight of diphenyl phthalate (melting point = 77 ° C.), the same procedure as in Reference Example 1, Comparative Example 4 toner base particles were produced.
The solubility of diphenyl phthalate as a fixing aid in ethyl acetate at 40 ° C. was 20% by mass.
When the dispersion diameter of the fixing aid in the obtained toner base particles was measured in the same manner as in Reference Example 1, it was not possible to confirm a dispersion that was discriminated as diphenyl phthalate.

-External additive treatment-
Hydrophobic silica as an external additive (“H2000”, manufactured by Clariant Japan) 1.0 mass with respect to 100 mass parts of the obtained toner base particles of Reference Examples 1 to 4, Example 5 and Comparative Examples 1 to 4 Using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), the mixture was mixed for 30 seconds at a peripheral speed of 30 m / s and suspended for 1 minute, and sieved with a mesh opening of 35 μm, Reference Examples 1 to 4, Example 5 and Each toner of Comparative Examples 1 to 4 was produced.

-Fabrication of carrier-
Next, a carrier was produced as follows.
To 100 parts by mass of toluene, 100 parts by mass of a silicone resin (“organostraight silicone”, 5 parts by mass of r- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black were added, and the mixture was mixed with a homomixer for 20 minutes. A magnetic layer was prepared by coating the surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 50 μm using a fluidized bed coating apparatus.

<Thermal properties of toner by DSC method>
Regarding the obtained toners of Reference Examples 1 to 4, Example 5 and Comparative Examples 1 to 4, the thermal characteristics, that is, Q2 / Q1, (Tg2r-Tg2t), {(Tg1t-Tg2t)-(Tg1r-Tg2r) }, (Tg1r-Tg1t), and the melting point (Tp) of the fixing aid were measured. The results are shown in Table 1.
The thermal characteristics were measured by the following method using a DSC system (differential scanning calorimeter) (“DSC-60”, manufactured by Shimadzu Corporation).
Regarding the glass transition temperature (Tg1r and Tg1t) of the resin and toner at the first temperature rise, first, about 5.0 mg of resin or toner (sample) is placed in an aluminum sample container, and the sample container is placed on a holder unit. Set in an electric furnace. Subsequently, it heated from 20 degreeC to 150 degreeC by the temperature increase rate of 10 degree-C / min in nitrogen atmosphere, and the DSC curve was measured with the differential scanning calorimeter ("DSC-60", Shimadzu Corporation make). From the obtained DSC curve, it calculated from the intersection of the tangent of the curve before the inflection point of the resin (or toner) and the curve after the inflection point using the analysis program in the DSC-60 system. At the same time, the melting point (Tp) of the fixing assistant and the endothermic amount Q1 of the melting peak derived from the fixing assistant were determined from the peak value derived from the fixing assistant.
Regarding the glass transition temperature (Tg2r and Tg2t) of the resin and toner in the second temperature increase and the endothermic amount Q2 of the melting peak derived from the fixing assistant, the temperature decrease rate from 150 ° C. to 10 ° C. / It cooled to 0 degreeC by min, and also heated to 150 degreeC by the temperature increase rate of 10 degreeC / min in nitrogen atmosphere, and measured the DSC curve with the differential scanning calorimeter ("DSC-60", Shimadzu Corporation make). . From the obtained DSC curve, it calculated from the intersection of the tangent of the curve before the inflection point of the resin (or toner) and the curve after the inflection point using the analysis program in the DSC-60 system. At the same time, the endothermic amount Q2 of the melting peak of the fixing assistant was determined from the melting peak derived from the fixing assistant.

-Production of developer-
Next, 5 parts by mass of each of the toners of Reference Examples 1 to 4, Example 5 and Comparative Examples 1 to 4 that had been subjected to external additive treatment and 95 parts by mass of the carrier were mixed with a ball mill, and Reference Examples 1 to 4 and Example 1 were carried out. Each two-component developer of Example 5 and Comparative Examples 1 to 4 was produced.

  Using the obtained developers, the minimum fixing temperature, the heat resistant storage stability, the hot offset property, and the cold offset property were evaluated as follows. The results are shown in Table 2.

<Fixing temperature limit>
A device that has been tuned so that the temperature and linear velocity can be adjusted by removing the silicone oil coating mechanism from the fixing unit of the tandem color electrophotographic device ("Imagio Neo C350", manufactured by Ricoh Co., Ltd.) and remodeling it to an oilless fixing method. Then, the minimum fixing temperature was evaluated using plain paper (“TYPE 6000 <70W>Y”; manufactured by Ricoh Co., Ltd.). The tandem color electrophotographic apparatus can continuously print 35 sheets of A4 size paper per minute. At this time, the linear velocity of the fixing roller was set to 125 mm / s, and the evaluation was performed by changing the roller temperature.
The fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a dedicated cloth pad becomes 70% or more was defined as the minimum fixing temperature, and evaluation was performed based on the following criteria.
〔Evaluation criteria〕
◎: Less than 110 ° C ○: Less than 120 ° C 110 ° C or more △: Less than 140 ° C 120 ° C or more ×: 140 ° C or more

<Hot offset generation temperature>
For image formation, the temperature and linear velocity can be adjusted by removing the silicone oil application mechanism from the fixing unit of the tandem color electrophotographic device (“Imagio Neo C350”, manufactured by Ricoh Co., Ltd.) and remodeling it to an oilless fixing method. Using the tandem-type color electrophotographic apparatus, a single solid color image of yellow, magenta, cyan, and black on each plain paper is 0.85 ± 0.3 mg / cm ² . The toner was adjusted so as to be developed. The obtained image was fixed by changing the temperature of the heating roller, and the fixing temperature at which hot offset occurs (offset generation temperature) was measured and evaluated based on the following criteria.
〔Evaluation criteria〕
◎: 210 ° C or more ○: Less than 210 ° C 190 ° C or more △: Less than 190 ° C 170 ° C or more ×: Less than 170 ° C

<Cold offset property>
Using the tandem color electrophotographic apparatus (“Imagio Neo C350”, manufactured by Ricoh Co., Ltd.), the presence or absence of cold offset on the fixed image was visually evaluated. The fixing roll temperature at which cold offset occurred was defined as the cold offset generation temperature, and evaluation was performed according to the following criteria.
〔Evaluation criteria〕
◎: Less than 110 ° C ○: 110 ° C or more and less than 120 ° C △: 120 ° C or more and less than 140 ° C ×: 140 ° C or more

<Heat resistant storage stability (Penetration)>
Each toner was filled in a 50 ml glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K2235-1991) and evaluated based on the following criteria. In addition, it shows that heat resistance preservability is excellent, so that the said penetration value is large, and when it is less than 5 mm, possibility that a problem in use will generate | occur | produce is high.
〔Evaluation criteria〕
◎: Needle penetration 25 mm or more ○: Needle penetration 15 mm or more and less than 25 mm △: Needle penetration 5 mm or more and less than 15 mm ×: Needle penetration less than 5 mm

  The toner of the present invention has favorable properties such as fluidity and fixability, and can satisfy both excellent low-temperature fixability and heat-resistant storage stability, and therefore is suitably used for high-quality image formation. The developer, toner-containing container, process cartridge, image forming apparatus and image forming method of the present invention using the toner of the present invention are suitably used for high-quality image formation.

FIG. 1 is a schematic configuration diagram showing an example of a process cartridge of the present invention. FIG. 2 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 4 is a schematic explanatory view showing an example of carrying out the image forming method of the present invention by the image forming apparatus (tandem color image forming apparatus) of the present invention. FIG. 5 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG. FIG. 6 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus (adhesive transfer method) of the present invention.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 photoconductor cleaning device 64 discharger 70 discharger lamp 80 transfer roller 90 cleaning device 95 transfer paper 100 image forming device 101 photoconductor 102 charging means 103 exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 14 Feeding path 147 transport rollers 148 feed path 150 copier main body 200 feeder table 300 Scanner 400 automatic document feeder (ADF)
500 Image forming device (adhesive transfer method)
510 Image carrier 520 Toner supply device 530 Laser beam scanning device 540 Toner removal roller 550 Heating roller

Claims (9)

A toner comprising a toner material containing at least a resin, a colorant, and a fixing aid,
The resin contains a polyester resin;
The fixing assistant is a crystalline polyester having a melting point of 50 to 150 ° C., and the endothermic amount of the melting peak derived from the fixing assistant at the first temperature rise when the DSC measurement of the toner is performed is Q1, and the temperature rise When the amount of heat absorbed melting peak derived from the fixing aid in the second time and Q2, the following equation, to satisfy 0 ≦ (Q2 / Q1) ≦ 0.30,
The minimum fixing temperature is less than 120 ° C.,
A toner having a penetration of 15 mm or more .
However, the DSC measurement is performed by putting 5.0 mg of the toner in an aluminum sample container. The first temperature increase condition is a temperature increase condition for heating from 20 ° C. to 150 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. The temperature raising conditions for the second temperature increase are as follows: after the first temperature increase, after cooling from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min, in a nitrogen atmosphere, at a temperature increase rate of 10 ° C./min. This is a temperature raising condition for heating to 150 ° C. The endothermic amount of the melting peak is calculated by selecting between the shoulders of the melting peak of the fixing aid from the measured DSC curve using an analysis program.
However, the minimum fixing temperature is an oilless fixing type electrophotographic apparatus, the fixing roller linear velocity is 125 mm / s, and the fixed image on plain paper obtained by changing the roller temperature is rubbed with a cloth pad. This is the fixing roll temperature at which the residual ratio of the subsequent image density is 70% or more.
However, the penetration is measured by the following method. The toner is filled in a 50 ml glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner after being left for 24 hours is cooled to 24 ° C., and the penetration is measured by a penetration test (JIS K2235-1991). The toner according to claim 1, further comprising a synthetic hydrocarbon wax. The toner according to claim 1, wherein the content of the fixing aid in the toner is 5 to 30% by mass. The toner according to claim 1, comprising a fixing assistant in a dispersed state, wherein the fixing assistant has a dispersion diameter of 10 nm to 3 μm.
However, the dispersion diameter is embedded in an epoxy resin, and is made into an ultrathin section of 100 μm, dyed with ruthenium tetroxide, and observed with a transmission electron microscope (TEM) at a magnification of 10,000 times. The particle size in the maximum direction when the dispersion state of the fixing aid is observed by photographing and evaluating the photograph. The toner according to claim 1, wherein the solubility of the fixing aid in an organic solvent at 40 ° C. is 1% by mass or less.
However, the solubility is the solubility obtained by measuring the amount of the fixing aid dissolved in 100 g of ethyl acetate. When the DSC measurement of the resin is performed, the first Tg of the temperature rise of the resin is Tg1r, the Tg of the second temperature rise of the resin is Tg2r, and the DSC measurement of the toner containing the resin is performed. The following formulas (1) and (2) are satisfied, where Tg derived from the resin at the first temperature increase of the toner is Tg1t and Tg derived from the resin at the second temperature increase of the toner is Tg2t. The toner according to any one of 5.
Tg2r> Tg2t ... (1)
Tg1t-Tg2t> Tg1r-Tg2r ... (2)
However, the DSC measurement of the resin and the toner is performed by putting 5.0 mg of the resin or the toner in an aluminum sample container. The first temperature increase condition is a temperature increase condition for heating from 20 ° C. to 150 ° C. at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. The temperature raising conditions for the second temperature increase are as follows: after the first temperature increase, after cooling from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min, in a nitrogen atmosphere, at a temperature increase rate of 10 ° C./min. This is a temperature raising condition for heating to 150 ° C. The Tg is calculated from the intersection of tangents between the curve before the inflection point and the curve after the inflection point using the analysis program from the measured DSC curve. The toner according to claim 6, wherein Tg1r−Tg1t <5 (° C.) is satisfied. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with the toner according to any one of claims 1 to 7 to form a visible image An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium. A toner supplying step for supplying the toner according to any one of claims 1 to 7 onto the image carrier, and applying heat according to an image signal to the toner in contact with the image carrier, A visible image is temporarily formed on the image carrier, and the temporarily fixed visible image is transferred to a recording medium. And an image forming method characterized by comprising at least a heat welding step of heat welding.

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