JP6424730B2 - Toner and developer - Google Patents

Description

  The present invention relates to toners and developers used to develop electrostatic charge images in electrophotography, electrostatic recording, electrostatic printing and the like.

  The toner used in electrophotography, electrostatic recording, electrostatic printing and the like is temporarily attached, for example, to an image carrier such as an electrostatic latent image carrier on which an electrostatic charge image is formed in a developing process. Next, after being transferred from the electrostatic latent image carrier to a transfer medium such as transfer paper in the transfer step, the sheet is fixed on the sheet in the fixing step. As a fixing method, a method of fixing by contact heating and melting using a heated roll, a belt or the like is generally performed because of its good thermal efficiency. However, in the contact heating and fixing method, there is a problem that the occurrence of the offset in which the toner is fused to the heat roll or the belt is likely to occur.

In order to prevent this offset property, there is a method of adding a release agent such as wax to the toner itself.
In the contact heating and fixing method, these release agents melt quickly when the toner passes through the heated roll and belt member, and are exposed on the surface of the toner particles to fuse the toner to the fixing member. Restraint. Not only the offset (cold offset) on the side where the fixing temperature is low but also the offset (hot offset) on the side where the fixing temperature is high are affected.

  When a release agent is disposed in the vicinity of the toner surface as a means for promoting the exposure from the toner, although the offset is suppressed, for example, while being stirred in the developing machine, the release agent is used as a base point Fusing tends to occur, and the toner adheres to the carrier and the photosensitive member in the form of being crushed and the charge amount of the toner tends to be reduced. That is, the releasing agent is present so as to be protected inside the toner at the time of stirring and storage, and at the time of fixing, the releasing agent is effectively exposed on the surface in a short time passing through the fixing member to release the toner from the fixing member It is necessary to express sex.

  Many proposals which specified the dispersed particle diameter of wax which is a mold release agent are reported to this subject (refer to patent documents 1 and 2). These are effective in preventing the offset while maintaining the toner granulation property by defining the dispersed particle size. However, when the wax is usually introduced into the toner in a dispersed form, it must be finer than the particle size of the toner, and it is very difficult to hold the fine wax without being exposed near the surface. is there.

Further, in order to develop the anti-offset property, it is more effective to exist as a relatively large block rather than localizing the releasing agent as fine domains in the toner. However, if the addition amount is increased more than necessary in order to enlarge the domain, the strength of the entire toner decreases and it is easily crushed, and the charge reduction and the soiling are apt to be deteriorated.
In particular, when a toner containing a releasing agent is used for nonmagnetic one-component development, when passing through a blade that regulates the thickness of the toner layer, the blade portion is crushed and fixed because an excessive load is applied thereto, It has been found that the image quality is significantly degraded, and durability more than two-component development is required of the toner.

  The toner described in the above-mentioned Patent Document 2 which specified the aspect ratio and size of the releasing agent in the toner exhibits good offset resistance although the low-temperature fixability, the background stain, and the chargeability are improved. From the viewpoint of improving particle strength and exhibiting good toner chargeability and toner durability, it is not sufficient.

  Further, a toner manufactured by discharging a toner composition liquid from a discharge hole and forming it into droplets, which is excellent in hot offset resistance and dirt on the background, has been proposed (see Patent Document 3). However, according to the description of Patent Document 3, the state of the releasing agent in the toner particles is not defined, and the toner manufactured according to the manufacturing method of Patent Document 3 exists near the outermost surface of the toner. The presence ratio of the release agent is extremely low, and accordingly, it is difficult to secure the releasability in a wide temperature range. Further, in the present manufacturing method, the release agent is once dissolved in the solvent, and then phase separation from the binder resin in the drying process results in a structure in which the release agent domain is dispersed inside the toner. In fact, there are sites where phase separation becomes insufficient, and toner breakage and deformation are likely to occur due to agitation stress in the developing device at the time of printing.

  With regard to the problem of toner adhesion and deformation, according to the descriptions of Patent Documents 4 and 5, it is also reported that the problem can be achieved by defining the hardness of toner particles. However, when conventional polymerized toners or pulverized toners such as these are used, the amount of release agent added must be increased, and the amount of release agent in the vicinity of the surface is increased. It is easy to cause a transfer failure or the like due to the decrease in the amount of charge due to the fixation of the release agent component onto the toner and the aggregation.

  As described above, in order to be able to suppress the cohesion associated with wax spent while securing the releasability in a wide temperature range, and to suppress the deformation, fracture, and sticking to the development stress, further improvement is required. Is the current situation.

  An object of the present invention is to solve the above-mentioned problems in the prior art and to achieve the following objects. That is, the present invention can suppress aggregation due to wax spent while securing releasability in a wide temperature range, and suppress deformation, fracture, and adhesion to developing stress, and toner chargeability, toner durability, and resistance to toner. An object of the present invention is to provide a toner and a developer capable of achieving both offset properties and showing good results in a well-balanced manner in all of these items.

  The toner according to the present invention for solving the above-mentioned problems comprises (i) at least a binder resin and a releasing agent, and (ii) the above-mentioned detected from a transmission electron microscope (TEM) photograph of a fractured surface of the toner. The ratio of the releasing agent area Wsa within 0.3 μm from the surface layer to the total area Wta of the releasing agent, Wsa / Wta is 2 to 5%, and (iii) 1 of the toner diameter d from the surface of the toner The number average particle diameter of the release agent present in the depth region Aa up to 4/4 (1/4 d) is WDa, and the number average particle diameter of the release agent present in the region Ab inside of Aa is WDb, The relationship between WDa and WDb when tested is that WDa <WDb, and (iv) the displacement amount at 250 .mu.N application in the micro compression test is 700 nm or less.

  According to the present invention, the above-mentioned various problems in the prior art can be solved and the above object can be achieved, and cohesion associated with wax spent can be suppressed while securing releasability in a wide temperature range, deformation against development stress It is possible to suppress crushing and fixing, achieve both toner chargeability, toner durability, and offset resistance, and show good results in a well-balanced manner in all of these items.

FIG. 2 is a cross-sectional view of a representative toner according to the present invention. (A) is an image obtained by binarizing the image of FIG. 1, (b) is an image in which the depth is defined to a depth of 0.3 μm from the outermost surface of the toner in FIG. 1, (c) is (b) The image obtained by binarizing the image of b), (d) is an image defining the toner diameter d of the image of FIG. 1 and the area Ab inside the depth area Aa from the toner outermost surface to 1⁄4 d and Aa. It is. It is a graph which shows an example of the distribution which plotted the number particle size and frequency (number) of the toner based on this invention. FIG. 6 is a cross-sectional view showing the configuration of liquid column resonance droplet forming means. It is the schematic of particle | grain manufacturing apparatus.

  The toner according to the present invention includes (i) at least a binder resin and a release agent, and (ii) a total area Wta of the release agent detected from a transmission electron microscope (TEM) photograph of a fractured surface of the toner. The ratio of the releasing agent area Wsa within 0.3 μm from the surface layer, Wsa / Wta is 2 to 5%, and (iii) 1/4 (1/4 d) of the diameter d of the toner from the surface of the toner When the number average particle diameter of the release agent present in the depth region Aa up to the depth region Aa is WDa, and the number average particle diameter of the release agent present in the region Ab inside Aa is WDb, The relationship is such that WDa <WDb, and (iv) the displacement at the time of 250 μN application in the micro compression test is 700 nm or less.

Next, the toner according to the present invention and the method for producing the same will be described in more detail.
The embodiment described below is a preferred embodiment of the present invention, and therefore, various technically preferable limitations are added. However, the scope of the present invention is to limit the present invention in the following description. It is not limited to these aspects unless stated otherwise.

〔toner〕
The toner of the present invention contains (i) at least a binder resin and a releasing agent, and (ii) the total area Wta of the releasing agent detected from a transmission electron microscope (TEM) photograph of a fractured surface of the toner. In contrast, the ratio of the releasing agent area Wsa within 0.3 μm from the surface layer, Wsa / Wta is 2 to 5%, and (iii) from the surface of the toner to 1⁄4 (1⁄4 d) of the diameter d of the toner The relationship between WDa and WDb, where WDa is the number average particle diameter of the mold release agent present in the depth region Aa and WDb is the number average particle diameter of the mold release agent present in the region Ab inside Aa. However, it is characterized in that WDa <WDb and (iv) displacement amount at 250 μN application in the micro compression test is 700 nm or less.
The toner according to the present invention having a predetermined pressing displacement amount, which satisfies the above requirements and has a release agent of a desired size disposed in a desired area in the toner, has a configuration capable of solving the above-mentioned problems.

<Binder resin>
The binder resin is not particularly limited as long as it dissolves in the organic solvent used in the production method described later, and can be appropriately selected from known resins according to the purpose. For example, homopolymers of vinyl monomers such as styrene monomers, acrylic monomers and methacrylic monomers, copolymers of two or more of these monomers, polyester resins, polyol resins, phenol resins And silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, coumarone indene resins, polycarbonate resins, petroleum resins and the like. These may be used alone or in combination of two or more.

(Vinyl monomer)
There is no restriction | limiting in particular as said styrene monomer, According to the objective, it can select suitably. For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-amylstyrene, p-tert-butylstyrene P-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4 -Styrene such as dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or a derivative thereof.

There is no restriction | limiting in particular as said acrylic monomer, According to the objective, it can select suitably. For example, (meth) acrylic acid and esters of (meth) acrylic acid can be mentioned.
There is no restriction | limiting in particular as ester of the said acrylic acid, According to the objective, it can select suitably, For example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic Examples thereof include n-octyl acid, n-dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate and the like.

There is no restriction | limiting in particular as said methacrylic monomer, According to the objective, it can select suitably, For example, ester of methacrylic acid, methacrylic acid, etc. are mentioned.
There is no restriction | limiting in particular as ester of the said methacrylic acid, According to the objective, it can select suitably, For example, methyl methacrylate, an ethyl methacrylate, a propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacryl Examples include n-octyl acid, n-dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like.

There is no restriction | limiting in particular as an example of the homopolymer of the said vinyl monomer, or the other monomer which forms a copolymer, According to the objective, it can select suitably. For example, the following (1) to (18) may be mentioned.
(1) Monoolefins such as ethylene, propylene, butylene and isobutylene (2) Polyenes such as butadiene and isoprene (3) Vinyl chlorides such as vinyl chloride, vinyl chloride, vinyl bromide and vinyl fluoride (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether (6) Vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone and the like Vinyl ketones (7) N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinyl indole, N-vinyl pyrrolidone and the like (8) vinyl naphthalenes (9) acrylic acid such as acrylonitrile, methacrylonitrile, acrylamide and the like Or Tachylic acid derivatives etc. (10) Unsaturated dibasic acid (11) maleic anhydride such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid, etc., citraconic acid anhydride, itaconic acid anhydride, Unsaturated dibasic acid anhydrides such as alkenyl succinic acid anhydride (12) Maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, citraconic acid monobutyl ester Monoesters of unsaturated dibasic acids such as itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester and mesaconic acid monomethyl ester (13) unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid 14) Α, β-unsaturated acids such as tonic acid, cinnamic acid (15) crotonic anhydride, α, β-unsaturated acid anhydrides such as cinnamic anhydride (16) the α, β-unsaturated acids and lower Monomers having a carboxyl group such as anhydrides with fatty acids, alkenyl malonic acids, alkenyl glutaric acids, alkenyl adipic acids, acid anhydrides thereof and monoesters thereof (17) 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, Acrylic or methacrylic acid hydroxyalkyl esters such as 2-hydroxypropyl methacrylate (18) 4- (1-hydroxy-1-methylbutyl) styrene, hydroxy group such as 4- (1-hydroxy-1-methylhexyl) styrene Among these, styrene-based copolymers, styrene-acrylic copolymers, etc. A combination of such monomers is preferred.

The copolymer of the binder resin may have a crosslinked structure crosslinked by a crosslinking agent having two or more vinyl groups.
There is no restriction | limiting in particular as said crosslinking agent, According to the objective, it can select suitably, For example, aromatic divinyl compounds, such as divinylbenzene and divinyl naphthalene; Ethylene glycol diacrylate, 1,3- butylene glycol diacrylate, Connect with alkyl chains such as 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of these compounds replaced with methacrylate Diacrylate compounds; diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 Acrylate, dipropylene glycol diacrylate, and diacrylate compounds connected with an alkyl chain containing an ether bond, such as those of acrylates of these compounds is replaced with methacrylate and the like.

In addition, diacrylate compounds and dimethacrylate compounds which are linked by a chain containing an aromatic group and an ether bond are also included.
Moreover, as said crosslinking agent, polyester type diacrylates, such as brand name MANDA (made by Nippon Kayaku Co., Ltd.), are mentioned, for example.
In addition, as the cross-linking agent, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetra acrylate, oligo ester acrylate and acrylates of the above compounds replaced with methacrylate, triallyl cyanurate And polyfunctional crosslinking agents such as triallyl trimellitate.

Among these crosslinking agents, an aromatic divinyl compound (especially divinyl benzene), a diacrylate compound linked by a linked chain containing one aromatic group and one ether bond from the viewpoint of fixing ability and offset resistance in resin for toner Are preferred.
When the binder resin is a styrene-acrylic resin, at least one peak in the range of a molecular weight of 30,000 to 50,000 (number-average molecular weight conversion) in the molecular weight distribution by GPC of the soluble component in tetrahydrofuran (THF) of the resin component Should be present.

(Polyester resin)
There is no restriction | limiting in particular as a monomer which comprises the said polyester resin (polyester type polymer), Although it can select suitably according to the objective, It is preferable to consist of an alcohol component and an acid component.

Examples of the alcohol component include the following.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-Hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ether such as ethylene oxide and propylene oxide with bisphenol A It can be mentioned.

  The polyester resin can be crosslinked by using a polyhydric alcohol having a valence of 3 or more or an acid having a valence of 3 or more in combination, but it is necessary to use the amount within the range that does not prevent the resin from dissolving in the organic solvent. .

  Examples of the trivalent or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, for example, dipentaerythritol, tripentaerythritol, 1,2, 4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-triol Hydroxybenzene etc. are mentioned.

  Examples of the acid component forming the polyester-based polymer include benzenedicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof, and alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid. Or their anhydrides, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides such as

  Moreover, as a trivalent or more polyvalent carboxylic acid component, for example, trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid Acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra Examples include (methylene carboxy) methane, 1,2,7,8-octane tetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

In the present invention, an embodiment in which the binder resin contains a polyester resin as a main component is preferable. In particular, in the case where the release agent described later is an ester wax containing a fatty acid ester as a main component, it is more preferable to use a binder resin as a polyester resin and combine them.
When the binder resin is a polyester resin, at least one peak is present in the region of a molecular weight of from 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component, the fixability of the toner, offset resistance It is preferable in terms of sex. In addition, a binder resin having 70% to 100% of a component having a molecular weight of 100,000 or less that is a THF soluble component is preferable from the viewpoint of dischargeability. Furthermore, a binder resin having at least one peak in the region of a molecular weight of 5,000 to 20,000 is more preferable.

  In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.

When the said binder resin is a polyester resin, there is no restriction | limiting in particular as the acid value, Although it can select suitably according to the objective, 0.1 mgKOH / g-100 mgKOH / g are preferable, and 0.1 mgKOH / g 70 mg KOH / g is more preferable, and 0.1 mg KOH / g to 50 mg KOH / g is more preferable.
In the present invention, the basic operation of the acid value of the binder resin component of the toner composition is determined according to JIS K-0070 by the following method.

(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are previously used. I ask for it. 0.5 to 2.0 g of the pulverized product of the sample is precisely weighed, and the weight of the polymer component is Wg. For example, in the case of measuring the acid value of the binder resin from the toner, the acid value and the content of the coloring agent or the magnetic material are separately measured, and the acid value of the binder resin is determined by calculation.
(2) The sample is put into a 300 mL beaker, and 150 mL of a mixed solution of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a 0.1 mol / L potassium hydroxide (KOH) ethanol solution using a potentiometric titrator.
(4) The amount of KOH solution used at this time is S (mL), the blank is measured at the same time, and the amount of KOH solution used at this time is B (mL), and it calculates with the following formula. Where f is a factor of KOH.
Acid value (mg KOH / g) = [(S-B) x f x 5.61] / W

The glass transition temperature (Tg) of the binder resin and the toner composition containing the binder resin is not particularly limited and may be appropriately selected according to the purpose, but from the viewpoint of toner storage stability, 35 ° C. -80 degreeC is preferable and 40 degreeC-70 degreeC are more preferable.
When the glass transition temperature (Tg) is lower than 35 ° C., the toner may be easily deteriorated in a high temperature atmosphere. When the glass transition temperature (Tg) exceeds 80 ° C., the fixability may be lowered.

  The binder resin may be selected from those more suitable depending on the organic solvent and release agent to be used, but when a release agent having excellent solubility in the organic solvent is used, the softening point of the toner is lowered. There is a case. In such a case, increasing the weight average molecular weight of the binder resin to increase the softening point of the binder resin is an effective means for maintaining good hot offset properties.

<Release agent>
The release agent is not particularly limited as long as it is soluble in the organic solvent, and can be appropriately selected from known release agents according to the purpose, and waxes are preferable.
Examples of the mold release agent include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax and sasol wax; and aliphatic hydrocarbon waxes such as oxidized polyethylene wax Oxides or block copolymers thereof; plant-based waxes such as candelilla wax, carnauba wax, wax wax, jojoba wax; animal-based waxes such as beeswax, lanolin, spermaceti; and mineral-based compounds such as ozokerite, ceresin, Peterolatam Waxes: Waxes based on fatty acid esters such as montanic acid ester wax and castor wax; Various synthetic ester waxes, synthetic amide waxes and the like.

  Other examples of the above-mentioned mold release agent include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid and other linear alkyl carboxylic acids having a linear alkyl group; prudinic acid, eleostearic acid, valinarin Unsaturated fatty acids such as acids; stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnapyl alcohol, ceryl alcohol, mesyl alcohol and other saturated alcohols such as long-chain alkyl alcohols; polyhydric alcohols such as sorbitol; linoleic acid amide, Fatty acid amides such as olefin acid amide and lauric acid amide; Saturated fatty acid bisamides such as methylene bis capric acid amide, ethylene bis lauric acid amide and hexamethylene bis stearic acid amide; ethylene bis oleic acid amide and hexamethylene bis oley Unsaturated fatty acid amides such as acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl cepaic acid amide; m-xylene bis-stearic acid amide, N, N-distearyl isophthalic acid amide etc. Aromatic bisamides; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; Partial ester compounds of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oil and the like.

In the present invention, it is preferable to use an ester wax or an amide wax in which the releasing agent contains a fatty acid ester as a main component. In particular, in the case where the release agent is an ester wax containing a fatty acid ester as a main component, it is more preferable to use a binder resin as a polyester resin and combine them.
In addition, those waxes whose molecular weight distribution has been sharpened using press sweating method, solvent method, recrystallization method, vacuum distillation method, supercritical gas extraction method or solution crystallization method, low molecular weight solid fatty acid, low A molecular weight solid alcohol, a low molecular weight solid compound, or one from which other impurities have been removed is also preferably used as the above-mentioned release agent.

  The solubility of the releasing agent is preferably 70 g or more, more preferably 200 g or more, per 100 g of ethyl acetate at 45 ° C., in order to balance the fixing property, the offset resistance, and the fixation resistance. When the solubility is 70 g / (100 g ethyl acetate) or more, it becomes easy to bring the releasing agent domain into the toner as described in claim 1, and it has fixing property and offset resistance. While, the effect of sticking resistance is sufficiently expressed.

  The solubility of the release agent in the present invention can be determined, for example, as shown below. The mold release agent is finely crushed using an agate mortar. Subsequently, ethyl acetate corresponding to 25% by mass with respect to the weight of the release agent is heated to 70 ° C., and the hexane extract is charged with stirring, and stirred for 30 minutes while maintaining 70 ° C. After 30 minutes, it is cooled to 45 ° C. in a stirred state, and when it reaches 45 ° C., the stirring is stopped and left still for 1 hour while maintaining the temperature. At this time, a predetermined amount of the supernatant liquid is weighed, and then the solvent is removed by drying under reduced pressure at 150 ° C. for 1 hour, and the dry matter is weighed to calculate the concentration of the remaining solid content. From the concentration thus obtained, the solubility of the above-mentioned releasing agent corresponding to 100 g of ethyl acetate can be determined. In this measurement method, the maximum solubility is 400 g when the entire releasing agent is dissolved in ethyl acetate, but in this case, the ratio of the above-mentioned ethyl acetate to be added is further lowered from 25% by mass to 45 ° C. Adjust the solubility to an extent that precipitation occurs at a point in time.

  The melting point of the releasing agent is preferably 60 ° C. or less, more preferably 50 ° C. to 60 ° C., in order to balance the fixing property and the offset resistance. When the melting point is 50 ° C. or more, the blocking resistance does not decrease, and when the melting point is 60 ° C. or less, the anti-offset effect is sufficiently exhibited.

In the present invention, the temperature of the peak top of the maximum peak of the endothermic peak of the wax measured in differential scanning calorimetry (DSC) is taken as the melting point of the release agent.
As a DSC measurement device for measuring the melting point of the releasing agent and the toner, a high-precision, internally-heated input-compensated differential scanning calorimeter is preferable. As a measuring method, it carries out according to ASTM D3418-82. The DSC curve used in the present invention uses the one which is measured when the temperature is raised at a temperature rate of 10 ° C./min after the temperature rise and fall once to obtain the previous history.

  In the present invention, in order to obtain a toner in which a release agent having a desired size is disposed in a desired area in the toner, it is important to consider the type and content of the release agent.

(Content of mold release agent)
The content of the releasing agent is 4% by mass to 10% by mass with respect to the toner, as a value obtained by mass-converting the amount of heat absorption of the releasing agent determined by DSC (differential scanning calorimeter) method.
The amount of the releasing agent determined by the FTIR-ATR (total reflection absorption infrared spectroscopy) method of the toner is 0.05% by mass to 0.1% by mass.

  Since the release agent present in the vicinity of the surface of the toner is located at a position where the release agent is likely to see out to the toner surface, the toner satisfying the above-mentioned specification effectively exhibits toner releasability. Therefore, the range of the amount of the releasing agent present in the vicinity of the toner surface determined by the FTIR-ATR method is preferably 0.05% by mass to 0.1% by mass. When the amount of the release agent on the surface is 0.05% by mass or more, the amount of the release agent in the vicinity of the surface of the toner particle is not too small, and accordingly sufficient releasability can be obtained at the time of fixing. it can. Further, when the amount of the surface release agent is 0.1% by mass or less, the amount of the release agent in the vicinity of the surface of the toner particle does not become too large, and is not exposed to the outermost surface of the toner particle. The adhesion caused by the release agent is not increased, and the filming resistance of the developer is not deteriorated. As described above, the toner satisfying the above-described range can achieve both the anti-offset property at the time of fixing, the chargeability, the developability, the filming resistance, and the like.

The total amount of the releasing agent determined by the DSC method is preferably 4% by mass to 10% by mass in the toner particles. When the total amount of the release agent is 4% by mass or more, the amount of the release agent contained in the toner particles is not too small, and sufficient releasability can be obtained at the time of fixing, and the offset resistance It does not reduce sex. Further, it is preferable that the total amount of the release agent is 10% by mass or less, because the filming resistance is not reduced, and the gloss after fixing is not lost in a color image.
The measurement of the content of the release agent by the DSC (differential scanning calorimeter) method and the FTIR-ATR (total reflection absorption infrared spectroscopy) method can be performed as follows.

[Measurement of content (% by mass) of mold release agent by DSC (differential scanning calorimeter) method]
The total amount of release agent in the toner particles is obtained by the DSC (differential scanning calorimeter) method. The toner sample and the release agent single-piece sample are respectively measured by the following measurement apparatus and conditions, and the content of the release agent in the toner is determined from the ratio of the heat absorption amount of the release agent obtained.
Measurement device: DSC device (DSC 60; manufactured by Shimadzu Corporation)
・ Sample amount: about 5 mg
· Temperature rise temperature: 10 ° C / min
・ Measurement range: Room temperature to 150 ° C
Measurement environment: The total amount of the release agent in the nitrogen gas atmosphere is calculated by the following equation.
Total amount of release agent (% by mass) = (endothermic amount of release agent for toner sample (J / g)) × 100) / (endothermic amount of release agent alone (J / g))
According to this measurement method, the total amount of the releasing agent in the toner particles can be measured even when the releasing agent flows out during the toner production process and all the releasing agents charged are not contained in the toner.

[Measurement of content (mass%) of mold release agent by FTIR-ATR (total reflection absorption infrared spectroscopy) method]
The surface releasing agent amount of the toner particles is determined by the FTIR-ATR (total reflection absorption infrared spectroscopy) method. From the measurement principle, the analysis depth is about 0.3 μm, and the amount of the release agent in the vicinity of the surface of the toner particle can be determined by this analysis. The measuring method is as follows.

First, as a sample, 3 g of toner is pressed at a load of 6 t for 1 minute with an automatic pellet molding machine (Type M No. 50 BRP-E; MAEKAWA TESTING MACHINE CO.) To prepare 40 mmφ (about 2 mm thick) pellets .
The toner pellet surface is measured by the FTIR-ATR method.
A microscope FTIR apparatus to be used is a Spectrum One manufactured by PERKIN ELMER, in which a MultiScope FTIR unit is installed, and it is measured by micro ATR of a 100 μm diameter germanium (Ge) crystal.
It measures by incident angle 41.5 degrees of infrared rays, resolution 4 cm < ^-1 >, and 20 integration.
The intensity ratio of the obtained release agent-derived peak to the binder resin-derived peak was taken as the relative amount of the release agent on the surface of the toner particle. As the value, change the measurement location and use the average value measured four times.
The amount of surface release agent in the sample is calculated from the relationship with the relative amount of release agent of the sample for calibration curve in which the amount of known release agent is uniformly dispersed.

<Other ingredients>
The toner of the present invention may contain other components such as a colorant and a charge control agent.
(Colorant)
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably from well-known coloring agents. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10 G, 5 G, G), cadmium yellow, yellow iron oxide, yellow earth, 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 (5 G, R), tartrazine lake, quinoline yellow lake, anthrazan yellow BGL, iso Indolinon yellow, bengara, red lead, lead moth, cadmium red, cadmium mercurial red, antimony moth, permanent red 4R, para red, phi red, parachloro ortho nitro aniline red, lisor fast scarlet G, brili Tontofast Scarlet, Brilliant Carnmin BS, Permanentred (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belcans Fast Lubin B, Brilliant Toscalet G, Lisor Rubin GX, Permanented F5 R, Brilliant Carmin 6B, Scarlet Scarlet 3B, Bordeaux 5B, Toruijin Maroon, Permanent Bordeaux F2 K, Helio Bordeaux BL, Bordeaux 10 B, Bon Maroon Light, Bon Maroon Medium, Eosin Shine, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon Oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orene , Perinon 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 violet, dioxane violet, anthraquinone violet, chromium green, zinc green, chromium oxide, pyridinium, emerald green, pigment green B, naphthol green B, green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, And zinc flower, lithobon and mixtures thereof.

  There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable with respect to a toner, and 3 mass%-10 mass% are more preferable. .

The coloring agent can also be used as a master batch complexed with a resin.
There is no restriction | limiting in particular as resin knead | mixed with the said masterbatch, According to the objective, it can select suitably, For example, the modified polyester resin which modified polyester resin by the isocyanate group or epoxy, polyester resin, and polycarboxylic acid And a non-modified polyester resin comprising Further, in addition to the modified and unmodified polyester resins, for example, polymers of styrene such as polystyrene, poly p-chlorostyrene, polyvinyl toluene and the like, and substitution products thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer Polymer, styrene-vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloro methacrylate methyl copolymer, styrene-acrylonitrile copolymer , Styrene-vinyl methyl ketone copolymer, sulfur Styrene-based copolymers such as lene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate , Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terpene resin, aliphatic or Alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used singly or in combination of two or more.

The masterbatch can be obtained by mixing and kneading the resin for the masterbatch and the colorant under high shear force.
At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Alternatively, a so-called flushing method may be used, in which a water-containing aqueous paste of a coloring agent is mixed and kneaded with a resin and an organic solvent to transfer the coloring agent to the resin side to remove water and organic solvent components. According to this method, it is not necessary to dry since the wet cake of the colorant can be used as it is.
For mixing and kneading, a high shear dispersing device such as a three-roll mill is preferably used.
There is no restriction | limiting in particular as usage-amount of the said masterbatch, Although it can select suitably according to the objective, 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of said binding resin.

The resin for the masterbatch preferably has an acid value of 30 mg KOH / g or less and an amine value of 1 to 100, and the colorant is preferably dispersed, and the acid value is 20 mg KOH / g or less, and the amine value is It is more preferable to disperse and use the said coloring agent by 10-50.
When the acid value exceeds 30 mg KOH / g, the chargeability under high humidity may be reduced, and the pigment dispersibility may be insufficient. In addition, when the amine number is less than 1 and when the amine number is more than 100, the pigment dispersibility may be insufficient.
The acid value can be measured, for example, by the method described in JIS K 0070, and the amine value can be measured, for example, by the method described in JIS K 7237.

-Pigment dispersion-
The colorant can also be used as a colorant dispersion dispersed in a pigment dispersion.
There is no restriction | limiting in particular as said pigment dispersant, Although a well-known thing can be suitably selected according to the objective, It is preferable that compatibility with the said binder resin is high from the point of pigment dispersibility, As such commercial products, for example, "Adisper PB 821", "Aisper PB 822" (manufactured by Ajinomoto Fine Techno Co., Ltd.), "Disperbyk-2001" (manufactured by Bick Chemie), "EFKA-4010" (manufactured by EFKA), etc. are mentioned. Be

The weight average molecular weight of the pigment dispersant is preferably 500 to 100,000 as the molecular weight of the maximum value of the main peak in terms of styrene weight in gel permeation chromatography, and from the viewpoint of pigment dispersibility, 3000 to 100. 1,000 are more preferable, 5,000 to 50,000 are more preferable, and 5,000 to 30,000 are particularly preferable.
When the molecular weight is less than 500, the polarity may be increased and the dispersibility of the colorant may be decreased. When the molecular weight is more than 100,000, the affinity to the organic solvent is increased, and the colorant is dispersed. Sex may decrease.

  There is no restriction | limiting in particular as addition amount of the said pigment dispersant, Although it can select suitably according to the objective, It is preferable that it is 1 mass part-200 mass parts with respect to 100 mass parts of coloring agents, More preferably, it is 80 parts by mass. When the addition amount is less than 1 part by mass, the dispersibility may be lowered, and when it exceeds 200 parts by mass, the chargeability may be lowered.

(Charge control agent)
There is no restriction | limiting in particular as said charge control agent, According to the objective, a well-known thing can be selected suitably. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus Or a compound of tungsten, a fluorochemical, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like.

  Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, E-89 (above, made by Orient Chemical Industries Ltd.) of a phenol condensation product; TP-302, TP-415 (above, made by Hodogaya Chemical Industry) of quaternary ammonium salt molybdenum complex; Copy charge of ammonium salt PSY VP2038, Copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP 434 (above, Hoechst Co., Ltd.); LRA-901, LR- that is a boron complex 147 (manufactured by Nippon Kalyrit Co., Ltd.); copper phthalocyanine, perylene, quinacry Examples thereof include high-molecular compounds having functional groups such as don, azo pigments, other sulfonic acid groups, carboxyl groups and quaternary ammonium salts, phenol resins, and fluorine compounds.

The amount of the charge control agent used is not particularly limited, and may be appropriately selected according to the type of the binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method. However, 0.1 parts by mass to 10 parts by mass is preferable, and 0.2 parts by mass to 5 parts by mass is more preferable with respect to 100 parts by mass of the binder resin. When the amount of the charge control agent used exceeds 10 parts by mass, the fixability of the toner may be impaired.
The charge control agent is preferably dissolved in an organic solvent from the viewpoint of production stability, but may be finely dispersed in an organic solvent by a bead mill or the like.

<Characteristics of Toner>
In the toner of the present invention, in the TEM image, the release agent is contained at a constant ratio at a depth of 0.3 μm from the toner surface (Wsa / Wta is 2 to 5%), and the toner center portion is closer to the toner surface. It is characterized in that the particle diameter of the releasing agent present in is increased (WDa <WDb). By adopting such a structure, it is possible to suppress the exposure to the toner surface while maintaining the effect of the releasing agent of the releasing agent at the time of fixing, to increase the particle strength, and to reduce the toner electrification due to bleeding and dirt. It can prevent the occurrence.

  In order to obtain the desired toner defined in the present invention, it is necessary to sufficiently consider the kind and content of the binder resin, the releasing agent, and other components to be contained in the toner. And in this invention, it manufactures suitably by using the manufacturing method mentioned later. At this time, the type of the organic solvent in the toner composition liquid and the solubility of the release agent in the organic solvent may be taken into consideration, and the above-described release agent having the solubility in the organic solvent may be used. It can.

The Wta, the Wsa, the WDa, and the WDb can determine the fractured surface of the toner particle based on a transmission electron microscope (TEM) photograph.
Specific measurement means are shown below.
For example, the toner is embedded in an epoxy resin and then sliced with an ultramicrotome (ultrasonic) to prepare a thin section of the toner, which is then adjusted using a transmission electron microscope (TEM) to adjust the magnification of the microscope The fractured surface of an arbitrary 50 points of toner is extracted as a measurement sample by enlarging the field of view of the microscope until the particle diameter of the release agent domain becomes measurable from the fractured surface and observing the fractured surface. At this time, coloring with ruthenium or osmium may be performed as necessary, and the contrast may be adjusted to emphasize the releasing agent domain in the toner. After extraction, Wta, Wsa, WDa, and WDb are determined for each of the measurement samples using, for example, the image analysis software ImageJ, and the average value of the 50-point samples is determined.

(Wta, Wsa measurement method)
The image file is converted into an 8-bit binarized image by the image analysis software ImageJ. Next, the Upper Level and Lower Level of Threshold are set so that the release agent domain on the image is most identified and the noise is minimized. Furthermore, input 0.0001 μm ² -infinity as the lower limit value of the area to be extracted to Size with the command “Analyze Particle”, and with “Display results”, “Exclude on edges” and “Include holes” checked By pressing OK, the individual areas of the release agent domain identified in the binarization are output as Results. The sum of the areas corresponds to the Wta.

  Furthermore, in the image file, by erasing or hiding the image inside the toner in a range deeper than 0.3 μm from the toner outer periphery, an image file to be analyzed only in the range of 0.3 μm in depth from the outermost layer of toner particles is created. Do. At this time, the inside of the erased or concealed toner has a contrast opposite to that of the release agent identified on the image (for example, black when the release agent looks white). By analyzing the processed image file by the same method as that for obtaining Wta described above, it is possible to obtain the total area Wsa of the release agent present in the range of 0.3 μm in depth.

  Also, the scale value inserted into the TEM image taken by the Set Scale command is input and used for analysis. Furthermore, when both the case where the mold release agent appears white on the image and the case where it appears black on the image are mixed (for example, the mold release agent observed black is detached at the time of cut surface creation, etc. has a site that appears white) The sum of the area of the release agent determined from the respective contrasts is defined as Wta and Wsa.

(Measurement method of WDa, WDb)
The toner diameter d is determined from the image file by the image analysis software ImageJ. The toner diameter d is maximized when two parallel lines passing through the contacts on both ends of the outer circumference of the toner fractured section are drawn. Defined as the distance between two parallel lines when Two parallel lines were drawn through the contact points at the both ends of the release agent domain, which exist in the depth region Aa from the surface of the toner obtained here to 1/4 (1/4 d) of the diameter d of the toner. The distance between two parallel lines when the maximum is obtained is defined as the particle size of the release agent, and an average value obtained by extracting 50 points arbitrarily is defined as the number average particle size WDa. Further, an inner side of a depth region Aa from the surface of the toner to 1/4 (1/4 d) of the diameter d of the toner is defined as a region Ab, and contacts at both ends of the release agent domain present inside the region Ab The distance between two parallel lines at the maximum when two parallel lines passing through are drawn is taken as the particle size of the release agent, and the average value obtained by extracting 50 points arbitrarily is the number average particle size Define as WDb.

A cross-sectional view (image) of a representative toner is shown in FIG. In this cross-sectional view, all of the release agents correspond to domains with a white contrast.
The image which binarized the image of FIG. 1 by the said method is shown to Fig.2 (a). Among the toners of the image of FIG. 1, an image in which a depth range from the outermost surface to a depth of 0.3 μm is defined is shown in FIG. 2 (b). The image which binarized the image of FIG.2 (b) by the said method is shown in FIG.2 (c). Among the images in FIG. 1, an image defining toner diameter d and Aa and Ab is shown in FIG. 2 (d).

The ratio Wsa / Wta of the releasing agent area Wsa within 0.3 μm from the surface layer to the total area Wta of the releasing agent in the toner particles needs to be 2 to 5%. If this condition is not satisfied and it is smaller than 2%, sufficient releasability can not be obtained at the time of fixing, making it difficult to ensure releasability in a wide temperature range. On the other hand, if it is more than 5%, the proportion of the release agent present in the outermost layer may be high, which may easily cause aggregation or charge reduction associated with spent.
Further, the number average particle diameter WDa of the releasing agent present in the region Aa and the number average particle diameter WDb of the releasing agent present in the region Ab need to satisfy the relationship of WDa <WDb. If this condition is not satisfied and WDa is equal to WDb or WDa is larger than WDb, the releasing agent present in the outermost layer is likely to bleed out on the toner surface even when the developer is being stirred, causing aggregation due to spent Charge reduction may easily occur.

Furthermore, the toner of the present invention is characterized in that the displacement amount at 250 .mu.N application in the micro compression test is 700 nm or less. Preferably, 500 nm or less is desirable. If the amount of displacement is larger than 700 nm, the toner may be too soft and stress in the developing process may cause deformation of the toner. In addition, when the displacement amount is large, it can not withstand the load of 250 μN and may be broken at the time of measurement. In this case, the toner can not withstand development stress and is crushed in the developing machine to cause charge deterioration due to carrier contamination and the like.

Hereinafter, the method of the micro compression test is described.
The measurement of the toner particle hardness (displacement amount) is performed using an ultra-fine indentation hardness tester such as a nano indenter (ENT-2100) manufactured by Elionix.
(Method of measuring displacement)
A load is applied to the toner particles so that the maximum load is 250 μN, and a conical Berkovich indenter with a gap angle of 115 ° is pushed into the toner particles to change the load applied to the toner particles from 0 μN to 250 μN Measure the amount of displacement at the maximum load of 250 μN as the measured value.

  In the present invention, although there is no particular limitation on the toner constitution for satisfying that the displacement amount at 250 .mu.N application in the micro compression test is 700 nm or less, as a preferable method, glass transition of the binder resin constituting the toner is preferable. An additional drying step of additional drying for 30 minutes to 60 minutes at a temperature of [Tg-5 ° C.] relative to the temperature Tg may be mentioned. As a preferable means of the toner satisfying the definition of the present invention, there is a method of dissolving a release agent having excellent solubility together with a binder resin in a solvent, forming it into droplets, and drying to obtain the toner The release agent having high solvent solubility is considered to have a portion partially compatible with the binder resin during drying and precipitation. By promoting the phase separation of the release agent / binder resin in the partially compatible state, the strength of the entire toner can be increased. For this purpose, it is effective to heat at a temperature close to the glass transition temperature of the binder resin to increase the mobility of the release agent and binder resin molecules and to promote phase separation.

  The additional drying step preferably has a temperature of [Tg-5 ° C.]. If drying at a temperature higher than Tg-5 ° C or 60 minutes or more is carried out, fusion of toner grain boundaries proceeds and blocking occurs unfavorably. Further, if drying is performed at a temperature lower than Tg-5 ° C. or drying is completed in less than 30 minutes, the progress of phase separation becomes insufficient, and it becomes difficult to obtain a toner having a configuration of less than a desired displacement amount. Absent.

  Furthermore, in the present invention, it is preferable that the extract obtained by Soxhlet extraction of the toner with hexane has at least two recrystallization peaks in DSC (differential scanning calorimeter) method, and those recrystallization peaks are 45 It is more preferable that the temperature is not less than ° C.

The release agent in the toner is mostly contained in the extract after Soxhlet extraction with hexane. Therefore, by examining the thermal characteristics of the extract obtained by drying and solidifying the extract, it is possible to obtain information on the thermal characteristics of the release agent contained in the toner. That there are at least two recrystallization peaks in the DSC (differential scanning calorimeter) method of the extract means that at least two or more types of releasing agents having different recrystallization temperatures contained in the toner are contained. Show. In order to achieve the presence of the releasing agent domain inside the toner as described in claim 1, although it is necessary to use a releasing agent having high solubility in ethyl acetate as described above, The release agent often has a low melting point depending on the solubility, and the heat resistance of the resulting toner may be insufficient. On the other hand, when only a mold release agent having a high melting point is used, the solubility of the mold release agent in ethyl acetate described above is low, and the presence state of the mold release agent domain as shown in claim 1 is difficult. It becomes easy to cause the deterioration of the property and the fixation and the fracture accompanying the developer agitation stress. Using a combination of two or more mold release agents having different melting points as described above as a configuration that makes these problems compatible can be a means to make the present invention described in claim 1 more effective.
It is preferable that the said recrystallization peak is 45 degreeC or more. If the temperature is lower than 45 ° C., it indicates that the melting point of the two or more used releasing agents is low, which is not preferable because the heat resistance of the toner may be impaired.

  In two recrystallization peaks in the DSC method of the extract with hexane, the recrystallization peak height Pt1 on the low temperature side, and the recrystallization peak height Pt2 on the high temperature side, and the Soxhlet extraction with the hexane It is preferable to satisfy the relationship of S × (Pt1 + Pt2) / Pt1 ≧ 70, and more preferably S × (Pt1 + Pt2) / Pt1 ≧ 200, where S is the solubility S per 100 g of ethyl acetate at 45 ° C. of the extract. . If the value is smaller than 70, it becomes difficult to obtain the releasing agent according to claim 1 and the fixing releasability is aggravated, and sticking and crushing are apt to occur due to developer agitation stress. Not desirable.

Here, an extract by Soxhlet extraction of hexane can be obtained as follows.
The toner is put in a No. 86R cylindrical filter paper, put into a Soxhlet extractor, and extracted for 8 hours using hexane as a solvent. At this time, extraction is performed at a reflux rate such that the solvent extraction cycle is once every about 15 minutes to 20 minutes. After completion of the extraction, the extract is transferred to a vessel and the solvent is distilled off. Further dry under vacuum at 60 ° C. for 15 hours to obtain an extract with hexane.

Moreover, the recrystallization peak in the DSC (differential scanning calorimeter) method of an extract can be calculated | required on condition of the following. A DSC chart of the extract is obtained according to the following measuring apparatus and conditions.
Measurement device: DSC device (DSC 60; manufactured by Shimadzu Corporation)
・ Sample amount: about 5 mg
· Temperature rise temperature: 10 ° C / min
Measurement range: Temperature rise from room temperature to 150 ° C., temperature drop to 150 ° C. to 0 ° C. Measurement environment: in nitrogen gas atmosphere Select the exothermic peaks obtained from the DSC temperature drop chart obtained, and recrystallize those peak temperatures Define as peak temperature.

<Toner shape>
The volume average particle diameter of the toner of the present invention is preferably 1 μm to 8 μm from the viewpoint of forming a high-resolution, high-definition, high-quality image.
The particle size distribution (volume average particle diameter / number average particle diameter) of the toner is preferably 1.00 to 1.15 from the viewpoint of maintaining a stable image over a long period of time.

Furthermore, in the toner of the present invention, in the distribution in which the number particle diameter and frequency (number) of the toner are plotted, the number particle diameter (also referred to as “the most frequent diameter”) is the most frequent (number). It is preferable to have a second frequency (number) peak within the range of 1.31 times the number particle size.
When the second frequency (number) peak is not shown, in particular, when the particle size distribution (volume average particle diameter / number average particle diameter) approaches 1.00 (monodisperse), the fine packing property of the toner Since it becomes very high, the initial fluidity decrease and cleaning failure tend to occur. In addition, when the second frequency (number) peak is present in the number particle diameter larger than the above-mentioned 1.31 times, the deterioration of the image quality granularity due to the inclusion of a large amount of coarse powder as toner is unfavorably observed.

  FIG. 3 is a graph showing an example of distribution in which the number particle diameter and frequency (number) of the toner of the present invention are plotted. In FIG. 3, the horizontal axis represents the number particle diameter (μm), and the vertical axis represents the frequency (number). It has a second frequency (number) peak within the range of the number particle size 1.21 times to 1.31 times the number particle size (also referred to as "the most frequent diameter") with the highest frequency (number) It is shown.

The particle size and particle size distribution are measured as follows.
[Measurement of toner particle size and particle size distribution]
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner of the present invention are measured with an aperture diameter of 50 μm using a particle size measurement device (“Multisizer III” manufactured by Beckman Coulter, Inc.). After measuring the volume and number of toner particles, volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be determined. The particle size distribution uses Dv / Dn obtained by dividing the volume average particle size (Dv) of the toner by the number average particle size (Dn). If it is completely monodisperse, it becomes 1 and the larger the numerical value, the wider the distribution.

  An external additive such as a fluidity improver or a cleanability improver can be added to the toner of the present invention as required.

(Flowability improver)
A fluidity improver may be added to the toner according to the present invention. The flowability improver improves the flowability of the toner (makes it easy to flow) by being added to the toner surface.
There is no restriction | limiting in particular as said fluidity improver, According to the objective, it can select suitably. For example, fine powder silica such as wet process silica, dry process silica, fine powder of metal oxide such as fine powder non-oxidized titanium, fine powder non-alumina, etc., and their surface with silane coupling agent, titanium coupling agent, silicone oil etc. Treated silica treated, treated titanium oxide, treated alumina; fluorocarbon resin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, etc. may be mentioned. Among these, fine powder silica, fine powder non-oxidized titanium, and fine powder non-alumina are preferable, and treated silica in which these are surface-treated with a silane coupling agent or silicone oil is more preferable.
There is no restriction | limiting in particular as a particle size of the said fluidity improver, Although it can select suitably according to the objective, As an average primary particle diameter, 0.001 micrometer-2 micrometers are preferable, and 0.002 micrometer-0.2 micrometers are more preferable.

The fine powder silica is a fine powder produced by vapor phase oxidation of silicon halide and is referred to as so-called dry process silica or fumed silica.
Examples of commercially available fine silica powder produced by gas phase oxidation of the silicon halogen compound include AEROSIL (trade name of Nippon Aerosil Co., Ltd., the same applies hereinafter) -130, -300, -380, -TT600, -MOX170, -MOX80 -COK 84; Ca-O-SiL (trade name of CABOT) -M-5, -MS-7, -MS-75, -HS-5, -EH-5; Wacker HDK (trade name of WACKER-CHEMIE) -N20 V15, -N20E, -T30, -T40; D-CFineSi1ica (trade name of Dow Corning); Franso 1 (trade name of Fransi 1) and the like.

  Furthermore, a treated fine silica powder obtained by hydrophobizing a fine silica powder produced by vapor phase oxidation of a silicon halide is more preferable. In the treated fine silica powder, it is particularly preferable to process the fine silica powder so that the degree of hydrophobicity measured by the methanol titration test preferably exhibits a value of 30% to 80%. Hydrophobization is imparted by chemical or physical treatment with an organosilicon compound or the like that reacts or physically adsorbs with the silica fine powder. A preferable method is a method of treating a fine silica powder produced by vapor phase oxidation of a silicon halide with an organosilicon compound.

  Examples of the organic silicon compound include hydroxypropyl trimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and dimethyl Vinylchlorosilane, divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethyl Chlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethane Trichlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxy Silane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and units having 2 to 12 siloxane units per molecule, and located at unterminated units The dimethylpolysiloxane etc. which contain 0-1 hydroxyl group each couple | bonded with Si are mentioned. Further, silicone oils such as dimethyl silicone oil can be mentioned. These may be used singly or in combination of two or more.

There is no restriction | limiting in particular as a number average particle diameter of the said fluidity improver, Although it can select suitably according to the objective, 5 nm-100 nm are preferable, and 5 nm-50 nm are more preferable.
As the specific surface area of the flowability improving agent, a specific surface area by nitrogen adsorption measured by the BET method, preferably at least ^{30m 2 / g, 60m 2 /} g~400m 2 / g is more preferable.
For fine powder the flowability improver is treated surfaces, the specific surface area is preferably at least ^{20m 2 / g, 40m 2 /} g~300m 2 / g is more preferable.
There is no restriction | limiting in particular as an application quantity of the said fluidity improver, Although it can select suitably according to the objective, 0.03 mass part-8 mass parts are preferable with respect to 100 mass parts of toner particle.

(Cleanability improver)
There is no particular limitation on the cleanability improver for improving the removability of the toner remaining on the electrostatic latent image carrier or the primary transfer medium after transferring the toner onto the recording paper etc., and it is appropriately selected according to the purpose. can do. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer particles produced by soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles. The fine polymer particles preferably have a relatively narrow particle size distribution and a weight average particle diameter of 0.01 μm to 1 μm.

  These flowability improvers, cleanability improvers and the like are also used as being attached or fixed to the surface of the toner, and thus are also called external additives. The method for externally adding such an external additive to the toner is not particularly limited, and can be appropriately selected according to the purpose. For example, various powder mixers and the like are used. Examples of the powder mixer include V-type mixers, rocking mixers, Loedige mixers, Nauta mixers, Henschel mixers, etc. As a powder mixer to be used for immobilization, a hybridizer can be used. , Mechanofusion, Q mixer and the like.

[Developer]
The developer of the present invention at least contains the toner of the present invention and, if necessary, further contains other components such as a carrier.
The toner of the present invention obtained as described above can be suitably used for either a one-component developer or a two-component developer mixed with a carrier. In particular, the toner of the present invention has improved particle strength, can prevent crushing by a blade, and is excellent in sticking resistance, and thus can be effectively used for a one-component developer.

<Carrier>
There is no restriction | limiting in particular as said carrier, According to the objective, it can select suitably, For example, carriers, such as a ferrite and magnetite, resin-coated carrier, etc. can be mentioned.
The resin-coated carrier comprises a carrier core particle and a resin coating material which is a resin for coating (coating) the surface of the carrier core particle.

Examples of the resin used for the covering material include styrene-acrylic resins such as styrene-acrylic acid ester copolymer and styrene-methacrylic acid ester copolymer; acrylic acid ester copolymer, methacrylic acid ester copolymer And acrylic resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymers, fluorine-containing resins such as polyvinylidene fluoride, silicone resins, polyester resins, polyamide resins, polyvinyl butyral, amino acrylate resins and the like. In addition to these, resins usable as a coating material for carriers such as ionomer resins and polyphenylene sulfide resins may be mentioned. These resins may be used alone or in combination of two or more.
Further, as the carrier, a binder type carrier core in which magnetic powder is dispersed in a resin can also be used.

In the resin-coated carrier, as a method of coating the surface of the carrier core with at least a resin coating agent, for example, a method of dissolving or suspending the resin in a solvent and adhering to the coated carrier core, or simply in powder form The method of mixing is mentioned.
The use ratio of the resin coating material to the resin-coated carrier is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.01 mass to 5 mass with respect to 100 mass parts of the resin-coated carrier. 0.1 mass to 1 mass is more preferable.

The following (1) and (2) can be mentioned as a usage example which coat | covers the said magnetic body with the said resin coating material of 2 or more types of mixtures.
(1) 100 parts by weight of titanium oxide fine powder treated with 12 parts by weight of a mixture of methyldichlorosilane and dimethyl silicone oil (mass ratio 1: 5), (2) per 100 parts by weight of silica fine powder Treated with 20 parts by mass of a mixture of dimethyldichlorosilane and dimethyl silicone oil (mass ratio 1: 5). Examples of the resin coating material include styrene-methyl methacrylate copolymer, fluorine-containing resin and styrene-based copolymer Mixtures with polymers, silicone resins and the like are preferably used, and among these, silicone resins are particularly preferred.

  As a mixture of the said fluorine-containing resin and a styrene-type copolymer, the mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, the mixture of a polytetrafluoroethylene and a styrene-methyl methacrylate copolymer is mentioned, for example Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10) and styrene-acrylic acid 2-ethylhexyl copolymer (copolymer mass ratio 10:90 to 90:10) and styrene -A mixture with 2-ethylhexyl acrylic acid-methyl methacrylate copolymer (copolymer mass ratio 20-60: 5-30: 10: 50) etc. are mentioned. As said silicone resin, the modified silicone resin produced | generated by reacting nitrogen-containing silicone resin and nitrogen-containing silane coupling agent, and a silicone resin is mentioned.

  Examples of the magnetic material of the carrier core include oxides such as ferrite, iron excess type ferrite, magnetite and γ-iron oxide, metals such as iron, cobalt and nickel, and alloys of these. Further, as elements contained in these magnetic materials, iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, vanadium and the like can be mentioned. Be Among these magnetic materials, copper, zinc, copper-zinc-iron ferrite having iron as a main component, manganese-magnesium-iron ferrite having manganese, magnesium and iron as a main component are particularly preferable. Be

The volume resistance value of the carrier can be set by appropriately adjusting the degree of unevenness of the surface of the carrier and the amount of the resin to be coated, and for example, 10 ⁶ Ω · cm to 10 ¹⁰ Ω · cm is preferable.

  There is no restriction | limiting in particular as a particle size of the said carrier, Although it can select suitably according to the objective, 4 micrometers-200 micrometers are preferable, 10 micrometers-150 micrometers are more preferable, and 20 micrometers-100 micrometers are more preferable. Among them, as the particle diameter of the resin-coated carrier, the 50% particle diameter is particularly preferably 20 μm to 70 μm. In a two-component developer, it is preferable to use 1 part by mass to 200 parts by mass of the toner of the present invention with respect to 100 parts by mass of the carrier, and 2 parts by mass to 50 parts by mass of the toner with respect to 100 parts by mass of the carrier. It is more preferred to use.

[Method of producing toner]
An example of the toner production means of the present invention will be described below with reference to FIGS. 4 and 5. The toner production means of the present invention is divided into a droplet adjustment means, a droplet discharge means, a droplet conveyance solidification means, and a droplet collection means. Each is explained below.

<Droplet adjustment means>
The droplet forming means is a means for forming a droplet by discharging a toner composition liquid in which at least a binder resin and a releasing agent are dissolved or dispersed in an organic solvent.
The toner composition liquid contains at least the binder resin and the releasing agent, and further contains, if necessary, components such as other colorants, a pigment dispersant, and a charge control agent, It can be obtained by dissolving or dispersing in an organic solvent.

The organic solvent is a volatile solvent which can dissolve or disperse the toner composition in the toner composition liquid, and the binder resin and the release agent in the toner composition liquid are not phase-separated. There is no particular limitation as long as it can be dissolved, and it can be appropriately selected according to the purpose.
For example, organic solvents of ethers, ketones, esters, hydrocarbons, and alcohols are preferably used, and particularly, tetrahydrofuran (THF), acetone, methyl ethyl ketone (MEK), ethyl acetate, toluene, water and the like can be mentioned. These may be used alone or in combination of two or more.
In the present invention, when ethyl acetate is used as the organic solvent, as described above, it is preferable to use a release agent which dissolves 70 g or more, more preferably 200 g or more per 100 g of ethyl acetate at 45 ° C.

(Method of preparing toner composition liquid)
The toner composition liquid can be obtained by dissolving or dispersing the toner composition in an organic solvent. In preparation of the toner composition liquid, it is important to prevent the clogging of the discharge holes by making the dispersion such as the colorant sufficiently fine with respect to the opening diameter of the nozzle by using a homomixer or a bead mill. .

The solid content of the toner composition liquid is preferably 3% by mass to 40% by mass. If the solid content is less than 3% by mass, not only the productivity is lowered but also the dispersion of the colorant and the like tends to cause sedimentation or aggregation, so that the composition of each toner particle tends to be uneven, and the toner quality It may decrease. When the solid content exceeds 40% by mass, a toner having a small particle diameter may not be obtained.
The step of discharging the toner composition liquid to form droplets can be performed by discharging droplets using a droplet discharging means.

  The temperature of the toner composition liquid is preferably about 50 to 60 ° C. If the liquid temperature is lower than 50 ° C., the particles are not instantaneously dried immediately after the discharge, so that the coalescence of the droplets may occur and the particle size distribution may be deteriorated. On the other hand, if the liquid temperature is higher than 60 ° C., the solvent tends to evaporate and the solid concentration tends to rise, so that there is a concern that a toner having a desired particle diameter can not be obtained as described above.

<Droplet discharge means>
The droplet discharge means used in the present invention is not particularly limited as long as the particle size distribution of the discharged droplets is narrow, and known ones can be used. Droplet discharge means include 1 fluid nozzle, 2 fluid nozzle, membrane vibration type discharge means, Rayleigh split type discharge means, liquid vibration type discharge means, liquid column resonance type discharge means, etc. As the membrane vibration type, for example, Japanese Patent No. 5055154, Japanese Patent No. 4647506 for Rayleigh split type, Japanese Patent No. 5315920 for liquid vibration type, and Japanese Patent Laid-Open No. 2011-212668 for liquid column resonance type.
In order to secure the productivity of the toner, the particle size distribution of the droplets is narrow, vibration is applied to the liquid in the liquid column resonance liquid chamber in which a plurality of discharge holes are formed, and a standing wave is formed by the liquid column resonance. And liquid droplet resonance which discharges the liquid from the discharge holes formed in the region which becomes the antinode of the standing wave, and it is preferable to use any of these.

(Liquid column resonance discharge means)
A liquid column resonance type discharge means for discharging using resonance of the liquid column will be described.
FIG. 4 shows the liquid column resonance droplet discharge means 11. The liquid common supply path 17 and the liquid column resonance liquid chamber 18 are configured. The liquid column resonance liquid chamber 18 is in communication with the common liquid supply path 17 provided on one of the wall surfaces at both ends in the longitudinal direction. The liquid column resonance liquid chamber 18 is provided in the discharge hole 19 for discharging the droplet 21 on one of the wall surfaces connected to the wall surfaces at both ends, and in the wall surface facing the discharge hole 19 And vibration generating means 20 for generating high frequency vibration in order to form a standing wave. A high frequency power source (not shown) is connected to the vibration generating means 20.

  The liquid to be discharged from the discharge means in the present invention is in a dispersed state in which the components of the particles to be obtained are dissolved or dispersed. (Hereinafter, these will be described as "toner component liquid" for explanation of the case of producing the toner) The toner component liquid 14 is passed through the liquid supply pipe by the liquid circulation pump not shown and the common common supply path 17 It flows into the inside and is supplied to the liquid column resonance liquid chamber 18. Then, in the liquid column resonance liquid chamber 18 in which the toner component liquid 14 is filled, a pressure distribution is formed by the liquid column resonance standing wave generated by the vibration generating means 20. Then, in the liquid column resonance standing wave, the droplet 21 is discharged from the discharge hole 19 which is a portion having a large amplitude and having a large pressure fluctuation and which becomes an antinode of the standing wave.

  The area | region which becomes an antinode of the standing wave by this liquid column resonance means the area | regions other than the node of a standing wave. Preferably, the pressure fluctuation of the standing wave is an area having an amplitude large enough to eject the liquid, and more preferably, the position at which the amplitude of the pressure standing wave is maximized (a node as a velocity standing wave Range from. ± .1 wavelength to a position where the light intensity is minimized. If the region is the antinode of the standing wave, even if the discharge holes are opened in a plurality, substantially uniform droplets can be formed from each of them, and furthermore, the droplets can be discharged efficiently. As a result, clogging of the discharge holes is less likely to occur. The toner component liquid 14 having passed the common liquid supply path 17 flows through a liquid return pipe (not shown) and is returned to the raw material storage container. When the amount of the toner component liquid 14 in the liquid column resonance liquid chamber 18 decreases due to the discharge of the droplets 21, the suction force by the action of the liquid column resonance standing wave in the liquid column resonance liquid chamber 18 acts and the liquid common supply The flow rate of the toner component liquid 14 supplied from the passage 17 is increased, and the toner component liquid 14 is replenished into the liquid column resonance liquid chamber 18. Then, when the toner component liquid 14 is replenished into the liquid column resonance liquid chamber 18, the flow rate of the toner component liquid 14 passing through the common liquid supply path 17 returns to the original.

<Droplet transport solidification means>
The droplets of the toner component liquid discharged into the gas from the droplet discharging means described above are transported (droplet transporting means), solidified (droplet solidifying means), and collected. Toner can be obtained. The droplet transfer means and the droplet solidifying means are methods of solidifying while being transported using the same means, and even after being solidified and transported to the droplet collecting means, the droplets are solidified after collection. It does not matter if it is

  As a preferred example of the droplet transfer means, FIG. 5 shows a schematic view of the apparatus of the present invention. The droplets discharged by the droplet discharge means are transported by the droplet transport means by the air flow temperature-controlled by the air flow temperature control means described later, the droplets are dried and solidified, and transported to the particle repair means, It is collected as solid particles.

  As shown in FIG. 5, the droplets discharged from the droplet discharge means can be continuously formed by being transferred by the droplet transfer means. As shown in FIG. 4, it is desirable that the droplet transport means is transported by an air flow from the lateral direction with respect to the droplet ejection direction. This is because the distance between droplets can be effectively separated. In the case of the same direction as the droplet discharge direction, the air flow stagnates in the vicinity of the discharge holes arranged on a plane, so that the droplets can not be separated and the liquid enemies are likely to be in contact with each other. In FIG. 5, the apparatus for producing fine particles of the present invention is described, but the droplets discharged in the right direction of the figure by the droplet discharge means are transported by the transport air stream flowing from the upper side of the figure.

  When the jetted droplets come in contact with each other before drying, the droplets coalesce and become one particle (hereinafter, this phenomenon may be referred to as "cohesion"). In order to obtain solidified particles having a uniform particle size distribution, it is necessary to maintain the distance between the jetted droplets. However, the ejected droplets have a constant initial velocity, but eventually stall due to air resistance. The stalled particles catch up with droplets ejected later, resulting in coalescence. Since this phenomenon occurs constantly, the particle size distribution will be greatly deteriorated when the particles are collected. In order to prevent the coalescence, it is preferable to transport while solidifying the droplets while preventing coalescence by preventing the droplets from being in contact with each other so as not to bring the droplets into contact with each other. Therefore, it is preferable to transport the solidified particles to the solidified particle collecting means by the carrier air stream, in terms of high production efficiency.

The means for solidifying liquid droplets may differ depending on the properties of the toner component liquid, although the concept is different, but any means may be used as long as the toner component liquid can basically be made solid.
For example, if the toner component liquid is a solid raw material dissolved or dispersed in a volatilizable solvent, it can be achieved by drying droplets in a carrier air stream after droplet ejection, ie, volatilizing the solvent. In the drying of the solvent, the drying state can be adjusted by appropriately selecting the temperature, the vapor pressure, the type of gas, and the like of the gas to be jetted. In addition, even if the particles are not completely dried, additional particles may be additionally dried in a separate step after recovery as long as the collected particles maintain a solid state. Even if it does not follow the said example, you may achieve by application of temperature change, a chemical reaction, etc.

(Airflow temperature adjustment means, and airflow temperature adjustment process)
FIG. 5 is a schematic view of the apparatus of the present invention, and the droplet transfer means includes the above-described airflow temperature control means. The air flow temperature adjusting means is not particularly limited as long as it can adjust the conveying air flow temperature in the droplet conveying means, and can be appropriately selected according to the purpose.
The air flow temperature adjusting step is not particularly limited as long as it is a step capable of adjusting the conveying air flow temperature in the droplet conveying means, and can be appropriately selected according to the purpose, but using the air flow temperature adjusting means preferable.
Although not shown in FIG. 5 as the air flow temperature adjusting means, it is preferable that the air flow adjusting means has a control mechanism that measures the air flow temperature and stabilizes the air flow temperature. Although the present invention has a plurality of air flow temperature control means, it has a mechanism capable of adjusting the temperature of each air flow temperature control means.

In the present invention, in particular, it is possible to control the drying state of the particles by providing a temperature difference between the temperature of the droplet discharge portion and the drying temperature as a plurality of airflow temperature control means. It is important in constructing the existence state.
Specifically, in the apparatus shown in FIG. 5, the discharged droplets 21 are transported by the airflow supply means 31 and 32 by the transport airflows 41a and 41b. At this time, the supplied air flow is supplied from 31 and 32 with air flows different in temperature on the side (41a) closer to the nozzle and the side (41b) far from the nozzle. By setting the air flow 41a at a low temperature, the domain of the release agent is grown near the center of the droplet immediately after the discharge, and by setting the air flow 41b at a high temperature thereafter, the recrystallization of the release agent is promoted to make it small. While forming a domain, it can be moved to the surface vicinity with rapid drying of the solvent.
In the figure, reference numeral 35 denotes a guide for feeding the two types of air streams generated from the upstream to the air flow straightening means 36 in a separated state.
In the present invention, the provision of the air flow straightening means 36 allows the air flow of plural temperatures to pass to the droplet forming means in a state of being kept in a layered state without mixing, so that the discharge hole surface formed in the droplet forming means The temperature rise can be further reduced. The air flow straightening means 36 may have a honeycomb shape, or may be a flat plate parallel to the air flow path on which a plurality of flat plates are disposed in the direction perpendicular to the direction of the air flow and the droplet discharge means is disposed. A flat plate parallel to the disposed air flow path may be stacked in layers.

  The air flow 41 a is preferably 40 ° C. or less. When the temperature is higher than 40 ° C., drying of the particles immediately after the discharge proceeds rapidly, and it is not possible to grow the release agent domain of a sufficient size, and the size of the release agent in the vicinity of the toner surface and inside As a result, it becomes difficult to obtain a toner satisfying the relationship of WDa <WDb according to claim 1. Further, the air flow 41 b is preferably 50 ° C. or higher. If the temperature is less than 50 ° C., minute domains of the release agent are not easily formed, and convection in the particles generated by rapid drying of the solvent is not likely to occur, and the minute release agent gathers in the vicinity of the toner surface. By becoming difficult, it becomes difficult to obtain the toner satisfying the relationship of 2 to 5% of Wsa / Wta according to claim 1. That is, providing a drying temperature difference immediately after the discharge and after that is an effective means for constructing the morphology of the release agent according to the present invention.

<Solidified particle collection means>
The solidified particles can be recovered from the atmosphere by known powder collection means such as cyclone collection, back filters and the like.

<Secondary drying>
If the amount of residual solvent contained in the toner particles obtained by the drying and collecting means shown in FIG. 5 is large, secondary drying is carried out as necessary to reduce this. As secondary drying, general known drying means such as fluidized bed drying and vacuum drying can be used. When the organic solvent remains in the toner, not only the toner characteristics such as heat resistant storage stability, fixing property, charging characteristics, etc. fluctuate with time. Since the organic solvent volatilizes at the time of fixing by heating, the possibility of adversely affecting the user and peripheral devices is increased, so sufficient drying is carried out.

  Hereinafter, the present invention will be more specifically described by way of Examples and Comparative Examples, but the present invention is not limited thereto. In addition, "part" represents a mass part.

Example 1
(Preparation of Toner 1)
-Preparation of coloring agent dispersion-
First, a carbon black dispersion was prepared as a colorant.
Twenty parts of carbon black (Regal 400, manufactured by Cabot) and 2 parts of a pigment dispersant (Adispar PB 821, manufactured by Ajinomoto Fine Techno Co., Ltd.) were primarily dispersed in 78 parts of ethyl acetate using a mixer having a stirring blade. The obtained primary dispersion was finely dispersed by a strong shear force using a Dyno mill to prepare a secondary dispersion from which aggregates were completely removed. Furthermore, a polytetrafluoroethylene (PTFE) filter (Fluorinate membrane filter FHLP09050, manufactured by Nippon Millipore Corporation) having pores of 0.45 μm was passed to prepare a carbon black dispersion dispersed to a submicron range.

-Preparation of Toner Composition Liquid-
In 676.7 parts of ethyl acetate, 20 parts of [WAX1] as a mold release agent, 2 parts of a mold release agent dispersant, 263.3 parts of [polyester resin A] as a binder resin and mixing at 70 ° C. Dissolve using a mixer with stirring blades. As a release agent dispersant, a polyethylene release agent obtained by grafting a styrene-butyl acrylate copolymer was used. Both [WAX1] and [polyester resin A] were dissolved in ethyl acetate transparently without phase separation. After dissolution, the liquid temperature was adjusted to 55 ° C., 100 parts of the carbon black dispersion was further mixed, and the mixture was stirred for 10 minutes to prepare a toner composition liquid.

[WAX1] is a synthetic amide wax having a melting point of 62.6 ° C. and a recrystallization temperature of 52.7 ° C. (manufactured by NOF Corporation).
Also, [Polyester resin A] is composed of terephthalic acid / isophthalic acid / succinic acid / ethylene glycol / neopentyl glycolol, and they are 0.38 / 0.57 / 0.05 / 0.5 / 0.5. It is a polyester resin obtained by causing a polymerization reaction at a molar ratio. The weight average molecular weight of the polyester resin A is 24,000, and the Tg is 65 ° C.
The weight-average molecular weight Mw of the binder resin was determined by measuring the THF dissolution of the binder resin by means of a GPC (gel permeation chromatography) measuring apparatus GPC-150C (manufactured by Waters Corporation). As columns, KF801 to 807 (manufactured by Shodex Co., Ltd.) were used, and as detectors, RI (refractive index) detectors were used. The boiling point of ethyl acetate is 76.8 ° C.

-Preparation of Toner-
Droplets of the obtained toner composition liquid were discharged under the following conditions using the toner manufacturing apparatus of FIG. 5 having a droplet discharge head as the droplet discharge means shown in FIG. After discharging the droplets, the droplets are dried and solidified by a droplet solidifying means using dry nitrogen and collected by a cyclone, and then further for 40 hours at 35 ° C./90% RH, 40 ° C./50% RH The resultant was subjected to air-drying for 24 hours to prepare a toner base particle intermediate. The obtained toner base particles were additionally dried under the following conditions to obtain toner base particles.
Preparation of the toner was continuously performed for 6 hours, but the discharge holes were not clogged.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 60 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 60 ° C
Additional drying time: 30 minutes

  Next, with respect to 100 parts of the toner base particles, 2.8 parts of commercially available fine silica powder NAX50 (manufactured by Nippon Aerosil Co .; average primary particle size 30 nm) and H20TM (manufactured by Clariant Co .; average primary particle size 20 nm) 0.9 parts were mixed by a Henschel mixer. Next, this was passed through a 60 μm sieve to remove coarse particles and aggregates, whereby [Toner 1] was obtained.

This [Toner 1] was embedded in epoxy resin, and a section was produced with an ultrasonic microtome. This is exposed to an atmosphere of a RuO ₄ aqueous solution and dyed, then observed with a transmission electron microscope (TEM), and the total area Wta of the releasing agent in the toner particles using image analysis software ImageJ and 0.3 μm from the surface The area Wsa of the release agent domain in the region of 1 was calculated, and the ratio Wsa / Wta was determined.
Further, the content of the releasing agent was determined by a value obtained by mass-converting the amount of heat absorption determined by DSC (differential scanning calorimeter) method of [Toner 1]. Further, the amount of release agent in the region of 0.3 μm from the surface was also determined by the FTIR-ATR method.
Further, the toner 1 was subjected to Soxhlet extraction with hexane for 6 hours, and the obtained extract was dried at 60 ° C. for 15 hours, and the number of recrystallization peaks was determined using DSC. When the number of recrystallization peaks was two or more, the recrystallization peak height Pt1 Pt2 and the ethyl acetate solubility S of the extract were determined to determine S × (Pt1 + Pt2) / Pt1.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

Example 2
(Preparation of Toner 2)
[Toner 2] was obtained in the same manner as in Example 1 except that [WAX 2] was used in place of [WAX 1] as a release agent in Example 1.
[WAX2] is a synthetic ester wax (WAX-158: manufactured by NOF CORPORATION) mainly composed of an aliphatic ester having a melting point of 53.0 ° C. and a recrystallization temperature of 46.0 ° C. Both [WAX 2] and [polyester resin A] were dissolved in ethyl acetate transparently without phase separation.
In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
Regarding this [Toner 2] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

[Example 3]
(Preparation of Toner 3)
[Toner 3] was obtained in the same manner as in Example 1 except that [WAX 3] was used in place of [WAX 1] as a release agent in Example 1.
[WAX3] is a synthetic ester wax (WAX-42: manufactured by NOF Corporation) mainly composed of an aliphatic ester having a melting point of 55.2 ° C. and a recrystallization temperature of 48 ° C.
Both [WAX 3] and [Polyester Resin A] were dissolved in ethyl acetate transparently without phase separation.
In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
Regarding this [Toner 3] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

Example 4
(Preparation of Toner 4)
In Example 1, [WAX 3] was used instead of [WAX 1] as a mold release agent, and under the toner preparation conditions, the drying temperature was 70 ° C. and the drying time for additional drying was 45 minutes as follows: [Toner 4] was obtained in the same manner as in Example 1 except for the above.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 70 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 60 ° C
Additional drying time: 45 minutes

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
Regarding this [Toner 4] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows the physical properties of the toner.

[Example 5]
(Preparation of Toner 5)
In Example 1, [WAX 3] was used instead of [WAX 1] as the mold release agent, the addition amount of the mold release agent was 40 parts, and the drying temperature was 50 ° C. as described below under toner preparation conditions. [Toner 5] was obtained in the same manner as in Example 1 except that the drying time for additional drying was 60 minutes.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 50 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 60 ° C
Additional drying time: 60 minutes

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
Regarding this [toner 5] in the same manner as in Example 1, the content of releasing agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, according to FTIR-ATR method, in the region of 0.3 μm from the night surface The amount of release agent was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows the physical properties of the toner.

[Example 6]
(Preparation of Toner 6)
In Example 1, [WAX 3] was used in place of [WAX 1] as the release agent, the amount of release agent added was 10 parts, and the drying temperature was 75 ° C. as described below under the toner preparation conditions. [Toner 6] was obtained in the same manner as in Example 1 except for the above.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 75 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 60 ° C
Additional drying time: 30 minutes

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
Regarding this [Toner 6] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

[Example 7]
(Preparation of Toner 7)
In Example 1, using [WAX 3] instead of [WAX 1] as the releasing agent, using [Polyester B] instead of [Polyester A] as the binder resin, and under the toner preparation conditions, [Toner 7] was obtained in the same manner as in Example 1 except that the additional drying temperature was 65 ° C. and the additional drying time was 60 minutes. [Polyester resin B] is composed of terephthalic acid / isophthalic acid / ethylene glycol / neopentyl glycol, and they are polymerized at a molar ratio of 0.4 / 0.6 / 0.5 / 0.5. It is a polyester resin obtained. The weight average molecular weight of the polyester B is 26,000, and the Tg is 70.degree.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 60 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 65 ° C
Additional drying time: 60 minutes

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
About this [Toner 7] in the same manner as in Example 1, the content of releasing agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm area from the surface by FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

Example 8
(Preparation of Toner 8)
In Example 1, Example 1 and Example 1 were used except that [WAX 3] was used instead of [WAX 1] as a mold release agent, and that the drying time at the time of additional drying was 120 minutes under the toner preparation conditions as follows. [Toner 8] was obtained in the same manner.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 60 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 60 ° C
Additional drying time: 120 minutes

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
About this [Toner 8] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

[Example 9]
(Preparation of Toner 9)
In Example 1, 10 parts of [WAX1] and 10 parts of [WAX7] were used instead of [WAX1] as a releasing agent, and under the toner preparation conditions, the drying temperature was 60 ° C. as shown below, at the time of additional drying [Toner 9] was obtained in the same manner as in Example 1 except that the drying time was 60 minutes. [WAX 7] is a synthetic ester wax (WAX-16: manufactured by NOF Corporation) mainly composed of an aliphatic ester having a melting point of 64.6 ° C. and a recrystallization temperature of 57.0 ° C.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 60 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 60 ° C
Additional drying time: 60 minutes

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
About this [Toner 9] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

[Example 10]
(Preparation of Toner 10)
In Example 1, 8 parts of [WAX 2] and 12 parts of [WAX 7] were used instead of [WAX 1] as a mold release agent, and under the toner preparation conditions, the drying temperature was 60 ° C. [Toner 10] was obtained in the same manner as in Example 1 except that the drying time was 60 minutes.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 60 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 60 ° C
Additional drying time: 60 minutes

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
Regarding this [toner 10] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

[Example 11]
(Preparation of Toner 11)
In Example 1, 15 parts of [WAX 3] and 5 parts of [WAX 7] were used instead of [WAX 1] as a releasing agent, and under the toner preparation conditions, the drying temperature was 60 ° C. [Toner 11] was obtained in the same manner as in Example 1 except that the drying time was 60 minutes.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 60 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 60 ° C
Additional drying time: 60 minutes

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
With respect to this [toner 11] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

[Example 12]
(Preparation of Toner 12)
In Example 1, 30 parts of [WAX3] and 10 parts of [WAX7] were used instead of [WAX1] as a release agent, and under the toner preparation conditions, the drying temperature was 50.degree. C. [Toner 12] was obtained in the same manner as in Example 1 except that the drying time was 60 minutes.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 50 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 60 ° C
Additional drying time: 60 minutes

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
Regarding this [toner 12] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

[Example 13]
(Preparation of Toner 13)
In Example 1, 7.5 parts of [WAX 3] and 2.5 parts of [WAX 7] were used as a release agent instead of [WAX 1], and the drying temperature was 70 ° C. as described below under the toner preparation conditions. [Toner 13] was obtained in the same manner as in Example 1 except that the drying time for additional drying was 60 minutes.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 70 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 60 ° C
Additional drying time: 60 minutes

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
Regarding this [toner 13] in the same manner as in Example 1, the content of releasing agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

Comparative Example 1
(Preparation of Toner 14)
[Toner 9] was obtained in the same manner as in Example 1 except that [WAX 4] was used in place of [WAX 1] as a release agent in Example 1.
[WAX 4] is a synthetic ester wax having a melting point of 75.2 ° C. and a recrystallization temperature of 64.3 ° C. (WEP-2: manufactured by NOF Corporation). Both [WAX 4] and [polyester resin A] were transparently dissolved in ethyl acetate without phase separation.
In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
About this [Toner 14] in the same manner as in Example 1, the content of releasing agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

Comparative Example 2
(Preparation of Toner 15)
[Toner 15] was obtained in the same manner as in Example 1 except that [WAX 5] was used in place of [WAX 1] as a release agent in Example 1.
[WAX5] is a synthetic ester wax (WEP-5: manufactured by NOF Corporation) mainly composed of an aliphatic ester having a melting point of 82 ° C and a recrystallization temperature of 70 ° C. Both [WAX 5] and [Polyester Resin A] were dissolved in ethyl acetate transparently without phase separation.
In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
About this [Toner 15] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

Comparative Example 3
(Preparation of Toner 16)
[Toner 16] was obtained in the same manner as in Example 1 except that [WAX 6] was used in place of [WAX 1] as a release agent in Example 1.
Note that [WAX6] is paraffin wax having a melting point of 68 ° C. and a recrystallization temperature of 60 ° C. (HNP-11: manufactured by Nippon Seikei Co., Ltd.). Both [WAX 6] and [Polyester Resin A] were transparently dissolved in ethyl acetate without phase separation.
In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
Regarding this [Toner 16] in the same manner as in Example 1, the content of releasing agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

Comparative Example 4
(Preparation of Toner 17)
[Toner 17] was obtained in the same manner as in Example 1 except that [WAX 7] was used in place of [WAX 1] as a release agent in Example 1.
[WAX7] is a synthetic ester wax mainly composed of an aliphatic ester having a melting point of 64.6 ° C and a recrystallization temperature of 57.0 ° C (WAX-16: manufactured by NOF CORPORATION) [WAX7] And [Polyester resin A] were both dissolved in ethyl acetate transparently without phase separation.
In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
About this [Toner 17] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

Comparative Example 5
(Preparation of Toner 18)
The same procedure as in Example 1 was repeated except that [WAX3] was used instead of [WAX1] as a release agent in Example 1 and that additional drying was not performed as described below under toner preparation conditions. Obtained [Toner 18].

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 60 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: none Additional drying time: none

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
With respect to this [Toner 18] in the same manner as in Example 1, the content of the releasing agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, the separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

Comparative Example 6
(Preparation of Toner 19)
Example 1 was used except that [WAX 3] was used instead of [WAX 1] as a release agent in Example 1 and that the drying temperature was 40 ° C. and additional drying was not performed as described below under toner preparation conditions. [Toner 19] was obtained in the same manner as in.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 40 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: none Additional drying time: none

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
Regarding this [Toner 19] in the same manner as in Example 1, the content of release agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

Comparative Example 7
(Preparation of Toner 20)
Example 1 was repeated except that [WAX3] was used instead of [WAX1] as the release agent, and that the drying temperature was changed to 40 ° C. as described below under the toner preparation conditions, as in Example 1 [ Toner 20] was obtained.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 40 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 60 ° C
Additional drying time: 30 minutes

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
About this [toner 20] in the same manner as in Example 1, the content of releasing agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

Comparative Example 8
(Preparation of Toner 21)
In the same manner as in Example 1 except that [WAX3] was used in place of [WAX1] as a release agent in Example 1 and that the additional drying temperature was changed to 70 ° C. as described below under toner preparation conditions. An attempt was made to make the toner 21. However, blocking occurred upon additional drying and toner particles were not obtained.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 60 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: 70 ° C
Additional drying time: 30 minutes

Comparative Example 9
(Preparation of Toner 22)
[Toner 22] was obtained in the same manner as in Example 11 except that additional drying was not performed under toner preparation conditions in Example 11.

[Toner preparation conditions]
Longitudinal length L of liquid column resonance liquid chamber: 1.85 mm
Discharge hole opening: Diameter 8.0 μm
Droplet discharge temperature: 40 ° C
Drying temperature (nitrogen): 60 ° C
Ethyl acetate relative humidity (in nitrogen stream): 8%
Driving frequency: 340kHz
Applied voltage to piezoelectric: 10.0 V
Additional drying temperature: not implemented Additional drying time: not implemented

In addition, although the preparation of the toner was continuously performed for 6 hours, the discharge holes were not clogged.
About this [toner 22] in the same manner as in Example 1, the content of releasing agent determined by DSC (differential scanning calorimeter) method, Wsa / Wta, separation of 0.3 μm from the surface by the FTIR-ATR method The amount of template was determined.
Table 1 shows the types of WAX and resin used for preparation of the toner and the preparation conditions of the toner, and Table 2 shows physical properties and the like of the toner.

[Preparation of carrier]
Silicone resin (organo straight silicone) 100 parts Toluene 100 parts γ- (2-aminoethyl) aminopropyltrimethoxysilane 5 parts Carbon black 10 parts The above mixture was dispersed with a homomixer for 20 minutes to prepare a coating layer forming solution. The coating layer forming solution was coated on the surface of 1000 parts of spherical magnetite having a particle diameter of 50 μm using a fluidized bed type coating apparatus to obtain a magnetic carrier.

[Preparation of two-component developer]
Four parts of the obtained toners 1 to 22 and 96.0 parts of the above magnetic carrier were mixed in a ball mill to prepare two-component developers 1 to 22 of Examples 1 to 13 and Comparative Examples 1 to 9.

[Evaluation result of two-component developer]
The evaluations of cold offset property, charging stability, image stability and storage stability were carried out using developers 1 to 22 according to the evaluation methods shown below, and the evaluation results are shown in Table 3 below. Further, evaluation methods of the particle size and particle size distribution of the toner are also described below.

(Evaluation method)
<Cold offset property>
Using a commercially available copier copier imageo Neo C600 manufactured by Ricoh Co., Ltd., an image that forms a rectangle of 3 cm × 5 cm on A4 size paper (T6000 70 W T, manufactured by Ricoh Co., Ltd.) 5 cm from the leading edge of the paper A toner sample with an adhesion amount of 0.85 mg / cm 2 was prepared at the position of Subsequently, the temperature of the fixing member was constantly controlled at 130 ° C., and the toner was fixed at a linear velocity of 300 mm / sec (the toner weight was calculated from the weight of the sheet before and after the image output). At 130 ° C, the occurrence of offset was judged by the visual evaluation of the tester based on the criteria ◎: No cold offset occurred ○: There were minute cold offset spots but three or less spots Δ: Minute cold offset Occurrence of more than 3 locations ×: Cold offset has occurred

<Image stability evaluation>
A developer is placed in a commercially available copying machine (Imaggio-Neo 455, manufactured by Ricoh Co., Ltd.), and a continuous running test of 50,000 sheets and 100,000 sheets is performed using a Ricoh type 6000 paper with a printing rate of 7% of the image occupancy rate The image quality (image density, thin line reproducibility) of the 50,000th sheet was evaluated based on the following criteria.
○: A good image similar to the initial image even on the 50,000th sheet :: A change from the initial image in any of the evaluation items of image density and thin line reproducibility, but a change in the allowable range × : When the evaluation item of either image density or fine line reproducibility causes a clear change from the initial image, which is not an acceptable level

Evaluation of friability
After putting 650 g of the developer into a commercially available copying machine (RICOH MP C6502, manufactured by Ricoh Co., Ltd.) and setting that only the developing unit is driven without printing an image, the developing agent is subjected to idle stirring for 20 hours. Was produced.
(Measurement of small particle rate)
After stirring, the toner was separated according to the following procedure, and measurement was carried out using FPIA-3000. The small particle ratio is the number frequency of toners of 3.5 μm or less, and the subtraction value of the small particle ratio between the initial toner and the deteriorated toner is taken as Δ small particle ratio. The toner having high stress resistance has a small Δ small particle rate, and the toner having low stress resistance has a large Δ small particle rate due to crushing.
(Separation method of toner in agent after sticking evaluation)
After 2 g of the deterioration agent was diluted 3 times with 1 g of dry well (manufactured by Fujifilm Corporation) with ion-exchanged water, and further 15 g of ion-exchanged water was weighed, it was put into an ultrasonic cleaner and dispersed for 1 minute. The supernatant was collected and toner particles were measured by FPIA-3000.
〔Evaluation criteria〕
:: Δ small particle rate is less than 1% ○: Δ small particle rate is 1% or more and less than 5% Δ: Δ small particle rate is 5% or more and less than 10% ×: Δ small particle rate is 10% or more

<Storage stability evaluation>
Each toner was filled in a 50 ml glass container and left in a 50 ° C. thermostat for 48 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K 2235-1991) and evaluated based on the following criteria. The larger the value of the penetration, the better the heat resistant storage stability, and if it is less than 5 mm, there is a high possibility of problems in use.
〔Evaluation criteria〕
:: penetration 25 mm or more ○: penetration 15 mm or more and less than 25 mm Δ: penetration 5 mm or more and less than 15 mm ×: penetration 5 mm or less

2: Droplet discharge means 9: elastic plate 11: liquid column resonance drop discharge means 12: air flow passage 13: raw material storage container 14: toner composition liquid 15: liquid circulation pump 16: liquid supply pipe 17: liquid common supply path 18 : Liquid column resonance flow path 19: Discharge port 20: Vibration generating means 21: Droplet 22: Liquid return pipe 31: Air flow supply means 32: Air flow supply means 33: Transport air flow inlet 34: Transport air flow inlet 35: Air flow guide 36: Airflow clean flow means 41a: Transport air flow 41b: Transport air flow 60: Drying collection means 62: Toner collection means 63: Toner storage portion 65: Transport air flow outlet P1: Liquid pressure gauge P2: Chamber pressure gauge

JP, 2009-134061, A Patent No. 5146665 gazette JP 2012-185219 A JP, 2014-164274, A Patent No. 5451226

Claims (10)

  It is a toner containing at least a binder resin and a release agent, and a total area Wta of the release agent detected from a transmission electron microscope (TEM) photograph of a fractured surface of the toner is 0. The ratio of release agent area Wsa within 3 μm, Wsa / Wta is 2 to 5%, and exists in a depth area Aa from the surface of the toner to 1/4 (1/4 d) of the diameter d of the toner The relationship between WDa and WDb is WDa <WDb, where WDa is the number average particle diameter of the releasing agent and WDb is the number average particle diameter of the releasing agent present in the region Ab from Aa. A toner having a displacement of 700 nm or less when 250 μN is applied in a micro compression test.   The toner according to claim 1, wherein the solubility of the releasing agent is 70 g or more per 100 g of ethyl acetate at 45C.   The toner according to claim 1, wherein the solubility of the releasing agent is 200 g or more per 100 g of ethyl acetate at 45 ° C. 4.   The toner according to any one of claims 1 to 3, wherein the melting point of the release agent is 60 ° C or less.   2. The toner according to claim 1, wherein at least two recrystallization peaks in a DSC (differential scanning calorimeter) method of an extract obtained by Soxhlet extraction of the toner with hexane are at two places.   The toner according to claim 5, wherein two recrystallization peaks in the DSC method of the extract are 45 ° C or higher. Among the two recrystallization peaks in the DSC method of the extract, the recrystallization peak height Pt1 on the low temperature side and the recrystallization peak height Pt2 on the high temperature side, and the extract obtained by Soxhlet extraction with the hexane The toner according to claim 5 or 6, wherein the solubility S per 100 g of ethyl acetate at 45 ° C satisfies the following relationship.
S × (Pt1 + Pt2) / Pt1 70 70 Among the two recrystallization peaks in the DSC method of the extract, the recrystallization peak height Pt1 on the low temperature side, and the recrystallization peak height Pt2 on the high temperature side, and the extraction obtained by Soxhlet extraction with the hexane The toner according to claim 5 or 6, wherein the solubility S per 100 g of ethyl acetate of 45 ° C satisfies the following relationship.
S × (Pt1 + Pt2) / Pt1 ≧ 200   The toner according to any one of claims 1 to 8, wherein a displacement amount at the time of 250 μN application in the micro compression test of the toner is 500 nm or less. A two-component developer comprising at least the toner according to any one of claims 1 to 9 and a carrier.