JP5656604B2 - toner - Google Patents

Description

  The present invention is a toner used in an image forming method such as an electrophotographic method, an electrostatic printing method, and a toner jet method.

  In recent years, devices using electrophotography have begun to be used in printers for output of computers, facsimiles, etc., in addition to copying machines for copying original documents. In recent years, as the market expands, the number of cases where it is stored or used in various environments is increasing, so that it is required to maintain the quality at a higher level. For example, in the transportation stage, there may be a change in temperature (heat cycle) between day and night for a long time. In addition, the temperature and humidity may not be properly controlled in the warehouse or in the usage environment, and therefore, there are cases where the product is kept in a harsh environment. Under such circumstances, there is a need for a design that can maintain toner performance even after long-term storage under high temperature and high humidity and heat cycle.

  In order to obtain excellent developability, it is important to disperse the wax in the toner. In particular, polyester resins are preferably used from the viewpoint of low-temperature fixability, but modified waxes are used to improve the dispersion of wax components. However, a toner using a modified wax has a drawback that when it is placed in a high-temperature environment or a high-humidity environment, the modified wax gradually exudes to the surface of the toner, and a density drop or image defect is likely to occur due to poor charging. It was.

  Several methods using modified waxes for polyester resins have been studied. Patent Document 1 discloses a method of adding modified polyethylene to a polyester resin. Patent Document 2 discloses a method using an acid-modified wax for a polyester resin. However, in these techniques, there is room for further improvement in performance when the toner is placed under high temperature and high humidity or subjected to heat cycle.

  Patent Document 3 discloses a method of polymerizing a resin mainly composed of a polyester resin in the presence of a wax component. However, when the toner is placed under high temperature and high humidity or subjected to a heat cycle, there is a possibility that an image defect may occur.

  Many techniques for removing residual monomers and oligomers in a resin using a thin film evaporator have been disclosed. For example, Patent Document 4 discloses a method for removing a devolatilized component using a thin film evaporator when removing a volatile component from a resin composition comprising a styrene acrylic copolymer and a volatile component. Patent Document 5 discloses a toner having a volatile component content of 200 ppm or less, preferably using a thin film evaporator. Patent Document 6 discloses a technique in which urethane-modified polyester is passed through a thin film evaporator to remove xylene and used as a toner binder.

  However, in these techniques, no reference is made to melting and kneading the polymerized resin before introducing it into a thin film evaporator, and to a toner using a modified wax, and the toner is placed under high temperature and high humidity. It may have been inadequate in terms of performance when subjected to heat cycles.

JP 2007-148085 A JP 2003-043729 A JP 2009-139844 A JP-A-8-041123 Japanese Patent Laid-Open No. 11-133663 JP 2002-055521 A

  The object of the present invention is that when a modified wax is used in a toner using a polyester resin component having excellent low-temperature fixability, blocking is unlikely to occur even when the toner is left under high temperature and high humidity or subjected to a heat cycle. An object of the present invention is to provide a toner that is less prone to density reduction and image defects.

In order to achieve the above object, the present invention is a toner containing at least a binder resin, a colorant and a wax component A,
The wax component A may have a ester group, a carboxyl group, one or more functional groups selected from hydroxyl,
The binder resin,
i) A polyester resin component as a main component,
ii) It was synthesized by polymerizing in the presence of the wax component A, and after cooling, solidified by cooling, the solidified product was melted and kneaded and introduced into a thin film evaporator in a molten state, and volatile components were distilled off. It is related with the toner characterized by being obtained through the process of carrying out.

  According to the present invention, even in a toner using a modified wax as a binder resin containing a polyester resin component as a main component, blocking is unlikely to occur when the toner is left for a long period of time under high temperature and high humidity. Thus, it is possible to obtain a toner that hardly causes a decrease in density even when the image is printed.

It is a schematic sectional drawing which shows an example of the thin film evaporator suitable for this invention.

  When using a binder resin whose main component is a polyester resin component with excellent low-temperature fixability, increase the dispersibility of the wax component to make the composition of the toner surface uniform, increase the chargeability, and improve the developability. Was necessary. For this purpose, it is effective to use a wax component A having one or more functional groups selected from an ester group, a carboxyl group, and a hydroxyl group.

  However, when the toner is left for a long period of time under high temperature and high humidity, the binder resin mainly comprises a wax component A having one or more functional groups selected from an ester group, a carboxyl group, and a hydroxyl group, and a polyester resin component. Are mutually polar. For this reason, when the polyester resin component and the wax component A are simply mixed at the time of toner formation, they are easily compatible with each other, so that the wax component A easily moves through the polyester resin component and easily oozes out on the toner surface. As a result, when the toner was left for a long time under high temperature and high humidity, blocking (a phenomenon in which the toner aggregated) was liable to occur, and the density was liable to decrease.

  As a result of investigations on these problems by the present inventors, a polyester resin component polymerized by the presence of a wax component A having one or more functional groups selected from an ester group, a carboxyl group, and a hydroxyl group is mainly used. The resin as a component is cooled and solidified after polymerization, and the solidified product is melted and kneaded, introduced into a thin film evaporator in a molten state, and obtained through a process of distilling off volatile components. It has been found that blocking is difficult to occur even when left for a long period of time under high temperature and high humidity, and it is difficult to cause a decrease in density even when printing under high temperature and high humidity.

  The resin after polymerization is referred to as an intermediate binder resin. By polymerizing the intermediate binder resin in the presence of the wax component A, the wax component A can be finely dispersed in the intermediate binder resin. This is because the wax component A having one or more functional groups selected from an ester group, a carboxyl group, and a hydroxyl group and a binder resin mainly composed of a polyester-based resin component have polarities, so that they are familiar with each other. This is because it is easy.

  Furthermore, it is important to cool and solidify the intermediate binder resin after polymerization. The cooled and solidified resin is called a solidified product. By cooling and solidifying the intermediate binder resin after polymerization, re-aggregation of the finely dispersed wax component A can be effectively prevented.

  Further, it is important to melt and knead the solidified product. The kneaded resin is referred to as a post-kneaded resin. By melting and kneading the solidified product and applying shear to the resin, the finely dispersed wax component A can be uniformly dispersed throughout the resin after kneading. The solidified product may be pulverized before proceeding to the next step.

  Subsequently, it is important to go through the step of introducing the melted and kneaded resin into the thin film evaporator and distilling off the volatile components. Since the inside of the thin film evaporator is heated and decompressed, the resin can be polymerized after kneading, and the wax component A finely dispersed throughout the resin after the kneading is taken in and immobilized so as to be included in the molecular structure of the resin. It is.

  As described above, the binder resin containing the polyester resin component of the present invention as a main component is polymerized in the presence of the wax component A, solidifies by cooling after polymerization, melts and kneads the solidified product, and evaporates the thin film in a molten state. It is obtained by introducing into a machine and obtaining through a step of distilling off volatile components. As a result, the wax component A can be finely dispersed uniformly throughout the binder resin, and can be included and immobilized in the molecular structure of the binder resin.

  As a result, even when the toner is left for a long period of time under high temperature and high humidity, the wax component A is included in the molecular structure of the binder resin, so that the toner is prevented from seeping out and blocking is unlikely to occur. It is possible to obtain a toner in which charging failure is suppressed and the density is hardly lowered. Further, since the thin film evaporator is under heating and decompression conditions, volatile components are also distilled off at the same time.

  If the wax component A is not added at the time of polymerization of the binder resin but is added only at the time of toner formation, the composition of the toner surface becomes non-uniform because it is difficult to finely disperse the wax component A in the binder resin. In some cases, the chargeability does not increase, and the developability may decrease.

  When the intermediate binder resin after polymerization is not cooled and solidified once, the wax component A will re-aggregate even if the wax component A is finely dispersed in the intermediate binder resin.

  In other words, once the intermediate binder resin after polymerization is melt-kneaded without being cooled and solidified, the time during which the resin is exposed to heat increases from polymerization to melt-kneading. It becomes easy.

  When the wax component A is re-aggregated, the composition of the toner surface becomes non-uniform and the charge distribution is broadened, so that the developability tends to decrease.

  When the solidified product is not melt-kneaded, the wax component A cannot be uniformly dispersed throughout the resin after kneading due to the share of kneading.

  That is, when the solidified product is passed through a thin film evaporator without being melt-kneaded, the wax component A is finely dispersed in the resin, but the distribution of the wax component A in the resin is non-uniform, so that However, it becomes a toner having a non-uniform composition distribution, and the charge distribution is broadened, so that developability tends to be lowered.

  When not passing through the thin film evaporator, the wax component A finely dispersed throughout the binder resin is less likely to be included in the molecular structure of the binder resin. A tends to ooze out to the toner surface, blocking is likely to occur, and the density tends to decrease due to poor charging. Further, when the thin film evaporator is not passed, volatile components are likely to remain in the binder resin, and thus the volatile components are likely to plasticize the binder resin. And the molecular structure of the binder resin containing the wax component A becomes easy to move, and the wax component A becomes easy to move in the binder resin. As a result, when the toner is left for a long period of time under high temperature and high humidity, the toner surface easily oozes out, blocking is likely to occur, and density reduction due to poor charging is also likely to occur.

  A wax component A having one or more functional groups selected from an ester group, a carboxyl group, and a hydroxyl group is uniformly and finely dispersed throughout the polyester resin component. The toner using the binder resin at this stage is excellent in developability, but if left for a long time under high temperature and high humidity, the wax component A gradually exudes to the toner surface, so that the developability deteriorates. And blocking could be worsened.

  The composition of the polyester resin component used in the present invention is as follows.

  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, and bisphenol represented by the formula (A) and derivatives thereof;

（式中Ｒはエチレンまたはプロピレン基であり、ｘ，ｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０乃至１０である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 to 10.)

  And diols represented by the formula (B);

  Examples of the divalent acid component include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride or anhydrides thereof, lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid. Dicarboxylic acids and derivatives thereof such as acids or anhydrides thereof, lower alkyl esters; alkenyl succinic acids or alkyl succinic acids such as n-dodecenyl succinic acid and n-dodecyl succinic acid, or anhydrides, lower alkyl esters thereof, and the like.

  Further, a trivalent or higher alcohol component or a trivalent or higher acid component may be used as necessary.

  Examples of the trihydric or higher polyhydric alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butane. Triol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, etc. Is mentioned.

  Examples of the trivalent or higher polyvalent carboxylic acid component include pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2 , 4-Naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, and their anhydrides, lower alkyl esters;

（式中Ｘは炭素数３以上の側鎖を１個以上有する炭素数５乃至３０のアルキレン基又はアルケニレン基）
で表わされるテトラカルボン酸等、及びこれらの無水物、低級アルキルエステル等の多価カルボン酸類及びその誘導体が挙げられる。なかでも、１，２，４−ベンゼントリカルボン酸、１，２，５−ベンゼントリカルボン酸およびこれらの無水物、低級アルキルエステルが好ましい。

(Wherein X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having one or more side chains having 3 or more carbon atoms)
And polycarboxylic acids such as anhydrides and lower alkyl esters thereof and derivatives thereof. Of these, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, anhydrides thereof, and lower alkyl esters are preferable.

  The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%, and the acid component is 60 to 40 mol%, preferably 55 to 45 mol%. The trivalent or higher polyvalent component is preferably 0.1 to 60 mol% in all components.

  The polyester resin component is usually obtained by a generally known condensation polymerization. The polymerization reaction of the polyester resin component is usually carried out in the presence of a catalyst at a temperature of about 150 to 300 ° C., preferably about 170 to 280 ° C. The reaction can be carried out under normal pressure, reduced pressure, or increased pressure. After reaching a predetermined reaction rate (for example, about 30 to 90%), the reaction system is 200 mmHg or less, preferably 25 mmHg or less, more preferably 10 mmHg. It is desirable to carry out the reaction under reduced pressure below.

  Examples of the catalyst include catalysts usually used for polyesterification, for example, metals such as tin, titanium, antimony, manganese, nickel, zinc, lead, iron, magnesium, calcium, germanium; and these metal-containing compounds (dibutyltin oxide, orthodibutyl). Titanate, tetrabutyl titanate, tetraisopropyl titanate, zinc acetate, lead acetate, cobalt acetate, sodium acetate, antimony trioxide, etc.).

  The binder resin used in the present invention may contain other resin components as long as the polyester resin component is a main component. As other resin components used in the present invention, conventionally known various resin components can be used. In particular, vinyl resin components are more preferable in terms of developability. If the polyester resin component is the main component, other resin components can be used alone or in combination of two or more with the polyester resin component. Here, the main component means that it accounts for 50% by mass or more with respect to the total amount of the binder resin.

  Examples of the monomer for obtaining the vinyl resin component include the following.

  For example, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4- Dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl Styrene derivatives such as styrene; Ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; Unsaturated polyenes such as butadiene and isoprene; Vinyl halides such as vinyl chloride, vinyl bromide and vinyl fluoride; Acetic acid Vinyl esthetics such as vinyl, vinyl propionate and vinyl benzoate Class: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acid, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, Acrylic esters such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether, vinyl ethyl ether Ter, vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N- such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone. Vinyl compounds; vinyl naphthalenes; and acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide. These vinyl monomers are used alone or in admixture of two or more monomers.

  Among these, a combination of monomers that becomes a styrene copolymer or a styrene acrylic copolymer is preferable.

  Further, as monomers for adjusting the acid value of the resin component, for example, acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, and α- or β-alkyl derivatives thereof, fumaric acid, maleic acid, citracone There are unsaturated dicarboxylic acids such as acids and their monoester derivatives or maleic anhydride, and the desired resin component can be made by copolymerizing such monomers alone or in combination with other monomers. .

  Moreover, it is also possible to add a crosslinkable monomer as exemplified below.

  As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by alkyl chains (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate) , 1,5-pentanediol acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); di-linked by an alkyl chain containing an ether bond Acrylate compounds (eg, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds linked by a chain containing an aromatic group and an ether bond (eg, polyoxyethylene (2 ) -2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and acrylates of the above compounds are replaced with methacrylate. Polyester type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)). Polyfunctional crosslinkers include pentaerythritol acrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate. Alternatives: triallyl cyanurate, triallyl trimellitate and the like.

  These crosslinking agents are preferably used in an amount of 1 part by mass or less, preferably 0.001 to 0.05 parts by mass with respect to 100 parts by mass of other vinyl monomer components.

  In order to achieve the object of the present invention, the vinyl resin component used for the preparation of the binder resin is produced by using a polyfunctional polymerization initiator alone or in combination with a monofunctional polymerization initiator as exemplified below. It is preferable.

  Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,3-bis- (t-butylperoxy Isopropyl) benzene, 2,5-dimethyl-2,5- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, tris- (t -Butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2-di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n- Butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, di-t-butylperoxytrimethyladipate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) has a polymerization initiation function such as two or more peroxide groups in one molecule such as propane, 2,2-t-butylperoxyoctane and various polymer oxides. In one molecule such as a polyfunctional polymerization initiator having a functional group, diallyl peroxydicarbonate, t-butylperoxymaleic acid, t-butylperoxyallylcarbonate, and t-butylperoxyisopropyl fumarate, Examples thereof include polyfunctional polymerization initiators having both a functional group having a polymerization initiation function such as an oxide group and a polymerizable unsaturated group.

  Of these, more preferred are di-t-butylperoxyhexahydroterephthalate, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, di-t-butylperoxyase. Rate and 2,2-bis- (4,4-di-t-butylperoxycyclohexane) propane, and t-butylperoxyallyl carbonate.

  These polyfunctional polymerization initiators can be used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder for toner. In particular, it is preferable to use in combination with a polymerization initiator having a half-life of 10 hours lower than the decomposition temperature for obtaining a half-life of 10 hours of the polyfunctional polymerization initiator.

  Specifically, benzoyl peroxide, n-butyl-4,4-di (t-butylperoxy) valerate, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t- Examples thereof include organic peroxides such as butyl peroxycumene and di-t-butyl peroxide, and azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

  These monofunctional polymerization initiators may be added to the monomer at the same time as the polyfunctional polymerization initiator, but in order to keep the efficiency of the polyfunctional polymerization initiator appropriate, in the polymerization step, It is preferably added after the half-life indicated by the polyfunctional polymerization initiator has elapsed.

  These initiators are preferably used in an amount of 0.05 to 2 parts by mass with respect to 100 parts by mass of the monomer from the viewpoint of efficiency.

As a manufacturing method which can prepare the binder resin which has as a main component the polyester-type resin component used by this invention, the manufacturing method shown to the following (a) thru | or (d) can be mentioned, for example.
(A) A polyester resin component and another resin component are separately polymerized and then mixed to prepare a binder resin.
(B) The polyester resin component is polymerized first, and the other resin components are polymerized in the presence of the polyester resin component to prepare a binder resin.
(C) The other resin component is polymerized first, and the polyester resin component is polymerized in the presence of the other resin component to prepare a binder resin.
(D) A polyester resin component and another resin component are simultaneously polymerized to prepare a binder resin.

  (B) is mentioned as a manufacturing method of the binder resin which has as a main component the polyester-type resin component used especially preferably by this invention.

  In the present invention, it is necessary to polymerize a binder resin having a polyester resin component as a main component in the presence of a wax component A having one or more functional groups selected from an ester group, a carboxyl group, and a hydroxyl group. When the polymerization is performed in the presence of the wax component A, since the polymerization of the binder resin proceeds in a state where the wax component A is dissolved in the molten resin, the wax component A can be finely dispersed.

  The kneader used when melt-kneading the solidified material used in the present invention will be described. A well-known thing can be used as a kneading machine. The temperature of the molten binder resin discharged from the kneader is preferably 100 ° C. or higher and 200 ° C. or lower from the viewpoint of the shear applied to the binder resin and the dispersibility of the wax component A.

  The thin film evaporator used in the present invention will be described.

  The thin film evaporator is not particularly limited as long as it is an apparatus capable of reducing the pressure using a binder resin as a thin film, but a preferred apparatus is illustrated in FIG. As shown in FIG. 1, the thin film evaporator includes a tank unit 10 and a rotating shaft 11 that rotates in the tank, and the rotating shaft 11 includes a stirring blade 12. Further, the thin film evaporator has a steam outlet 2, heating medium inlets 5 and 6, and heating medium outlets 3 and 4 that serve as a heating medium path for heating the tank 10. It is preferable that a plurality of stirring blades 12 are provided in the longitudinal direction of the rotating shaft 11 and have a certain degree of inclination in the circumferential direction. When the molten binder resin is introduced into the thin film evaporator from the inlet 1, the molten resin is uniformly dispersed on the inner wall surface of the tank 10 by the distributor 8. The distributor 8 and the agitating blade 12 have a narrow clearance with an inner wall surface, and are provided with a mechanism for forcibly thinning the film by being driven and rotated by an upper motor (not shown). Due to the rotating operation of the stirring blade 12, the molten resin thinned is forcibly transferred to the lower resin outlet 7 side while the surface layer portion is constantly updated. During this time, the molten resin is finally discharged from the outlet 7 through the screw 7 through the screw 7 while being decompressed and preferably heated in the tank 10.

  The thickness of the binder resin to be made into a thin film can be adjusted by the distance between the inner wall surface of the tank 10 and the stirring blade 12, but is preferably 1 to 5 mm, more preferably 2 to 4 mm.

  When the atmospheric pressure in the tank is 0.3 Pa or more and 500 Pa or less, preferably 0.5 Pa or more and 200 Pa or less, the polymerization of the binder resin proceeds in the tank, which is preferable for obtaining the effects of the present invention.

  The tank 10 is preferably heated. In particular, when heated at 50 ° C. or more and 250 ° C. or less, more preferably 100 ° C. or more and 200 ° C. or less, and further preferably 150 ° C. or more and 190 ° C. or less, the polymerization of the binder resin easily proceeds. Further, the temperature of the binder resin when introducing the molten binder resin into the thin film evaporator is preferably matched with the temperature of the tank 10.

  The binder resin mainly composed of the polyester resin component used in the present invention preferably contains a hybrid resin in which a polyester resin component and a vinyl resin component are chemically bonded. Since the wax component A is not only included in the molecular structure of the polyester resin component, but is also included in the molecular structure of the vinyl resin component, the wax is more firmly fixed. As a result, the wax component A can be prevented from seeping out even after being subjected to a more severe standing condition, and the uniformity of the toner surface composition can be maintained. The developability can be maintained in image output. The heat cycle is a repetition of raising the temperature from room temperature to a high temperature and lowering the temperature to the room temperature again. Under the heat cycle, the molecular motion of the binder resin and the wax component A repeatedly stops and becomes intense, so that the oozing of the wax component A onto the toner surface is more severe.

  The hybrid resin is formed by a transesterification reaction between a polyester resin component and a vinyl resin component obtained by polymerizing a monomer component having a carboxylic acid ester group such as (meth) acrylic acid ester. ) Unsaturation produced by esterification reaction with a vinyl resin component obtained by polymerizing a monomer component having a carboxylic acid group such as acrylic acid, or using a monomer having an unsaturated group such as fumaric acid There are those formed by polymerizing vinyl monomers in the presence of a polyester resin component.

  The hybrid resin can be obtained by containing a monomer component capable of reacting with both resin components in the vinyl resin component and / or the polyester resin component and reacting them.

As a manufacturing method which can prepare the hybrid resin used by this invention, the manufacturing method shown to the following (1) thru | or (6) can be mentioned, for example.
(1) The hybrid resin component is manufactured separately from a vinyl resin component and a polyester resin component, dissolved and swollen in a small amount of an organic solvent, added with an esterification catalyst and alcohol, and heated to carry out a transesterification reaction. In this way, a hybrid resin having a polyester resin component and a vinyl resin component can be obtained.
(2) A method of producing a hybrid resin having a polyester resin component and a vinyl resin component by reacting the polyester resin component in the presence of the vinyl resin component after the production. The hybrid resin is produced by a reaction between a vinyl resin component (a vinyl monomer can be added if necessary) and a polyester monomer (alcohol, carboxylic acid) and / or a polyester resin component. Also in this case, an organic solvent can be appropriately used.
(3) This is a method for producing a hybrid resin having a polyester resin component and a vinyl resin component by producing and reacting a vinyl resin component in the presence of the polyester resin component after production. The hybrid resin is produced by a reaction between a polyester resin component (a polyester monomer can be added if necessary) and a vinyl monomer and / or a vinyl resin component.
(4) After producing the vinyl resin component and the polyester resin component, a hybrid resin is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer components. Also in this case, an organic solvent can be appropriately used.
(5) A vinyl-based resin component, a polyester-based resin component, a polyester-based resin component, and a vinyl-based resin are prepared by mixing a vinyl-based monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reactions. A hybrid resin having a resin component is produced. Furthermore, an organic solvent can be used as appropriate.

  In the above production methods (1) to (5), a vinyl resin component and / or a polyester resin component may use a polymer component having a plurality of different molecular weights and crosslinking degrees.

  (3) is mentioned as a manufacturing method used especially preferably by this invention. In particular, an unsaturated polyester resin that can react with a vinyl monomer is dissolved in a vinyl monomer, and a mixture of the polyester resin and the vinyl monomer is polymerized by a bulk polymerization method.

  In bulk polymerization, the molecular weight of the vinyl resin component can be increased, so the polyester resin component is hybridized to the vinyl resin component with a high molecular weight, resulting in a gel structure with a large molecular weight and a large molecular weight between cross-linking points. Can be obtained. Therefore, it becomes easy to take in the wax component A uniformly. In addition, since the bulk polymerization method does not require a step such as evaporation of the solvent as compared with the solution polymerization method, the binder resin can be obtained at low cost. Compared with the suspension polymerization method, it does not contain impurities such as dispersants, so it has a great merit as a binder resin for toners. ,preferable.

  When the hybrid resin in which the polyester resin component and the vinyl resin component are chemically bonded is contained, it is important that the polyester resin component is an unsaturated polyester resin component. The unsaturated polyester resin component used in the hybrid resin of the present invention includes a low molecular weight unsaturated polyester having a main peak in the molecular weight range of 2000 to 30000 (preferably 3000 to 20000) in the GPC molecular weight distribution of THF-soluble matter. A system resin component is preferably used.

  Furthermore, the linear unsaturated polyester-type resin component which does not contain a gel component is especially preferable.

  Further, the unsaturated polyester resin component used in the present invention has a number average molecular weight (Mn) of 2000 to 20000, preferably 3000 to 10,000. Further, the unsaturated polyester resin component used in the present invention has an excellent chargeability when the hydroxyl value is 10 to 110 mgKOH / g (preferably 15 to 90 mgKOH / g, more preferably 20 to 70 mgKOH / g). It is preferable because of its properties.

  When bulk polymerization of vinyl monomers is carried out in the presence of unsaturated linear polyester resin components, the main chain is a vinyl resin component having a high molecular weight and high linearity, and the low molecular weight polyester resin component is branched from the vinyl resin component. A hybrid resin component having a molecular structure of the shape is obtained. Furthermore, the acid group and the hydroxyl group in the hybrid resin component having this branched structure form an ester bond between molecules to form a gel component.

  As an acid component having an unsaturated group for obtaining an unsaturated polyester resin, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid, or anhydrides thereof, lower alkyl esters and the like are preferably used. These unsaturated dicarboxylic acids may be added at a ratio of 0.1 to 10 mol% (preferably 0.3 to 5 mol%, more preferably 0.5 to 3 mol%) with respect to the total acid component of the polyester monomer. preferable. When the unsaturated dicarboxylic acid is added in this range, the unsaturated group concentration in the low molecular weight polyester molecule is optimal.

  When a hybrid resin in which a polyester resin component and a vinyl resin component are chemically bonded is contained, an unsaturated polyvalent carboxylic acid ester monomer is preferably used for the vinyl resin component. Unsaturated polycarboxylic acid ester monomers include, for example, aliphatic unsaturated polycarboxylic acids such as fumaric acid, maleic acid, itaconic acid, mesaconic acid, citraconic acid, and aromatic unsaturated polycarboxylic acids such as phenylene diacrylic acid. And ester derivatives of polyvalent carboxylic acids.

  When a highly reactive unsaturated polyvalent carboxylic acid ester monomer is contained in the vinyl resin component, it is depressurized during polymerization or by a thin film evaporator, so that the hydroxyl group in the hybrid resin component having a branched structure and the intermolecular Can be ester-linked. When an unsaturated polyvalent carboxylic acid ester monomer is used for the vinyl resin component, since the binder resin is connected by an ester bond between molecules, the wax component A is more easily included in the molecular structure and immobilized.

  When the unsaturated polyvalent carboxylic acid ester monomer is used, it is possible to further suppress the exudation of the wax component A even after being subjected to a heat cycle which is a severe standing condition. As a result, the uniformity of the toner surface composition is maintained, so that the rising of the chargeability is good, and the density is easily obtained from the initial stage in image formation under high temperature and high humidity. This is because the binder resin is connected by an ester bond even between molecules, so that the wax component A is more strongly embedded and included in the molecular structure.

  The content of the unsaturated polyvalent carboxylic acid ester monomer in the vinyl resin component is 0.1% by mass or more and 20.0% by mass or less, preferably 0.3% by mass or more and 15.0% by mass or less. The wax component A is more easily included in the molecular structure and immobilized. As a result, the density is likely to be obtained from the initial stage even in image formation under high temperature and high humidity.

  More specifically, for example, monomethyl maleate, monoethyl maleate, diethyl maleate, monobutyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, heptyl maleate, ethyl butyl maleate, ethyl maleate Octyl, butyl octyl maleate, butyl hexyl maleate, pentyl octyl maleate, octyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, monoethyl fumarate, diethyl fumarate, monobutyl fumarate, dibutyl fumarate, Monophenyl fumarate, monocyclohexyl fumarate, dicyclohexyl fumarate, dipentyl fumarate, dihexyl fumarate, heptyl fumarate, octyl fumarate, fumaric acid Chirubuchiru, fumaric acid ethyl octyl, fumaric acid butyl octyl, fumaric acid butyl hexyl, fumaric acid pentyl octyl, monoethyl itaconate, diethyl itaconate, monobutyl itaconate, and itaconic acid dibutyl.

  In particular, in the present invention, an unsaturated dicarboxylic acid monoester is preferable in that a wax component is more fixed in the binder resin by selecting a monomer having higher reactivity.

  By depressurizing at the time of polymerization or with a thin film evaporator, an ester bond can be formed between the hydroxyl group in the hybrid resin component having a branched structure between the molecules. When a more reactive unsaturated dicarboxylic acid monoester is used, an ester bond between the molecules of the binder resin can be efficiently formed, so that the probability that the wax component A is included in the molecular structure and fixed is further increased. .

  When the unsaturated dicarboxylic acid monoester is used, since the exudation of the wax component A to the toner surface is further suppressed even when the toner is subjected to a heat cycle, it is difficult to form an aggregate even under high temperature and high humidity. And the white haze by the wax component A oozing out and forming the aggregate can be suppressed. The white haze is a phenomenon in which when toner aggregates and toner aggregates are present on the developing sleeve, only the portion is difficult to be properly developed and the image is whitened.

  From the viewpoint of easily forming an anhydride group, the preferred unsaturated dicarboxylic acid monoester is a maleic acid monoester or a fumaric acid monoester, and more preferably a maleic acid monoester. Of these, monobutyl maleate is particularly preferred from the viewpoints of reactivity with copolymerized styrene or acrylate monomers and ease of formation of acid anhydrides.

  In the present invention, a toner containing a gel component detected as a THF-insoluble component of the binder resin is advantageous in terms of durability even in image formation under high temperature and high humidity. In this invention, it is preferable to contain THF insoluble matter 5.0 mass% or more and 40.0 mass% or less.

  In the present invention, the binder resin preferably has a softening point of 100.0 ° C. or more and 160.0 ° C. or less from the viewpoints of durability for image formation and fixability under high temperature and high humidity.

  The wax component A used in the present invention will be described.

  It is important that the wax component A used in the present invention has one or more functional groups selected from an ester group, a carboxyl group, and a hydroxyl group. In particular, a polar wax having a hydroxyl group is preferable from the viewpoint of the dispersibility of the wax component A and the chargeability of the toner. Moreover, since it becomes difficult to aggregate after a heat cycle, it becomes difficult to generate white haze.

  The wax component A used in the present invention preferably contains a hydrocarbon molecular chain having the following structure.

  That is, it is essential to have at least a molecular chain having a secondary alcohol structure having a hydroxyl group on a secondary carbon, or a molecular chain having a primary alcohol structure having a hydroxyl group on a primary carbon, which can be represented by the following partial structural formulas A to E. And At the same time, it is essential to have a molecular chain having a carboxyl group in primary or secondary carbon, which can be represented by the following partial structural formulas C to D. The following partial structural formulas A to E and C to D may each have both in one hydrocarbon chain. Furthermore, you may have the molecular chain which has the structure of the ester which can represent with the following partial structural formula B and has an ester bond. More preferably, it is a hydrocarbon chain having a molecular chain having an alcohol structure represented by the following partial structural formulas A to E, C to D, and B, a carboxyl group, and an ester bond.

  Moreover, you may have the structure of arbitrary following partial structural formula A, B, C, D, and E in one hydrocarbon chain.

  The DSC melting peak temperature of the wax component A used in the present invention is preferably 60 ° C. or higher and 100 ° C. or lower, more preferably 70 ° C. or higher and 90 ° C. or lower. Within this range, both the ease of fine dispersion during polymerization of the binder resin and the suppression of the exudation of the wax component A when the toner is allowed to stand for a long time under high temperature and high humidity can be achieved. Therefore, even when the toner is left for a long period of time under high temperature and high humidity and then imaged under high temperature and high humidity, sleeve fusion is less likely to occur. The sleeve fusion is a phenomenon in which the wax component A exuded from the toner contaminates the sleeve surface and causes the toner to be poorly charged.

  In the present invention, in order to supplement low-temperature fixability and high-temperature offset resistance, the wax component A may be further added as needed when the toner is formed. Further, another wax component B different from the wax component A may be added. The wax component B may be added when the binder resin is polymerized or may be added when the toner is formed. Similarly to the wax component A, it is preferable to add it during the polymerization of the binder resin because the dispersibility of the wax component B can be improved.

  The wax component B used in the present invention preferably has a wax endothermic peak temperature of 70 ° C. or higher and 120 ° C. or lower in differential scanning calorimetry (DSC) measurement to obtain good developability.

  The toner of the present invention may further contain a magnetic material and be used as a magnetic toner. In this case, the magnetic material can also serve as a colorant.

  In the present invention, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite, and ferrite; metals such as iron, cobalt, and nickel, or these metals aluminum, cobalt, copper, lead, magnesium, tin And alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

  These ferromagnetic materials have an average particle size of 2 μm or less, preferably 0.05 to 0.5 μm. The amount contained in the toner is preferably 20 to 200 parts by mass with respect to 100 parts by mass of the resin component.

  As the colorant used in the present invention, a black colorant that is toned in black using carbon black, grafted carbon or the following yellow / magenta / cyan colorant can be used.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds, and the like are used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds, and the like are used.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. These colorants can be used alone or in combination and further in the form of a solid solution.

  The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin.

  The negatively chargeable toner of the present invention preferably contains a charge control agent for controlling the negatively chargeable toner to be negatively charged. There are the following substances as charge control agents.

  For example, an organic metal compound and a chelate compound are effective, and there are a monoazo metal compound, an acetylacetone metal compound, an aromatic hydroxycarboxylic acid, and an aromatic dicarboxylic acid metal compound. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol.

  Further, an azo metal compound represented by the following formula (1) shown below is preferable.

〔式中、Ｍは中心金属を示し、具体的にはＳｃ、Ｔｉ、Ｖ、Ｃｒ、Ｃｏ、Ｎｉ、ＭｎまたはＦｅ等があげられる。Ａｒはアリーレン基を示し、フェニレン基、ナフチレン基などがあげられ、置換基を有してもよく、置換基としては、ニトロ基、ハロゲン基、カルボキシル基、アニリド基および炭素数１以上１８以下のアルキル基、アルコキシ基などがある。Ｘ、Ｘ’、Ｙ及びＹ’はそれぞれ独立して−Ｏ−、−ＣＯ−、−ＮＨ−、−ＮＲ−（Ｒは炭素数１以上４以下のアルキル基）である。Ａ＋はカウンターイオンを示し、具体的には水素イオン、ナトリウムイオン、カリウムイオン、アンモニウムイオンあるいは脂肪族アンモニウムイオンを示す。〕

[In the formula, M represents a central metal, and specific examples include Sc, Ti, V, Cr, Co, Ni, Mn, and Fe. Ar represents an arylene group, and examples thereof include a phenylene group and a naphthylene group, which may have a substituent. Examples of the substituent include a nitro group, a halogen group, a carboxyl group, an anilide group, and those having 1 to 18 carbon atoms. Examples include an alkyl group and an alkoxy group. X, X ′, Y, and Y ′ each independently represent —O—, —CO—, —NH—, or —NR— (R represents an alkyl group having 1 to 4 carbon atoms). A + represents a counter ion, and specifically represents a hydrogen ion, a sodium ion, a potassium ion, an ammonium ion, or an aliphatic ammonium ion. ]

  In particular, Fe or Cr is preferable as the central metal in the above formula (1). Moreover, as a substituent substituted by the arylene group in the said Formula (1), a halogen atom, an alkyl group, or an anilide group is preferable. The counter ion in the above formula (1) is preferably a hydrogen ion, an alkali metal ammonium ion, or an aliphatic ammonium ion. A mixture of compounds having different counter ions is also preferably used.

  Alternatively, the basic organic acid metal compound represented by the following formula (2) also gives negative chargeability and can be used in the present invention.

In particular, the central metal in the above formula (2) is preferably Fe, Cr, Si, Zn, Zr or Al. Moreover, as a substituent substituted by the arylene group in the said Formula (2), an alkyl group, an anilide group, an aryl group, and a halogen atom are preferable. The counter ion in the above formula (2) is preferably a hydrogen ion, an ammonium ion, or an aliphatic ammonium ion.
Preferred control agents for negative charging include the following. Spiron Black TRH, T-77, T-95 (Hodogaya Chemical Co., Ltd.), BONTRON (registered trademark) S-34, S-44, S-54, E-84, E-88, E-89 ( Orient Chemical Industry Co., Ltd.).

  As a method of incorporating the charge control agent into the negatively chargeable toner, there are a method of adding it inside the negatively chargeable toner particles and a method of adding it externally. The amount of these charge control agents to be used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and a dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Quaternary ammonium salts such as 1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate; onium salts such as phosphonium salts and their lake pigments; analogs thereof; triphenylmethane dyes and these Lake pigments (phosphorungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; dibutyltin oxide And diorganotin oxides such as dioctyltin oxide and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate and dicyclohexyltin borate, and the like. These can be used alone or in combination of two or more.

  The charge control agent is preferably used in the range of 0.01 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the binder resin.

  A fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner particles to increase the fluidity before and after the addition. Examples of such fluidity improvers include fluorine resin powders such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fine powder silica such as wet process silica and dry process silica, and fine powder titanium oxide. , Fine powder alumina, fine powder treated with silane compound, titanium coupling agent, silicone oil; oxides such as zinc oxide and tin oxide; strontium titanate, barium titanate, calcium titanate, zircon Examples thereof include double oxides such as strontium acid and calcium zirconate; calcium carbonate and carbonate compounds such as magnesium carbonate.

A preferred fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is referred to as so-called dry process silica or fumed silica. For example, a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is used, and the basic reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

  In this production process, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. To do. The average primary particle size is preferably in the range of 0.001 to 2 μm, and it is particularly preferable to use silica fine powder in the range of 0.002 to 0.2 μm.

  Furthermore, as the fluidity improver used in the present invention, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of the silicon halogen compound is more preferable. In the treated silica fine powder, it is particularly preferable to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is in the range of 30 to 80.

  As a hydrophobizing method, it is applied by chemical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound.

As the fluidity improver, those having a specific surface area of 30 m ² / g or more, preferably 50 m ² / g or more by nitrogen adsorption measured by the BET method, give good results. A total of 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass of the fluidity improver is used with respect to 100 parts by mass of the toner.

  The toner of the present invention can be used as a one-component developer by mixing with the fluidity improver and, if necessary, further mixing with other external additives (for example, a charge control agent). And can be used as a two-component developer. As the carrier for use in the two-component development method, all conventionally known carriers can be used. Specifically, particles having an average particle diameter of 20 to 300 μm, such as metal such as surface oxidized or unoxidized iron, nickel, cobalt, manganese, chromium, rare earth, and alloys or oxides thereof, are preferably used.

  Further, those obtained by adhering or coating substances such as styrene resin, acrylic resin, silicone resin, fluorine resin, polyester resin on the surface of the carrier particles are preferably used.

  In order to produce the toner of the present invention, a mixture containing at least a binder resin and a colorant is used as a material, and a magnetic material, wax, a charge control agent, other additives, and the like are used as necessary. These materials are thoroughly mixed by a mixer such as a Henschel mixer or a ball mill, and then melted, kneaded and kneaded using a heat kneader such as a roll, a kneader and an extruder so that the resins are mutually compatible. Disperse the wax and magnetic material. After cooling and solidification, the toner can be obtained by pulverization and classification.

  Examples of the mixer include a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), a super mixer (manufactured by Kawata Corp.), and a nauter mixer (manufactured by Hosokawa Micron Corp.).

  As a kneading machine, for example, KRC kneader (manufactured by Kurimoto Iron Works); Bus co-kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works) A PCM kneader (manufactured by Ikekai Iron Works Co., Ltd.).

  Examples of the pulverizer include an inomizer (manufactured by Hosokawa Micron); a kryptron (manufactured by Kawasaki Heavy Industries); and a turbo mill (manufactured by Turbo Industry).

  Examples of the classifier include turbo classifier (manufactured by Nissin Engineering Co., Ltd.); micron separator, turboplex (ATP), TSP separator (manufactured by Hosokawa Micron Co.); elbow jet (manufactured by Nittetsu Mining Co., Ltd.).

  Examples of the sieving device used for sieving coarse particles and the like include Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resona sieve, gyro shifter (Tokuju Kogakusha Co., Ltd.), and the like.

  The toner of the present invention preferably has a weight average particle diameter (D4) of 3.0 μm or more and 10.0 μm or less.

  The measurement of various physical properties according to the present invention will be described below.

<Measurement method of THF-insoluble matter in binder resin>
The THF-insoluble content of the resin component in the binder resin is measured as follows.

  About 1.0 g of the binder resin is weighed (W1 g), put in a pre-weighed cylindrical filter paper (for example, trade name No. 86R (size 28 × 100 mm), manufactured by Advantech Toyo), and set in a Soxhlet extractor. Then, extraction is performed for 16 hours using 200 ml of tetrahydrofuran (THF) as a solvent. At this time, extraction is performed at a reflux rate such that the solvent extraction cycle is about once every 5 minutes.

  After the extraction is completed, the cylindrical filter paper is taken out and air-dried, and then vacuum-dried at 40 ° C. for 8 hours. The mass of the cylindrical filter paper including the extraction residue is weighed, and the mass of the extraction residue is subtracted from the mass of the cylindrical filter paper ( W2g) is calculated.

And a THF insoluble content can be calculated | required by subtracting content (W3g) of components other than a resin component like following formula (1).
THF insoluble matter (mass%) = {(W2-W3) / (W1-W3)} × 100 (1)

  Content of components other than a resin component can be measured by a well-known analysis means. When the analysis is difficult, the content of components other than the resin component (incineration residual ash content (W3′g)) in the toner is estimated as follows, and the THF-insoluble content is obtained by subtracting the content. be able to.

The incineration residual ash content in the binder resin is obtained by the following procedure. About 2 g of toner is weighed (Wag) into a 30 ml magnetic crucible weighed in advance. Put the crucible in an electric furnace, heat at about 900 ° C for about 3 hours, let cool in the electric furnace, let it cool in a desiccator at room temperature for more than 1 hour, weigh the mass of the crucible containing the incineration residual ash, and crucible The incineration residual ash content (Wbg) is calculated by subtracting the mass of. And the mass (W3'g) of the incineration residual ash content in sample W1g is computed by following formula (2).
W3 ′ = W1 × (Wb / Wa) (2)

In this case, the THF-insoluble matter is obtained by the following formula (3).
THF insoluble matter (mass%) = {(W2-W3 ′) / (W1-W3 ′)}
× 100 (3)

<Measuring method of melting point of wax component>
The peak temperature of the maximum endothermic peak of the wax is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 2 mg of the wax component is precisely weighed, placed in an aluminum pan, an empty aluminum pan is used as a reference, and the temperature rising rate is between a temperature range of 30 to 200 ° C. Measurement is performed at 10 ° C./min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 ° C. to 200 ° C. in the second temperature raising process is defined as the maximum endothermic peak of the endothermic curve in the DSC measurement of the toner of the present invention.

<Measurement method of weight average particle diameter (D4)>
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples.

  First, the method for producing the binder resin used in this example is shown below. Table 2 shows the characteristics of each binder resin, the presence or absence of melt kneading, and the conditions of the thin film evaporator. Table 1 shows the wax component A and the wax component B used in the present invention.

(Production example of polyester resin component)
The polyester monomer is mixed in the following ratio.
-Bisphenol derivative represented by the formula (A) (R-propylene group, average value of x + y-2.2) 1.150 mol
・ Terephthalic acid 0.430 mol
・ Isophthalic acid 0.390 mol
・ Fumaric acid 0.010 mol
・ Dodecenyl succinic anhydride 0.170 mol

  To these, 0.1% by mass of tetrabutyl titanate as a catalyst was added and subjected to condensation polymerization at 220 ° C. to obtain unsaturated polyester resin P-1 (Tg = 58 ° C., main peak molecular weight = 7800, number average molecular weight (Mn) = 4600, Mw / Mn = 2.1, acid value = 5 mgKOH / g, hydroxyl value = 37 mgKOH / g).

(Binder Resin Production Example 1)
Unsaturated polyester resin P-1 · 74.0 parts by mass, and vinyl monomer, styrene · 18.0 parts by mass, butyl acrylate · 6.5 parts by mass, monobutyl maleate · 1.5 parts by mass, initiator 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (10-hour half-life temperature 128.4 ° C.) · 0.08 parts by mass, and wax component 1 as 1 0.0 parts by mass and Fischer-Tropsch wax (melting point 105 ° C.) · 2.0 parts by mass as wax component B were mixed. After this vinyl monomer / polyester resin / wax component A / wax component B mixture was polymerized at 120 ° C. for 10 hours, the temperature was further raised to 150 ° C. and held for 3 hours to polymerize unreacted vinyl monomers. Thereafter, the temperature was further raised to 180 ° C. and the pressure was reduced for 5 hours to carry out a crosslinking reaction and alcohol removal to obtain a hybrid resin.

After cooling and solidifying the obtained hybrid resin, the solidified product was melt-kneaded, and this resin was introduced into a thin film evaporator (EXEVA EX-02 type) in a molten state. The conditions of the EXEVA were as follows: resin thickness: 3 mm, tank temperature setting: 190 ° C., stirring rotation speed: 250 rpm, pressure reduction degree: 1 Torr. The feed amount was 50 kg / m ² h.

  After passing through EXEVA, the resin was taken out and pulverized to obtain a hybrid resin. This is designated as binder resin 1.

  This resin had a tetrahydrofuran insoluble content of 20.0% and a softening point of 131 ° C.

(Binder Resin Production Example 2)
Binder resin 2 was obtained in the same manner as in Binder resin production example 1 except that the degree of vacuum was 0.9 Torr.

(Binder Resin Production Example 3)
Binder resin 3 was obtained in the same manner as in Binder resin production example 2 except that the jacket temperature was set to 175 ° C. in Binder resin production example 2.

(Binder Resin Production Example 4)
Binder resin 4 was obtained in the same manner as in Binder resin production example 3 except that the amount of wax component 1 added was 2.0 parts by mass in Binder resin production example 3.

(Binder Resin Production Example 5)
Binder resin 5 was produced in the same manner as in Binder resin production example 4, except that monobutyl maleate used for the vinyl monomer was changed to monoethyl maleate (1.5 parts by mass). Got.

(Binder Resin Production Example 6)
Binder resin 6 was obtained in the same manner as in Binder resin production example 5 except that the amount of monoethyl maleate used for the vinyl monomer was changed to 0.2 parts by mass in Binder resin production example 5. .

(Binder Resin Production Example 7)
Binder resin 7 was obtained in the same manner as in Binder resin production example 5 except that the amount of monoethyl maleate used in the vinyl monomer was changed to 16.0 parts by mass in Binder resin production example 5. .

(Binder Resin Production Example 8)
Binder resin production example 4 was the same as binder resin production example 4 except that monobutyl maleate used for the vinyl monomer was changed to dibutyl maleate (16.0 parts by mass). Got.

(Binder Resin Production Example 9)
In production example 4 of the binder resin, the vinyl monomer was styrene 18.0 parts by mass, butyl acrylate 6.5 parts by mass, acrylic acid 1.5 parts by mass, and 2,5-dimethyl-as an initiator. Except for setting the amount of 2,5-bis (t-butylperoxy) hexyne-3 (10-hour half-life temperature 128.4 ° C.) · 0.08 parts by mass in the same manner as in Binder Resin Production Example 4, A resin 9 was obtained.

(Binder Resin Production Example 10)
A binder resin 10 was obtained in the same manner as in the binder resin production example 9 except that the wax component 1 was changed to the wax component 2 in the binder resin production example 9.

(Binder Resin Production Example 11)
A binder resin 11 was obtained in the same manner as in the binder resin production example 9 except that the wax component 1 was changed to the wax component 3 in the binder resin production example 9.

(Binder Resin Production Example 12)
As the polyester monomer, 20.0 parts by mass of bisphenol A propylene oxide 2 mol adduct, 13.0 parts by mass of bisphenol A propylene oxide 3 mol adduct, 6.0 parts by mass of terephthalic acid, 6.0 parts by mass of isophthalic acid, and condensation Tetrabutyl titanate 0.1 mass part was put as a catalyst, and it was made to react for 10 hours, distilling off the water produced | generated under nitrogen stream at 220 degreeC. After adding 5.0 parts by mass of trimellitic anhydride and 2.0 parts by mass of wax component 3 as wax component A and 2.0 parts by mass of Fischer-Tropsch wax (melting point 105 ° C.) as wax component B to the reaction vessel, vinyl As monomers, styrene, 18.0 parts by weight, butyl acrylate, 6.5 parts by weight, acrylic acid, 1.5 parts by weight, and initiator as 2,5-dimethyl-2,5-bis (t-butyl per A mixture of oxy) hexyne-3 (10-hour half-life temperature 128.4 ° C.) · 0.08 parts by mass was added dropwise over 2 hours with stirring at 160 ° C. to react with the vinyl resin. Thereafter, the polyester resin is reacted at 210 ° C., and the binder resin is cooled, solidified and pulverized, and then the solidified product is melt-kneaded. Further, the resin is left in a molten state in a thin film evaporator (EXEVA EX- 02 type). The conditions of EXEVA are as shown in Table 2. After passing through EXEVA, the resin was taken out and pulverized to obtain a binder resin 12.

(Binder Resin Production Example 13)
Bisphenol A propylene oxide 2 mol adduct 40.0 parts by mass, bisphenol A propylene oxide 3 mol adduct 26.0 parts by mass, terephthalic acid 12.0 parts by mass, isophthalic acid 12.0 parts by mass and tetrabutyl titanate as a condensation catalyst 0.2 mass part was put and it was made to react for 10 hours, distilling off the water produced | generated under nitrogen stream at 220 degreeC. Next, 10.0 parts by weight of trimellitic anhydride, 2.0 parts by weight of wax component 3 and 2.0 parts by weight of Fischer-Tropsch wax (melting point 105 ° C.) are added as wax component B, and the reaction is performed for 2 hours under normal pressure sealing. The binder resin was solidified by cooling and pulverized, and then the solidified product was melt-kneaded. Furthermore, this resin was introduced into a thin film evaporator (EXEVA EX-02 type) in a molten state. The conditions of EXEVA are as shown in Table 2. After passing through EXEVA, the resin was taken out and pulverized to obtain a binder resin 13.

(Binder Resin Production Example 14)
A binder resin 14 was obtained in the same manner as in the binder resin production example 13 except that the wax component 3 was changed to the wax component 4 in the binder resin production example 13.

(Binder Resin Production Example 15)
Binder resin 15 was obtained in the same manner as in Binder resin production example 13 except that wax component 3 was changed to wax component 5 in binder resin production example 13.

(Binder Resin Production Example 16)
Binder resin 16 was obtained in the same manner as in Binder resin production example 13 except that wax component 3 was changed to wax component 6 in binder resin production example 13.

(Binder Resin Production Example 17)
A binder resin 17 was obtained in the same manner as in the binder resin production example 13 except that the wax component 3 was changed to the wax component 7 in the binder resin production example 13.

(Comparative Binder Resin Production Example 1)
In the binder resin production example 17, the comparative binder resin 1 was obtained in the same manner as in the binder resin production example 17 except that the wax component 7 was not added.

(Comparative Binder Resin Production Example 2)
In Production Example 17 of the binder resin, the binder resin was pulverized after cooling and solidification, and without melting and kneading, the pulverized solidified product was simply melted and remained in a molten state (EXEVA EX-02 type) The comparative binder resin 2 was obtained in the same manner as in the binder resin production example 17 except that the binder resin was introduced into (1).

(Comparative binder resin production example 3)
Binder resin production example 17 was the same as binder resin production example 17 except that it was melt-kneaded without being cooled and solidified after polymerization and introduced into a thin film evaporator (EXEVA EX-02 type) in a molten state. Similarly, a binder resin 3 for comparison was obtained.

(Production Example 4 for Comparative Binder Resin)
70.0 parts by mass of styrene, 24.0 parts by mass of n-butyl acrylate, 6.0 parts by mass of monobutyl maleate, 1.0 part by mass of di-t-butyl peroxide, and 2. wax component 7 as wax component A 0 parts by mass and 2.0 parts by mass of Fischer-Tropsch wax (melting point 105 ° C.) as wax component B were dropped into 200.0 parts by mass of xylene over 4 hours to complete the polymerization under reflux of xylene. After the binder resin was cooled and solidified and pulverized, the solidified product was melt-kneaded. Furthermore, this resin was introduced into a thin film evaporator (EXEVA EX-02 type) in a molten state. The conditions of EXEVA are as shown in Table 2. After passing through EXEVA, the resin was taken out and pulverized to obtain a binder resin 4 for comparison.

(Comparative binder resin production example 5)
In the binder resin production example 17, after the binder resin was cooled and solidified, melted and kneaded, it was not introduced into the thin film evaporator, and was then used in the same manner as in the binder resin production example 17 except that the binder resin for comparison was used. 5 was obtained. After melt kneading, the mixture was cooled and solidified.

(Comparative Binder Resin Production Example 6)
Unsaturated polyester resin P-1, 40.0 parts by mass, and vinyl monomer as styrene, 42.0 parts by mass, butyl acrylate, 15.0 parts by mass, monobutyl maleate, 3.0 parts by mass, initiator 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3 (10-hour half-life temperature 128.4 ° C.) · 0.18 parts by mass, and wax component 7 as wax component 2 0.0 parts by mass and Fischer-Tropsch wax (melting point 105 ° C.) · 2.0 parts by mass as wax component B were mixed. After this vinyl monomer / polyester resin / wax component A / wax component B mixture was polymerized at 120 ° C. for 10 hours, the temperature was further increased to 150 ° C. and held for 3 hours to polymerize unreacted vinyl monomers. After that, the temperature was further raised to 180 ° C. and the pressure was reduced for 5 hours to carry out a crosslinking reaction and alcohol removal to obtain a hybrid resin.

After cooling and solidifying the obtained hybrid resin, the solidified product was melt-kneaded, and this resin was introduced into a thin film evaporator (EXEVA EX-02 type) in a molten state. The conditions for the EXEVA were as follows: resin thickness: 3 mm, tank temperature setting: 175 ° C., stirring rotation speed: 250 rpm, pressure reduction degree: 0.9 Torr. The feed amount was 50 kg / m ² h. After passing through EXEVA, the resin was taken out and pulverized to obtain a hybrid resin. This is designated as comparative binder resin 6.

(Comparative Binder Resin Production Example 7)
In the binder resin production example 17, a comparative binder resin 7 was obtained in the same manner as in the binder resin production example 17 except that the wax component 7 was not added.

(Toner Production Example 1)
Binder resin 1 100 parts by mass Wax component 1 3.0 parts by mass Magnetic substance 95 parts by mass (particle size 0.21 μm, coercive force 4.8 kA / m, saturation magnetization 83.6 Am ² / kg, residual magnetization 5 .1 Am ² / kg)
Charge control agent (T-77 manufactured by Hodogaya Chemical Co., Ltd.) 2.0 parts by mass The above raw materials were premixed for 3 minutes with a Henschel mixer set at 450 rpm, and then mixed with a biaxial kneading extruder set at 130 rpm. The set temperature was adjusted so that the direct temperature near the outlet was 150 ° C. or higher and 160 ° C. or lower, and melt kneading was performed. The obtained kneaded product is cooled and coarsely pulverized by a cutter mill, and then the obtained coarsely pulverized product is finely pulverized using a turbo mill (manufactured by Turbo Kogyo Co., Ltd.) and a multi-division classifier using the Coanda effect is used. Then, toner particles 1 were obtained.

1.3 parts by mass of hydrophobic silica fine particles (BET 200 m ² / g silica fine particles generated by vapor phase oxidation of silicon halogen compound surface-treated with hexamethyldisilazane) with respect to 100 parts by mass of toner particles 1 The toner 1 was added and externally mixed with a Henschel mixer.

(Toner Production Examples 2 to 17, Comparative Toner Production Examples 1 to 7)
Toners 2 to 17 and comparative toners 1 to 7 were obtained in the same manner as in Toner Production Example 1 except that the binder resin and wax component A used in Toner Production Example 1 were as shown in Table 3.

[Examples 1 to 17, Comparative Examples 1 to 7]
Next, evaluation was performed using toners 1 to 17 and comparative toners 1 to 7 prepared as described above. As an evaluation machine, a magnetic one-component printer LaserJet P4515n (manufactured by Hewlett-Packard Company) was used. The evaluation results are shown in Table 3.

(1) Image printing under high temperature and high humidity after leaving at 45 ° C./95%/30 days The toner is left in an environment of 45 ° C./95% for 30 days. Thereafter, a predetermined process cartridge was filled with toner. A horizontal line pattern with a printing rate of 2% is set to 2 sheets / job, and the machine is set to stop the next job after the machine stops between jobs. The image density on the first and 15000th sheets was measured. The evaluation was performed under high temperature and high humidity (32.5 ° C., 85% RH) and normal temperature and normal humidity (25.0 ° C., 60% RH), which have more severe effects on the toner charging property.

(2) Sleeve Fusion The surface of the sleeve after a total of 15,000 image forming tests performed in (1) above was visually observed, and the degree of toner contamination was evaluated according to the following criteria. Evaluation was performed by image printing under high temperature and high humidity (32.5 ° C., 85% RH), which is a severe condition for sleeve fusion.
A: Contamination is not observed.
B: Minor contamination is observed.
C: Contamination is partially observed, but there is no influence on the image.
D: Contamination is partially observed and an influence on the image is observed.
E: Significant contamination is observed.
(If it is C or higher, there is no problem in practical use.)

(3) Blocking evaluation 10 g of toner is put in a 100 ml polycup, left at 50 ° C. for 3 days, and then visually evaluated.
A: Aggregates are not seen.
B: Aggregates are slightly seen but easily collapse.
C: Aggregates are seen but easily collapse.
D: Agglomerates are seen, but collapse if shaken.
E: Aggregates can be grasped and do not collapse easily.
(If it is C or higher, there is no problem in practical use.)

(4) Image output under high temperature and high humidity after heat cycle test The heat cycle test of the toner is as follows.
<1> Hold at 25 ° C for 1 hour <2> Increase temperature linearly to 45 ° C over 11 hours <3> Hold at 45 ° C for 1 hour <4> Reduce temperature linearly to 25 ° C over 11 hours The above <1> to <4> were taken as one cycle, and a total of 20 cycles were performed. The humidity was constant at 95%. Thereafter, a predetermined process cartridge was filled with toner. A horizontal line pattern with a printing rate of 2% is set to 2 sheets / job, and the machine is set to stop the next job after the machine stops between jobs. The image density on the first and 15000th sheets was measured. The evaluation was performed under high temperature and high humidity (32.5 ° C., 85% RH) and normal temperature and normal humidity (25.0 ° C., 60% RH), which have a more severe effect on the toner chargeability.

(5) White haze The toner after the heat cycle test prepared in the above (4) was filled in a predetermined process cartridge. The evaluation was performed under high temperature and high humidity (32.5 ° C., 85% RH), where the influence on toner cohesion is more severe. In the evaluation, a halftone pattern having a printing rate of 25% was continuously fed from the first sheet to the 30th sheet, and the occurrence of white haze was confirmed.
A: No occurrence.
B: One white haze occurs per sheet, but disappears when five sheets or less pass.
C: 2 to 5 white haze occurs per sheet, but disappears when 10 sheets or less pass.
D: 6 to 10 white haze occurs per sheet, but disappears when 30 sheets or less pass.
E: 11 or more white haze occurs per sheet and does not disappear even when 30 sheets are passed.
(If it is C or higher, there is no problem in practical use.)

(6) Low-temperature fixability As a fixing rubbing test, A4 plain paper for copying machines (105 g / m ² ) was adjusted so that the toner mass per unit area was 0.5 mg / cm ² , and 10 mm for density measurement. An image having many 3 × 3 space (600 dpi) images of × 10 mm is output, and the obtained fixed image is rubbed five times with sylbon paper applied with a weight of 50 g / cm ² , and the image density after rubbing Evaluation was made based on the following from the rate of decrease in The image density was measured by using a Macbeth reflection densitometer (Macbeth Co., Ltd.), measuring the relative density with respect to the printout image of the white background portion where the document density was 0.00, and the rate of decrease in image density after rubbing. The fixability by the fixing rubbing test has no practical problem if it is A to B. The evaluation was performed under normal temperature and normal humidity (25.0 ° C., 60% RH).
A: Less than 5% B: 5% or more and less than 10% C: 10% or more and less than 20% D: 20% or more

1: resin inlet, 2: steam outlet, 3, 4: heat medium outlet, 5, 6: heat medium inlet, 7: resin outlet, 8: distributor, 9: screw, 10: tank, 11: rotating shaft, 12: Stirring blade

Claims (5)

A toner containing at least a binder resin, a colorant, and a wax component A;
The wax component A may have a ester group, a carboxyl group, one or more functional groups selected from hydroxyl,
The binder resin,
i) A polyester resin component as a main component,
ii) It was synthesized by polymerizing in the presence of the wax component A, and after cooling, solidified by cooling, the solidified product was melted and kneaded and introduced into a thin film evaporator in a molten state, and volatile components were distilled off. A toner obtained through the step of:   The toner according to claim 1, wherein the wax component A has a melting point by DSC of 60 ° C. or more and 100 ° C. or less.   The toner according to claim 1, wherein the binder resin contains a hybrid resin in which a polyester resin component and a vinyl resin component are chemically bonded.   The vinyl resin component is obtained by copolymerizing at least an unsaturated polyvalent carboxylic acid ester monomer, and the content of the unsaturated polyvalent carboxylic acid ester monomer in the vinyl resin component is 0.1 mass. The toner according to claim 3, wherein the toner is at least 2% and at most 20.0% by mass.   The toner according to claim 4, wherein the unsaturated polycarboxylic acid ester monomer is an unsaturated dicarboxylic acid monoester.

Images