JP6700730B2 - Toner and method of manufacturing toner - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, a toner jet method, and a manufacturing method thereof.

With the recent widespread use of electrophotographic full-color copying machines, demands for high-speed printing and energy saving have been further increased. In addition, the usage environments of users have been diversified, and it is required that stable output of high-quality images is possible under various environments.
In order to support high-speed printing, a technique for melting the toner more quickly in the fixing process is being studied. Further, as an energy saving measure, a technique of fixing the toner at a lower temperature is being studied in order to reduce the power consumption in the fixing process.
In order to support high-speed printing and improve the low-temperature fixability of the toner, there are methods such as lowering the glass transition point or softening point of the binder resin of the toner and using a binder resin having a sharp melt property.

In recent years, in order to further improve the sharp melt property thereof, a toner in which a binder resin contains a crystalline polyester resin has been developed. By including the crystalline polyester in the toner, it is possible to maintain low-temperature fixability and storage stability because the hardness can be maintained up to the fix temperature even though the toner melts quickly at the fix temperature.
Patent Document 1 proposes a toner in which a crystalline polyester dispersant is used in addition to a main binder resin and a crystalline polyester, and the solubility parameter of the binder resin, the crystalline polyester, and the crystalline polyester dispersant is defined. ing. By adjusting the solubility parameter within the specified range, the crystalline polyester is finely dispersed in the binder resin and is not unevenly distributed on the toner surface, so that the low temperature fixability and filming are improved while satisfying the conventional storage properties. I am letting you.

Further, as one of methods for achieving both low temperature fixability and storage stability, it has been proposed to increase the molecular weight of the crystalline resin. As this method, in addition to increasing the molecular weight of the crystalline polyester itself, there is a method of using a urethane-modified or urea-modified crystalline polyester using diisocyanate or diamine.
Patent Document 2 proposes a toner using a modified crystalline polyester having a urethane or urea bond in the molecule. By using the modified crystalline polyester resin, it becomes possible to increase the weight average molecular weight of the crystalline resin, and it is possible to obtain a toner having both low temperature fixability and heat resistant storage stability at a high level and excellent cleaning properties. ing.

JP, 2012-063559, A JP, 2013-186219, A

However, when the output image under high temperature and high humidity and the output image under low temperature and low humidity are compared using the toner according to the above proposal, there are cases where different toner densities are obtained on the printed image. Therefore, it is not possible to stably output a high-quality image under various environments, which is the above market demand, and there is room for further improvement.
An object of the present invention is to provide a toner that solves the above problems. Specifically, it provides a toner that satisfies low-temperature fixability and heat-resistant storage stability, and that is excellent in environmental stability and that can stably obtain high-quality images even in environments such as high temperature and high humidity and low temperature and low humidity. That is.

As a result of intensive studies, the inventors of the present invention satisfied low-temperature fixability and heat-resistant storage stability, and were able to stably obtain high-quality images even under environments such as high temperature and high humidity and low temperature and low humidity. In order to provide a toner having excellent properties, it was found that it is important to contain a resin composition containing a structure in which a specific resin component has reacted and a specific modified polyester, and the present invention has been completed.
That is, the present invention relates to a toner having toner particles containing an amorphous resin, a resin composition, and a crystalline polyester resin,
The resin composition contains a polymer in which a styrene acrylic polymer is graft-polymerized on a polyolefin,
The crystalline polyester resin is a urethane-modified crystalline polyester resin,
The content of the crystalline polyester resin, based on the total of the non-crystalline resin and the crystalline polyester resin state, and are 1% by weight to 20% by weight,
The toner is characterized toner der Rukoto melt-kneading pulverization.
The present invention also provides a toner having toner particles containing an amorphous resin, a resin composition, and a crystalline polyester resin,
The resin composition contains a polymer in which a styrene acrylic polymer is graft-polymerized on a polyolefin,
The crystalline polyester resin is a urethane-modified crystalline polyester resin,
The content of the crystalline polyester resin is 1% by mass or more and 20% by mass or less based on the total amount of the amorphous resin and the crystalline polyester resin,
The crystalline polyester resin has a carboxylic acid unit, an alcohol unit and an isocyanate unit,
Based on the total number of moles of the unit, the content of the isocyanate unit is 1.0 mol% or more and 10.0 mol% or less,
The isocyanate unit is a unit derived from a linear aliphatic diisocyanate.
Further , the present invention relates to a method for producing the above toner.

  According to the present invention, there is provided a toner satisfying low-temperature fixability and heat-resistant storage stability, and having excellent environmental stability that can stably obtain a high-quality image even in an environment such as high temperature and high humidity or low temperature and low humidity. be able to.

The toner of the present invention is a toner having toner particles containing an amorphous resin, a resin composition, and a crystalline polyester resin, wherein the resin composition is a polymer in which a styrene-acrylic polymer is graft-polymerized onto a polyolefin. The crystalline polyester resin is a urethane-modified crystalline polyester resin, and the content of the crystalline polyester resin is 1% by mass or more and 20% by mass or more based on the total amount of the amorphous resin and the crystalline polyester resin. It is important that the content is not more than mass %.
It has been confirmed that the toner satisfying the above characteristics has markedly improved low-temperature fixability and heat-resistant storability and excellent environmental stability as compared with toners not satisfying these requirements.

Although the mechanism by which this effect appears is not completely clear, the present inventors presume as follows.
In the process of charging the toner under low temperature and low humidity, it is considered that the negative charge generated on the surface of the toner particle by rubbing with the carrier penetrates into the inside of the toner particle and the charge amount is determined. On the other hand, it is considered that the urethane-modified crystalline polyester resin has a property of easily trapping electrons by containing a nitrogen atom having a relatively high electronegativity in the molecule.
Therefore, by finely dispersing this urethane-modified crystalline polyester resin in the toner particles, the negative charge generated by the rubbing with the carrier is trapped in the urethane-modified crystalline polyester resin existing in the vicinity of the toner particle surface. Therefore, it becomes difficult for the negative charge to move inside the toner particles.
Therefore, it is presumed that excellent environmental stability was obtained by suppressing the charge amount of each toner particle under low temperature and low humidity and reducing the difference in charge amount between under high temperature and high humidity.

<Urethane-modified crystalline polyester resin>
As described above, it is important that the toner of the present invention contains the urethane-modified crystalline polyester resin. The content of the urethane-modified crystalline polyester resin is 1% by mass or more and 20% by mass or less based on the total amount of the amorphous resin and the crystalline polyester resin. It is preferably 5% by mass or more and 15% by mass or less. When the content of the urethane-modified crystalline polyester resin is within the above range, the urethane-modified crystalline polyester is dispersed in the toner in a finely dispersed state, and more favorable environmental stability can be obtained.
The crystalline polyester resin may be, for example, a urethane-modified crystalline polyester resin obtained by modifying the terminal of an unmodified crystalline polyester produced from an aliphatic dicarboxylic acid and an aliphatic diol with an isocyanate, or by modifying the unmodified crystalline polyesters with diisocyanate. It may be a urethane-modified crystalline polyester resin having a structure of being bonded with. From the viewpoint of negative charge trapping effect and fixability, a urethane-modified crystalline polyester resin having a structure in which unmodified crystalline polyesters are bonded with diisocyanate is preferable.
Such a urethane-modified crystalline polyester resin has a crystalline polyester moiety having a carboxylic acid unit and an alcohol unit, and an isocyanate unit derived from isocyanate. The crystalline polyester moiety is a degenerate product of an alcohol component containing an aliphatic diol having 6 to 18 carbon atoms as a main component and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms as a main component. It is preferable that they are united. In the present application, the main component means that the content is 50% by mass or more.

The peak temperature (Tp) of the endothermic peak of the urethane-modified crystalline polyester resin measured by DSC is preferably in the range of 40 to 100°C from the viewpoint of heat resistant storage stability.
From the viewpoint of fixing, the weight average molecular weight (hereinafter, referred to as Mw) of the tetrahydrofuran-soluble component of the urethane-modified crystalline polyester resin by gel permeation chromatography is preferably 5,000 to 100,000, more preferably 6,000 to 90,000, and further preferably. It is 8000 to 80,000.

The urethane-modified crystalline polyester resin has a carboxylic acid unit, an alcohol unit and an isocyanate unit, and the content of the isocyanate unit is 1.0 mol% or more and 10.0 mol% or less based on the total number of moles of the unit. Are preferable from the viewpoints of environmental stability and low temperature fixability. More preferably, it is 2 mol% or more and 7 mol% or less.
The carboxylic acid unit, the alcohol unit and the isocyanate unit are units derived from monomers of the carboxylic acid component, the alcohol component and the isocyanate component, respectively.
When the content of the isocyanate unit is at least the above lower limit, the effect of trapping the negative charge of the urethane-modified crystalline polyester resin is improved, and the environmental stability is improved. When the number of isocyanate units is more than the above range, the charging site of the toner is increased and the chargeability of the toner is improved, but from the viewpoint of environmental stability, the above range is preferable. The isocyanate unit is preferably a unit derived from a straight-chain aliphatic diisocyanate, and more preferably a unit derived from a straight-chain aliphatic diisocyanate having 4 to 8 carbon atoms.

In the following description, the alcohol component, the carboxylic acid component, and the isocyanate component used in the urethane-modified crystalline polyester resin will be shown respectively.
[Alcohol component]
As the alcohol component, a diol is preferable, an aliphatic diol is more preferable, a carbon number is preferably 2 or more and 36 or less, and more preferably 6 or more and 18 or less. Further, linear aliphatic diols are more preferable.
Since the aliphatic diol is a straight chain type, the crystallinity of the polyester resin is improved and the melting point is less likely to drop, so that the toner blocking resistance, the image storability and the low temperature fixability are improved. If the carbon number exceeds 36, it may be difficult to obtain the material in practical use.
The content of the linear aliphatic diol in the alcohol component is preferably 80 mol% or more and 100 mol% or less of the alcohol component used, and more preferably 90 mol% or more and 100 mol% or less. When it is 80 mol% or more, the crystallinity of the polyester resin is improved and the melting point is increased, so that the toner blocking resistance and the low-temperature fixability become better.

  Specific examples of the straight-chain aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7. -Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14 Examples thereof include, but are not limited to, tetradecanediol, 1,18-octadecanediol, and 1,20-eicosanediol. Of these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in consideration of availability.

  Other diols used as needed include aliphatic diols having 2 to 36 carbon atoms other than the above (1,2-propylene glycol, butanediol, hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, Neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.; C4-C36 alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol) A) alicyclic diol having 4 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); alkylene oxide (hereinafter abbreviated as AO) of the alicyclic diol [ethylene oxide (hereinafter EO ), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] adduct (additional mole number 1 to 30); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) AO (EO, PO, BO, etc.) adduct (addition mole number 2 to 30); polylactone diol (poly ε-caprolactone diol, etc.); and polybutadiene diol.

Further, as the diol used as required, a diol having another functional group may be used. Examples of the diol having a functional group include a diol having a carboxyl group, a diol having a sulfonic acid group or a sulfamic acid group, and salts thereof.
Examples of the diol having a carboxyl group include dialkyralkanoic acid [C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, and 2,2-dimethylolheptanoic acid]. , 2,2-dimethyloloctanoic acid, etc.].
Examples of the diol having a sulfonic acid group or a sulfamic acid group include sulfamic acid diol [N,N-bis(2-hydroxyalkyl)sulfamic acid (alkyl group C1-6) or its AO adduct (AO is EO or PO). Etc., such as the number of moles of addition of AO 1 to 6): for example, N,N-bis(2-hydroxyethyl)sulfamic acid and N,N-bis(2-hydroxyethyl)sulfamic acid PO2 mole addition product]; bis(2 -Hydroxyethyl) sulfonate and the like.

Examples of the neutralizing base of the diol having these neutralizing bases include the tertiary amine having 3 to 30 carbon atoms (such as triethylamine) and/or the alkali metal (such as sodium).
Of the above alcohol components, preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, the carbon number is 2 or more and 22 or less (more preferably the carbon number is 6 or more and 18 or less, further preferably It is preferably selected from aliphatic diols having 6 to 12 carbon atoms).
Further, in the present invention, monovalent alcohol may be used to the extent that the characteristics of the crystalline polyester are not impaired. Examples of the monohydric alcohol include monofunctional compounds such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol and dodecyl alcohol. Examples include alcoholic alcohol.

[Carboxylic acid component]
The carboxylic acid component is preferably dicarboxylic acid. Examples of the dicarboxylic acid component include various dicarboxylic acids, but aliphatic dicarboxylic acids and aromatic dicarboxylic acids are preferable, and aliphatic dicarboxylic acids are more preferably linear carboxylic acids.
Examples of the dicarboxylic acid include alkanedicarboxylic acid having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.); alicyclic dicarboxylic acid having 6 to 40 carbon atoms. Acid [dimer acid (dimerized linoleic acid) and the like], alkene dicarboxylic acid having 4 to 36 carbon atoms (alkenylsuccinic acid such as dodecenylsuccinic acid, pentadecenylsuccinic acid and octadecenylsuccinic acid, maleic acid, fumaric acid) , Citraconic acid, etc.); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, etc.) And so on.

As the dicarboxylic acid, an acid anhydride of the above-mentioned one or a lower alkyl ester having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) may be used.
Of these dicarboxylic acids, it is particularly preferable to use an aliphatic dicarboxylic acid (particularly a linear carboxylic acid) alone, but an aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, t-butylisophthalic acid) is used together with the aliphatic dicarboxylic acid. An acid, and a copolymer of these lower alkyl esters are preferable) are also preferable. The amount of the aromatic dicarboxylic acid copolymerized is preferably 20 mol% or less.
In the present invention, of the above carboxylic acid components, preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less have 2 to 22 carbon atoms (more preferably 6 to 18 carbon atoms) The carboxylic acid selected from aliphatic dicarboxylic acids having 6 to 12 carbon atoms is more preferable.
Furthermore, a monovalent carboxylic acid may be used to the extent that the characteristics of the crystalline polyester are not impaired. Examples of the monovalent carboxylic acid include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, Examples include monocarboxylic acids such as dodecanoic acid and stearic acid.

[Isocyanate component]
Examples of the isocyanate component include isocyanate, diisocyanate and polyisocyanate having a valence of 3 or more, and diisocyanate is preferable.
As the diisocyanate, an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbons in the NCO group, the same applies hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, an alicyclic diisocyanate having 4 to 15 carbon atoms, and 8 carbon atoms To 15 araliphatic diisocyanates and modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product) and these And a mixture of two or more of the above. Of these, straight-chain aliphatic diisocyanates are preferable, and straight-chain aliphatic diisocyanates having 4 to 8 carbon atoms are more preferable. Moreover, you may use together trivalent or more polyisocyanate as needed.

Specific examples of the aromatic diisocyanate (including polyisocyanate having a valence of 3 or more) include 1,3- and/or 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate (TDI). ), crude TDI, 2,4'- and/or 4,4'
-Diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (for example, 5 to 20% by weight) of trifunctional or higher polyamines With a mixture]: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4′,4″-triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate, etc. Is mentioned.
Specific examples of the aliphatic diisocyanate (including polyisocyanates having a valence of 3 or more) include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, 1,6,6. 11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis(2-isocyanatoethyl)fumarate, bis(2-isocyanatoethyl)carbonate , 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and the like.

Specific examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis(2- Examples thereof include isocyanatoethyl)-4-cyclohexene-1,2-dicarboxylate, 2,5- and/or 2,6-norbornane diisocyanate.
Specific examples of the araliphatic diisocyanate include m- and/or p-xylylene diisocyanate (XDI) and α,α,α′,α′-tetramethylxylylene diisocyanate (TMXDI).

Examples of the modified diisocyanate include urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.
Specifically, modified diisocyanates such as modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), urethane modified TDI, and mixtures of two or more thereof [eg modified MDI and urethane modified TDI ( Combined use with an isocyanate-containing prepolymer).
Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and more preferred are TDI, MDI, and HDI. , Hydrogenated MDI, and IPDI.

The urethane-modified crystalline polyester resin used in the present invention can be produced, for example, by the following method. It is possible to obtain an unmodified crystalline polyester by subjecting the above-mentioned carboxylic acid component and alcohol component to an esterification reaction or a transesterification reaction, and then polycondensation reaction according to a conventional method under reduced pressure or by introducing nitrogen gas. it can.
After that, the reaction system is returned to the upper pressure, and then the above-mentioned isocyanate component is added and reacted to obtain a urethane-modified crystalline polyester resin.
The above esterification or transesterification reaction can be carried out, if necessary, using a usual esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate or magnesium acetate.

Further, the polycondensation reaction can be carried out using a usual polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide. . The polymerization temperature and the catalyst amount are not particularly limited and may be appropriately determined.
In the esterification or transesterification reaction or polycondensation reaction, all monomers are charged at one time to increase the strength of the crystalline polyester obtained, or a divalent monomer is first reacted to reduce low molecular weight components. After this, a method of adding a monomer having a valence of 3 or more and reacting it may be used.
The urethane-modified crystalline polyester resin is not limited to the above-mentioned manufacturing method, and may be one manufactured by a conventionally known manufacturing method.

<Resin composition containing polymer obtained by graft-polymerizing styrene-acrylic polymer on polyolefin>
It is important that the toner of the present invention contains a polymer in which a styrene-acrylic polymer is graft-polymerized on a polyolefin.
When the graft (co)polymer is not contained, the urethane-modified crystalline polyester resin is less likely to be finely dispersed in the amorphous resin, and the charge amount of each toner particle at low temperature and low humidity is suppressed. It gets harder.
The content of the resin composition is preferably 1.0 part by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the amorphous resin. When the content is within this range, it is considered that the fine dispersion of the crystalline polyester in the amorphous resin is efficiently performed by the polymer in which the styrene-acrylic polymer is graft-polymerized with the polyolefin.
Further, the content of the polymer in which the styrene acrylic polymer is graft-polymerized with the polyolefin in the resin composition is preferably 90% by mass or more and 100% by mass or less.

Further, the resin composition preferably contains, as a monomer unit constituting the graft copolymer, a monomer unit having a functional group containing a nitrogen atom, which is derived from acrylonitrile, methacrylonitrile or the like. It is considered that the inclusion of a monomer unit having a functional group containing a nitrogen atom as a constituent monomer unit increases the affinity for the urethane-modified crystalline polyester resin and enhances the fine dispersion effect of the crystalline polyester. The "monomer unit" means a form in which a monomer substance in a polymer is reacted.
Examples of the monomer having a functional group containing a nitrogen atom include acrylonitrile and methacrylonitrile.
The content of the monomer unit having a functional group containing a nitrogen atom is preferably 10.0 mol% or more and 50.0 mol% or less based on the total number of moles of all the monomer units constituting the resin composition, 15 It is more preferably from 0.0 mol% to 45.0 mol%.

  The polyolefin preferably used in the polymer in which the styrene-acrylic polymer is graft-polymerized on the polyolefin is not particularly limited as long as it is a polymer or copolymer of an unsaturated hydrocarbon having one double bond, and various polyolefins. Can be used. In particular, polyethylene type and polypropylene type are preferably used. The content of polyolefin in the resin composition is preferably 45% by mass or more and 55% by mass or less.

Examples of vinyl monomers having a vinyl group that can be used in the styrene acrylic polymer 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- Dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecyl Styrene-based units such as styrene and its derivatives such as styrene.
Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl-based vinyl compounds such as acrylonitrile, methacrylonitrile, acrylamide such as acrylamide, or methacrylic acid derivatives unit.
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 Unsaturated dibasic acid anhydrides; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Unsaturated dibasic acid half esters such as alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated dibasic acid esters such as dimethyl maleic acid, dimethyl fumaric acid; acrylic acid, Α,β-unsaturated acids such as methacrylic acid, crotonic acid, cinnamic acid; α,β-unsaturated acid anhydrides such as crotonic anhydride, cinnamic acid anhydride, and the aforementioned α,β-unsaturated acids Anhydrides with lower fatty acids; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, vinyl anhydride units containing carboxyl groups such as their acid anhydrides and their monoesters.
Acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-(1-hydroxy-1-methylbutyl)styrene, 4-(1-hydroxy-1-methyl) Hexyl) Vinyl-based units containing hydroxyl groups such as styrene.
Methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, propyl acrylate, -n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylate -2- An ester unit composed of an acrylic ester such as chloroethyl and phenyl acrylate.
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid An ester unit consisting of a methacrylic acid ester such as an α-methylene aliphatic monocarboxylic acid ester such as dimethylaminoethyl acid ester or diethylaminoethyl methacrylate.

  A resin composition containing a polymer in which a styrene acrylic polymer is graft-polymerized to the polyolefin used in the present invention is a reaction between these polymers described above, a monomer of one polymer, and a polymer of the other. It can be obtained by a known method such as the reaction of.

<Amorphous resin>
The amorphous resin used in the toner of the present invention preferably contains a polyester resin as a main component.
Examples of the monomer used in the polyester portion of the polyester resin include polyhydric alcohols (dihydric or trihydric or higher alcohols), polyhydric carboxylic acids (dihydric or trihydric or higher carboxylic acids), acid anhydrides or lower thereof. Alkyl esters are used. Here, in the case of producing a branched polymer, it is effective to partially crosslink in the molecule of the amorphous resin, and for that purpose, it is preferable to use a polyfunctional compound having a valence of 3 or more. Therefore, it is preferable that the raw material monomer of the polyester unit contains a carboxylic acid having a valence of 3 or more, an acid anhydride thereof or a lower alkyl ester thereof, and/or an alcohol having a valence of 3 or more.
As the polyhydric alcohol monomer used for the polyester unit of the polyester resin, the following polyhydric alcohol monomers can be used.
As the dihydric alcohol component, 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 bisphenol represented by the formula (A) and derivatives thereof;

（式中、Ｒはエチレン又はプロピレン基であり、ｘ及び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以上１０以下である。）
式（Ｂ）で示されるジオール類；が挙げられる。

(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 or more and 10 or less.)
Diols represented by the formula (B);

  Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. , 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene Can be mentioned. Of these, glycerol, trimethylolpropane and pentaerythritol are preferably used. These dihydric alcohols and trihydric or higher alcohols can be used alone or in combination.

As the polyvalent carboxylic acid monomer used for the polyester portion of the polyester resin, the following polyvalent carboxylic acid monomers can be used.
Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids and These lower alkyl ester is mentioned. Of these, maleic acid, fumaric acid, terephthalic acid and n-dodecenylsuccinic acid are preferably used.
Examples of the trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid and 1,2,4-naphthalenetricarboxylic acid. 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra( Examples thereof include methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, enpol trimer acid, acid anhydrides thereof or lower alkyl esters thereof. Of these, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or a derivative thereof is particularly preferable because it is inexpensive and the reaction control is easy. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination.

The amorphous resin may be a hybrid resin containing a polyester resin and other resin components. For example, a hybrid resin of polyester resin and vinyl resin may be mentioned. A method for obtaining a reaction product of a vinyl resin or a vinyl copolymer unit and a polyester resin, such as a hybrid resin, includes a monomer component capable of reacting with each of the vinyl resin, the vinyl copolymer unit and the polyester resin. Where the polymer is present, a method of carrying out a polymerization reaction of one or both resins is preferable.
For example, among the monomers constituting the polyester resin component, examples of monomers that can react with the vinyl-based copolymer include, for example, phthalic acid, maleic acid, citraconic acid, unsaturated dicarboxylic acids such as itaconic acid, or anhydrides thereof. Can be mentioned. Among the monomers constituting the vinyl-based copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  Further, in the present invention, as the amorphous resin, a known resin compound may be used in combination with the above-mentioned vinyl resin. Examples of such a resin compound include phenol resin, natural resin-modified phenol resin, natural resin-modified malein resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin. Examples thereof include resins, xylene resins, polyvinyl butyral, terpene resins, coumarone indene resins, petroleum-based resins and the like.

  Further, the peak molecular weight of the amorphous resin is preferably 8,000 or more and 13,000 or less from the viewpoint of low-temperature fixability and hot offset resistance. The acid value of the amorphous resin is preferably 15 mgKOH/g or more and 30 mgKOH/g or less from the viewpoint of charging stability in a high temperature and high humidity environment. Further, it is preferable that the amorphous resin has a hydroxyl value of 2 mgKOH/g or more and 20 mgKOH/g or less from the viewpoint of low-temperature fixability and storability.

Further, as the amorphous resin, a low molecular weight amorphous resin B and a high molecular weight amorphous resin A may be mixed and used. The content ratio (A/B) of the high-molecular-weight amorphous resin A and the low-molecular-weight amorphous resin B is 10/90 to 60/40 on a mass basis. It is preferable from the viewpoint.
The peak molecular weight of the high molecular weight amorphous resin A is preferably 10,000 or more and 20,000 or less from the viewpoint of hot offset resistance. The acid value of the high molecular weight amorphous resin is preferably 15 mgKOH/g or more and 30 mgKOH/g or less from the viewpoint of charging stability in a high temperature and high humidity environment.
The number average molecular weight of the low molecular weight amorphous resin B is preferably 1500 or more and 3500 or less from the viewpoint of low temperature fixability. The acid value of the low molecular weight amorphous resin is preferably 10 mgKOH/g or less from the viewpoint of charging stability in a high temperature and high humidity environment.

<Other resins>
In the present invention, in order to improve the pigment dispersibility, the charge stability of the toner, and the blocking resistance, the following polymers other than the above-mentioned amorphous resin are added in an amount that does not impair the effects of the present invention. It is also possible to add.
Examples of the other resin include the following resins. Polystyrene, poly-p-chlorostyrene, homopolymers of styrene such as polyvinyltoluene and its substitution products; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether Styrene-based copolymers such as copolymers, styrene-vinyl methyl ketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenol resins, natural modified phenol resins, natural resin modified maleic acid resins, acrylic resins , Methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum resin and the like.

<Wax>
Wax may be used in the toner of the present invention. Examples of the wax include the following.
Hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof. Waxes containing fatty acid ester such as carnauba wax as a main component; Deoxidized fatty acid ester such as carnauba wax, which is partially or entirely deoxidized. Further, the following may be mentioned.
Saturated straight chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and vinalinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol Saturated alcohols such as melicyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid and montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol , Esters with alcohols such as ceryl alcohol, melysyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislaurin Acid amides, saturated fatty acid bisamides such as hexamethylenebisstearic acid amide; ethylene bisoleic acid amide, hexamethylenebisoleic acid amide, N,N'dioleyl adipamide, N,N'dioleyl sebacic acid amide Such unsaturated fatty acid amides; aromatic bisamides such as m-xylene bisstearic acid amide, N,N' distearylisophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts (generally called metallic soap); waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglyceride Partial esterified product of polyhydric alcohol; methyl ester compound having hydroxyl group obtained by hydrogenation of vegetable oil.

Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, and fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of achieving both fixing latitude and image stability.
In the present invention, the wax is preferably used in an amount of 1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the total amount of the amorphous resin and the crystalline polyester resin. When the content is 1 part by mass or more, the effect of addition of the release agent is suitably exerted, and offset and poor separation at high temperatures are less likely to occur. On the other hand, when the amount is 20 parts by mass or less, the mechanical strength of the toner becomes good, and the image stability during continuous output does not easily deteriorate.

<Colorant>
A colorant may be used in the toner of the present invention. The following are mentioned as a coloring agent.
Examples of the black colorant include carbon black; those obtained by toning black with a yellow colorant, a magenta colorant and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment together to improve the sharpness from the viewpoint of the image quality of a full-color image.

Examples of the magenta toner pigment include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; C.I. I. Pigment Violet 19; C.I. I. Butt Red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. Disperse Red 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the cyan toner pigment include the following. C. I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.
Examples of dyes for cyan toner include C.I. I. There is Solvent Blue 70.
Examples of the yellow toner pigment include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat Yellow 1, 3, 20.
Examples of dyes for yellow toner include C.I. I. There is Solvent Yellow 162.
The amount of the colorant used is preferably 0.1 part by mass or more and 30 parts by mass or less based on 100 parts by mass of the total amount of the amorphous resin and the crystalline polyester resin.

<Charge control agent>
The toner may contain a charge control agent if necessary. As the charge control agent contained in the toner, known charge control agents can be used, but in particular, a metal compound of an aromatic carboxylic acid which is colorless and has a high charging speed of the toner and which can stably maintain a constant charge amount is preferable.
As the negative charge control agent, a salicylic acid metal compound, a naphthoic acid metal compound, a dicarboxylic acid metal compound, a polymer type compound having a sulfonic acid or a carboxylic acid in the side chain, a sulfonate or a sulfonate ester compound in the side chain Examples thereof include a polymer type compound, a polymer type compound having a carboxylic acid salt or a carboxylic acid ester compound as a side chain, a boron compound, a urea compound, a silicon compound, and calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer type compound having the quaternary ammonium salt in its side chain, a guanidine compound, and an imidazole compound. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the total amount of the amorphous resin and the crystalline polyester resin.

<Inorganic fine particles (mainly external additives)>
The toner of the present invention may contain inorganic fine particles, if necessary. The inorganic fine particles may be internally added to the toner particles or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine particles such as silica, titanium oxide and aluminum oxide are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.
As the external additive for improving fluidity, inorganic fine particles having a specific surface area of 50 m ² /g or more and 400 m ² /g or less are preferable, and for stabilizing the durability, a specific surface area of 10 m ² /g or more 50 m ² or more. It is preferable that the inorganic fine particles have a density of less than 1 g/g. In order to achieve both improvement of fluidity and stabilization of durability, inorganic fine particles having a specific surface area in the above range may be used together.
The external additive is preferably used in an amount of 0.1 part by mass or more and 10.0 parts by mass or less based on 100 parts by mass of the toner particles. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used.

<Developer>
The toner of the present invention can be used also as a one-component developer, but in order to further improve dot reproducibility, it can be mixed with a magnetic carrier and used as a two-component developer, and a stable image can be obtained for a long time. Is preferred in that
As the magnetic carrier, for example, iron powder having a surface oxidized, or unoxidized iron powder, iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, metal particles such as rare earth, Magnetic materials such as alloy particles, oxide particles, and ferrite, and magnetic material-dispersed resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state are generally known. Can be used.
When the toner of the present invention is mixed with a magnetic carrier to be used as a two-component developer, the carrier mixing ratio at that time is preferably 2% by mass or more and 15% by mass or less as the toner concentration in the two-component developer. , And more preferably 4% by mass or more and 13% by mass or less, usually good results are obtained.

<Manufacturing method>
The method for producing the toner particles may be obtained by any conventionally known method such as a melt kneading method, an emulsion phase inversion method, a suspension polymerization method and an emulsion aggregation method. From the viewpoint of finely dispersing the crystalline polyester in the amorphous resin, the melt-kneading method having a step of melt-kneading the amorphous resin, the resin composition, and the crystalline polyester resin, and crushing the obtained kneaded product is preferable.
The procedure for producing a toner by the melt-kneading method will be described below.

In the raw material mixing step, as a material constituting the toner particles, for example, an amorphous resin, a resin composition, a crystalline polyester resin and, if necessary, other components such as a wax, a colorant, and a charge control agent are weighed in predetermined amounts. Then mix and mix. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano hybrid (manufactured by Nippon Coke Industry Co., Ltd.).
Next, the mixed materials are melt-kneaded to disperse the crystalline polyester resin or the like in the amorphous resin. In the melt-kneading step, a batch kneader such as a pressure kneader or a Banbury mixer or a continuous kneader can be used, and a single-screw or twin-screw extruder is mainly used because of its superiority in continuous production. Is becoming For example, KTK twin-screw extruder (Kobe Steel Co., Ltd.), TEM twin-screw extruder (Toshiba Machinery Co., Ltd.), PCM kneader (Ikegai Tekko), twin-screw extruder (KCK) ), Co-Kneader (manufactured by Buss), Needex (manufactured by Nippon Coke Industry Co., Ltd.) and the like. Furthermore, the resin mixture obtained by melt-kneading may be rolled with a two-roll mill or the like and cooled with water or the like in the cooling step.

Then, the cooled product of the resin mixture is ground to a desired particle size in a grinding process. In the crushing process, for example, after roughly crushing with a crusher such as a crusher, a hammer mill, and a feather mill, further, for example, Kryptron system (Kawasaki Heavy Industries, Ltd.), super rotor (Nisshin Engineering Co., Ltd.), turbo Finely pulverize with a mill (manufactured by Turbo Kogyo) or an air jet type fine pulverizer.
After that, if necessary, such as an inertia classification type elbow jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification type turboplex (manufactured by Hosokawa Micron), a TSP separator (manufactured by Hosokawa Micron), a faculty (manufactured by Hosokawa Micron) A classified product (toner particles) is obtained by classification using a classifier or a sieve classifier. Among them, Faculty (manufactured by Hosokawa Micron Co., Ltd.) is preferable from the viewpoint that the toner particles can be spheronized at the same time as classification, and the transfer efficiency can be improved.
If necessary, an external additive is externally added to the surface of the toner particles. As a method for externally treating the external additive, a predetermined amount of classified toner and various known external additives are mixed, and a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano-mixer. Examples include a method of stirring and mixing using a mixing device such as a hybrid (manufactured by Nippon Coke Industry Co., Ltd.) and Nobilta (manufactured by Hosokawa Micron Co., Ltd.) as an external additive.

The methods for measuring various physical properties of the toner and the raw materials will be described below.
<Measurement method of weight average molecular weight of resin>
The molecular weight distribution of the THF-soluble component of the resin was measured by gel permeation chromatography (GPC) as follows.
First, the toner was dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution was filtered through a solvent-resistant membrane filter “Maeshoridisc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution was adjusted so that the concentration of the THF-soluble component was about 0.8% by mass. This sample solution was used for measurement under the following conditions.
Device: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804, 805, 806, 80
7 series of 7 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml/min
Oven temperature: 40.0°C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, a standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) was used.

<Measurement of BET specific surface area of inorganic fine particles>
The BET specific surface area of the inorganic fine particles was measured according to JIS Z8830 (2001). The specific measuring method is as follows.
As the measuring device, an "automatic specific surface area/pore distribution measuring device TriStar 3000 (manufactured by Shimadzu Corporation)" which uses a gas adsorption method by a constant volume method as a measuring method was used. The setting of the measurement conditions and the analysis of the measurement data are performed by using the dedicated software "TriStar 3000 Version 4.00" attached to this device, and the device is connected with a vacuum pump, a nitrogen gas pipe, and a helium gas pipe. A value calculated by the BET multipoint method using nitrogen gas as the adsorption gas was defined as the BET specific surface area of the inorganic fine particles in the present invention.
The BET specific surface area was calculated as follows.

First, nitrogen gas was adsorbed on the inorganic fine particles, and the equilibrium pressure P (Pa) in the sample cell and the nitrogen adsorption amount Va (mol/g) of the external additive at that time were measured. Then, the relative pressure Pr, which is a value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is taken as the horizontal axis, and the nitrogen adsorption amount Va (mol/g) is taken as the vertical axis. An adsorption isotherm was obtained. Next, the adsorption amount Vm (mol/g) of the monomolecular layer, which is the adsorption amount required to form the monomolecular layer on the surface of the external additive, was determined by applying the following BET formula.
Pr/Va(1-Pr)=1/(Vm×C)+(C-1)×Pr/(Vm×C)
(Here, C is a BET parameter, which is a variable that varies depending on the measurement sample species, adsorption gas species, and adsorption temperature.)
The BET formula is interpreted as a straight line having a slope of (C-1)/(Vm×C) and an intercept of 1/(Vm×C), where X is Pr and Y is Pr/Va(1-Pr). You can (this line is called BET plot).
Straight line slope=(C-1)/(Vm×C)
Straight line intercept = 1/(Vm x C)
When the measured value of Pr and the measured value of Pr/Va(1-Pr) are plotted on a graph and a straight line is drawn by the least squares method, the slope and intercept values of the straight line can be calculated. Vm and C can be calculated by solving a simultaneous equation of the slope and the intercept using these values.
Further, the BET specific surface area S (m ² /g) of the inorganic fine particles is calculated from the calculated Vm and the molecular occupation cross-sectional area of nitrogen molecules (0.162 nm ² ) based on the following formula.
S=Vm×N×0.162×10 ⁻¹⁸
(Here, N is Avogadro's number (mol- ¹ ).)
The measurement using this device follows the “TriStar 3000 Instruction Manual V4.0” attached to the device, but specifically, the measurement was performed by the following procedure.

The tare of a dedicated glass sample cell (stem diameter: 3/8 inch, volume: about 5 ml) that had been thoroughly washed and dried was precisely weighed. Then, about 0.1 g of the external additive was put into this sample cell using a funnel.
The sample cell containing the inorganic fine particles was set in a "pretreatment device Vacuprep 061 (manufactured by Shimadzu Corporation)" in which a vacuum pump and a nitrogen gas pipe were connected, and vacuum deaeration was continued at 23°C for about 10 hours. During vacuum degassing, the particles were gradually degassed while adjusting the valve so that the inorganic fine particles were not sucked by the vacuum pump. The pressure inside the cell gradually decreased with degassing, and finally reached about 0.4 Pa (about 3 mTorr). After completion of vacuum deaeration, nitrogen gas was gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell was removed from the pretreatment device. Then, the mass of this sample cell was precisely weighed, and the accurate mass of the external additive was calculated from the difference from the tare. At this time, the sample cell was covered with a rubber stopper during weighing so that the external additive in the sample cell was not contaminated by moisture in the atmosphere.
Next, a dedicated "isothermal jacket" was attached to the stem portion of the sample cell containing the inorganic fine particles. Then, a dedicated filler rod was inserted into this sample cell, and the sample cell was set in the analysis port of the device. The isothermal jacket is a tubular member that can absorb liquid nitrogen to a certain level by a capillary phenomenon and has a porous material on the inner surface and an impermeable material on the outer surface.

Then, the free space of the sample cell including the connecting device was measured. The free space was determined by measuring the volume of the sample cell with helium gas at 23° C., and subsequently measuring the volume of the sample cell after cooling the sample cell with liquid nitrogen, similarly using helium gas. It was calculated by converting from the difference in volume. The saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using a Po tube built in the device.
Next, after performing vacuum deaeration in the sample cell, the sample cell was cooled with liquid nitrogen while continuing the vacuum deaeration. Then, nitrogen gas was gradually introduced into the sample cell to adsorb nitrogen molecules to the toner. At this time, since the adsorption isotherm can be obtained by measuring the equilibrium pressure P (Pa) at any time, this adsorption isotherm was converted into a BET plot. The points of relative pressure Pr for collecting data were set to 6 points of 0.05, 0.10, 0.15, 0.20, 0.25 and 0.30 in total. A straight line was drawn on the obtained measurement data by the least squares method, and Vm was calculated from the slope and intercept of the straight line. Further, using this Vm value, the BET specific surface area of the inorganic fine particles was calculated as described above.

<Measurement method of weight average particle diameter (D4) of toner particles>
The weight average particle diameter (D4) of the toner particles is measured with a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) by a pore electrical resistance method equipped with an aperture tube of 100 μm. Using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for condition setting and measurement data analysis, the measurement data is measured with 25,000 effective measurement channels. Was analyzed and calculated.
The electrolytic aqueous solution used for the measurement may be prepared by dissolving special grade sodium chloride in ion-exchanged water so that the concentration becomes about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.).
Before the 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 number 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). (Manufactured by the company) was used to set the value obtained. The threshold and noise level were automatically set by pressing the threshold/noise level measurement button. Further, the current was set to 1600 μA, the gain was set to 2, the electrolyte was set to ISOTON II, and the flash of the aperture tube after the measurement was checked.
In the dedicated software “pulse to particle size conversion setting screen”, the bin interval was set to logarithmic particle size, the particle size bin was set to 256 particle size bin, and the particle size range was set to 2 μm to 60 μm.

The specific measuring method is as follows.
(1) About 200 ml of the electrolytic aqueous solution was placed in a glass 250 ml round-bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod was stirred counterclockwise at 24 revolutions/second. Then, the dirt and air bubbles in the aperture tube were removed in advance by the "aperture flush" function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution was placed in a glass 100 ml flat-bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder, pH7 precision measurement as a dispersant was added to this). About 0.3 ml of a diluting solution prepared by diluting a 10% by mass aqueous solution of a neutral detergent for cleaning vessels with Wako Pure Chemical Industries, Ltd. with ion-exchanged water 3 times by mass was added.
(3) Two oscillators with an oscillating frequency of 50 kHz are built in with the phases shifted by 180 degrees, and are placed in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetra 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electric output of 120 W. A predetermined amount of ion-exchanged water was added, and about 2 ml of the above Contaminone N was added to this water tank.
(4) The beaker of (2) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was operated. Then, the height position of the beaker was adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker was maximized.
(5) About 10 mg of toner was added little by little to the electrolytic aqueous solution in a state where the electrolytic aqueous solution in the beaker of (4) was irradiated with ultrasonic waves and dispersed. Then, the ultrasonic dispersion treatment was continued for another 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank was appropriately adjusted 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 aqueous electrolyte solution of (5) in which the toner was dispersed was dropped using a pipette, and the concentration was adjusted to be about 5%. .. Then, the measurement was performed until the number of measured particles reached 50,000.
(7) The measurement data was analyzed by the dedicated software attached to the apparatus to calculate the weight average particle diameter (D4). The “average diameter” on the analysis/volume statistical value (arithmetic mean) screen when the graph/volume% was set with the dedicated software was defined as the weight average particle diameter (D4).

<Method of measuring average circularity of toner particles>
The average circularity of the toner was measured by a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement/analysis conditions at the time of calibration work.
The measurement principle of the flow-type particle image analyzer "FPIA-3000 type" (manufactured by Sysmex Corporation) is to image flowing particles as a still image and perform image analysis. The sample added to the sample chamber is sent to the flat sheath flow cell by the sample suction syringe. The sample sent to the flat sheath flow is sandwiched by the sheath liquid and forms a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is captured in a focused state. The particle image is picked up by a CCD camera, and the picked-up image is 512 pixels×512 pixels in one field of view, and image processing is performed at an image processing resolution of 0.37×0.37 μm per pixel, and the outline of each particle image is obtained. Extraction is performed, and the projected area of the particle image and the perimeter are measured.
Next, the projected area S and the perimeter L of each particle image are obtained. Using the area S and the perimeter L, the equivalent circle diameter and circularity are obtained. The circular equivalent diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity is the value obtained by dividing the perimeter of the circle obtained from the circular equivalent by the perimeter of the particle projected image. It is defined and calculated by the following formula.
Circularity C=2×(π×S) ^1/2 /L
The circularity is 1.000 when the particle image is a perfect circle, and the circularity has a smaller value as the degree of unevenness on the outer periphery of the particle image increases.
After calculating the circularity of each particle, the range of circularity 0.2 to 1.0 is distributed to 800 divided channels, and the average value is calculated by using the center value of each channel as a representative value to calculate the average circularity.

As a specific measuring method, a surfactant as a dispersant, preferably 0.02 g of sodium dodecylbenzenesulfonate is added to 20 ml of ion-exchanged water, and then 0.02 g of a measurement sample is added, and an oscillation frequency of 50 kHz and electrical Dispersion treatment was performed for 2 minutes using a desk-top type ultrasonic cleaner disperser having an output of 150 W (for example, "VS-150" (manufactured by Vervoclear Co., Ltd.) to obtain a dispersion liquid for measurement. Is appropriately cooled so that the temperature becomes 10°C or higher and 40°C or lower.
The flow-type particle image analyzer equipped with a standard objective lens (10 times) was used for the measurement, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure was introduced into the flow type particle image analyzer, 3000 toner particles were measured in the HPF measurement mode and the total count mode, and the binarization threshold value at the time of particle analysis was 85%. The average particle diameter of the toner was determined by limiting the analyzed particle diameter to a circle equivalent diameter of 2.00 μm or more and 200.00 μm or less.
In the measurement, automatic focus adjustment is performed using standard latex particles (for example, 5200A manufactured by Duke Scientific Co., diluted with ion-exchanged water) before starting the measurement. After that, it is preferable to perform focus adjustment every two hours from the start of measurement.
In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation was used, and the analysis particle size was limited to a circle equivalent diameter of 2.00 μm or more and 200.00 μm or less. Performed the measurement under the measurement and analysis conditions when the calibration certificate was received.

<Measurement of glass transition temperature (Tg) of resin>
The glass transition temperature of the resin is measured according to ASTM D3418-82 using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments).
The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat.
Specifically, about 5 mg of resin is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rising rate is 10° C./min in the measurement range of 30 to 180° C. Measure with. The temperature is once raised to 180° C. and held for 10 minutes, then lowered to 30° C., and then raised again. In the second heating process, a specific heat change is obtained in the temperature range of 30 to 100°C. The glass transition temperature (Tg) of the resin is defined as the intersection of the line at the midpoint of the baseline before and after the change in specific heat and the differential heat curve.

<Measurement of DSC endothermic amount (ΔH) of wax and crystalline polyester>
The peak temperature (Tp) of the maximum endothermic peak of the toner or the like (toner, crystalline polyester) in the present invention is measured under the following conditions using DSC Q1000 (manufactured by TA Instruments).
Temperature rising rate: 10°C/min
Measurement start temperature: 20°C
Measurement end temperature: 180°C
The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat.
Specifically, about 5 mg of a sample is precisely weighed, placed in a silver pan, and measured once. An empty silver pan is used as a reference.
When the toner is used as a sample and the maximum endothermic peak (maximum endothermic peak derived from the binder resin) does not overlap with the endothermic peaks of resins other than wax and crystalline resin, the endothermic amount of the obtained maximum endothermic peak Is treated as it is as the endothermic amount of the maximum endothermic peak derived from the wax and the crystalline resin. On the other hand, when the toner is used as a sample and the endothermic peak of the resin other than the wax and the binder resin overlaps with the maximum endothermic peak of the binder resin, the endothermic amount derived from the resin other than the wax and the binder resin is determined. , It is necessary to subtract from the obtained endothermic amount of the maximum endothermic peak.
The maximum endothermic peak means the peak having the maximum endothermic amount when there are a plurality of peaks. Further, the endothermic amount (ΔH) of the maximum endothermic peak is calculated from the area of the peak using the analysis software attached to the apparatus.

<Measurement of Content of Crystalline Polyester Resin in Toner>
The toner is put in methyl ethyl ketone (MEK), left at 25° C. for several hours, then shaken sufficiently, the toner and MEK are mixed well, and the sample is allowed to stand still for 12 hours or more until there is no coalescence of the sample. After centrifuging the obtained solution at 3500 rpm for 20 minutes (centrifuge "H-18", Kokusan Co., Ltd.), the solid content is collected and dried.
The dried sample is dissolved in MEK under heating at 75° C., and a crystalline polyester resin is obtained from the supernatant separated by centrifugation. Using the crystalline polyester resin, the content is calculated from the weight of the toner before adjustment and the weight of the obtained crystalline polyester.

<Measurement of Isocyanate Unit Content in Crystalline Polyester Resin from Toner>
The content of the isocyanate unit in the crystalline polyester resin was calculated by the following method using NMR.
5 mg of the crystalline polyester resin separated by the above method was precisely weighed, 600 μL of deuterated chloroform (CDCL ₃ ) was added and dissolved, ¹ H-NMR measurement was performed, and the composition ratio was calculated from the integrated value of each peak. The specific device conditions are as follows.
(Measurement condition)
Measuring device JNM-ECA400 FT-NMR(JEOL)
Measurement nuclide: ¹ H
Solvent: CDCl ₃ (deuterated chloroform)
Measurement frequency: 400MHz
Pulse width: 3.125 μs
Frequency range: 7500Hz
Number of integrations: 64 times Measurement temperature: Room temperature

  The basic configuration and features of the present invention have been described above, but the present invention will be specifically described below based on Examples. However, the present invention is not limited to this.

[Production Example of Amorphous Resin A1]
Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 72.0 parts by mass (0.20 mol; 100.0 mol% based on the total number of polyhydric alcohols)
·Terephthalic acid:
28.0 parts by mass (0.17 mol; 100.0 mol% based on the total number of polyvalent carboxylic acids) tin 2-ethylhexanoate (esterification catalyst): 0.5 parts by mass Cooling tube, stirrer, nitrogen The above materials were weighed in a reaction vessel equipped with an introduction tube and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200°C.
Furthermore, the pressure in the reaction tank was reduced to 8.3 kPa and maintained for 1 hour, then cooled to 180° C. and returned to atmospheric pressure (first reaction step).
・Trimellitic anhydride:
1.3 parts by mass (0.01 mol; 4.0 mol% based on the total number of polyvalent carboxylic acids)
Tert-Butylcatechol (polymerization inhibitor): 0.1 parts by mass After that, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was allowed to proceed for 1 hour while maintaining the temperature at 180° C., ASTM D36 After confirming that the softening point measured according to -86 reached 120°C, the temperature was lowered to stop the reaction (second reaction step), and an amorphous resin A1 having Tg=57°C was obtained.

[Production Example of Crystalline Polyester Resin B1]
-Ethylene glycol: 21.4 parts by mass (0.35 mol; 46.5 mol% based on the total number of moles of the monomer of the resin B1)
Sebacic acid: 69.8 parts by mass (0.35 mol; 46.5 mol% based on the total number of moles of the monomer of the resin B1)
The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introducing tube, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140°C.
-Tin 2-ethylhexanoate: 0.5 parts by mass After that, the above materials were added, the pressure in the reaction tank was lowered to 8.3 kPa, and the reaction was performed for 4 hours while maintaining the temperature at 200°C (first reaction step). ).
Hexamethylene diisocyanate: 8.7 parts by mass (0.05 mol; 7.0 mol% based on the total number of moles of the monomer of the resin B1)
After that, the pressure in the reaction tank was gradually released to return to normal pressure, the above materials were added, and the mixture was reacted at 100° C. for 3 hours under normal pressure to obtain a crystalline polyester resin B1 (second reaction). Process). Table 1 shows the peak molecular weight and melting peak temperature of the obtained crystalline polyester resin B1.

[Production Example of Crystalline Polyester Resins B2 to B14]
In the production example of the crystalline polyester resin B1, the monomers and mass parts of the polyhydric alcohol component and/or the polycarboxylic acid component in the first reaction step and the reaction time were changed so as to be in Table 1, and the second reaction step The reaction was performed in the same manner except that the monomer and the number of parts by weight were changed to obtain crystalline polyester resins B2 to B14. Table 1 shows the physical properties of the crystalline polyester resins B2 to B14.

[Production Example of Resin Composition C1]
・Low molecular weight polypropylene (Viscole 660P manufactured by Sanyo Kasei Co., Ltd.):
51.6 parts by mass (0.11 mol; 15.0 mol% relative to the total number of moles of the resin composition monomer)
-Xylene: 25.0 parts by mass The above materials were weighed in a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe, and a thermocouple. Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised to 175° C. with stirring.
Styrene: 30.7 parts by mass (0.29 mol; 42.0 mol% based on the total number of moles of the resin composition monomer)
Acrylonitrile: 14.5 parts by mass (0.27 mol; 39.0 mol% based on the total number of moles of the resin composition monomer)
Acrylic acid: 0.5 parts by mass (0.01 mol; 1.0 mol% based on the total number of moles of the resin composition monomer)
Butyl acrylate: 2.7 parts by mass (0.02 mol; 3.0 mol% based on the total number of moles of the resin composition monomer)
-Xylene: 10.0 parts by mass-Di-t-butylperoxyhexahydroterephthalate: 0.5 parts by mass Then, the above materials were added dropwise over 3 hours and further stirred for 30 minutes. Then, the solvent was distilled off to obtain a resin composition C1 containing a resin in which a styrene resin was graft-bonded to polypropylene. Table 2 shows the peak molecular weight and softening point of the obtained resin composition C1. In GPC measurement, no peak corresponding to polypropylene as a raw material was observed.

[Production Example of Resin Compositions C2 to C6]
In the production example of the resin composition C1, the reaction was performed in the same manner except that the constituting monomer and the number of parts by mass were changed to obtain resin compositions C2 to C6. Table 2 shows the physical properties of the resin compositions C2 to C6. Also in C2 to C5, a peak corresponding to the raw material polypropylene was not recognized by GPC measurement.

<Toner Production Example 1>
Amorphous resin 1 90 parts by mass, crystalline polyester resin B1 10 parts by mass, resin composition C1 5 parts by mass, wax (Fischer-Tropsch wax, melting point 90° C.) 5 parts by mass, C.I. I. Pigment Blue 15:35 5 parts by mass 3,5-di-t-butylsalicylic acid aluminum compound 0.5 parts by mass The raw materials shown in the formulation were used in a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.). Then, the mixture was mixed at a rotation speed of 20 s ⁻¹ and a rotation time of 5 min, and then kneaded with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 125° C. The obtained kneaded product was cooled and coarsely pulverized with a hammer mill to 1 mm or less to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized by a mechanical pulverizer (T-250, manufactured by Turbo Industry Co., Ltd.). Further, classification was performed using a rotary classifier (200 TSP, manufactured by Hosokawa Micron Co., Ltd.) to obtain toner particles. The operating conditions of the rotary classifier (200 TSP, manufactured by Hosokawa Micron Co., Ltd.) were that the classification rotor rotation speed was 50.0 s ⁻¹ for classification. The toner particles obtained had a weight average particle diameter (D4) of 6.5 μm.
To 100 parts by mass of the obtained toner particles, 1.0 part by mass of silica fine particles having a primary average particle size of 13.0 nm was added, and the peripheral speed was 45 m/with a Henschel mixer (FM75 type, manufactured by Mitsui Miike Kakoki Co., Ltd.). After mixing for 5 sec, toner 1 was obtained by passing through an ultrasonic vibrating screen having an opening of 54 μm. Table 3 shows the particle size and circularity of Toner 1.

<Toner Production Examples 2-19, 21-25>
As shown in Table 2, the same procedure as in Toner Production Example 1 was performed except that the number of added parts of the material was changed. Table 3 shows an outline of the toners 2 to 19 and 21 to 25.

<Toner Production Example 20>
[Synthesis of ketimine 1]
170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were placed in a reaction vessel equipped with a stir bar and a thermometer and reacted at 50° C. for 5 hours to obtain ketimine 1. Ketimine 1 had an amine value of 418 mgKOH/g.
[Preparation of Resin Particle Dispersion Liquid 1]
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of sulfuric acid ester of methacrylic acid ethylene oxide adduct Ereminol RS-30 (manufactured by Sanyo Kasei Co., Ltd.), 138 parts of styrene, 138 of methacrylic acid. Parts and 1 part of ammonium persulfate were added, and the mixture was stirred at 400 rpm for 15 minutes, then heated to 75° C. and kept for 5 hours. Next, 30 parts of a 1 mass% ammonium persulfate aqueous solution was added, and the mixture was aged at 75° C. for 5 hours to obtain a resin particle dispersion liquid 1. When the particle size distribution of the resin particle dispersion liquid 1 was measured using a laser diffraction/scattering particle size distribution analyzer LA-920 (manufactured by HORIBA), the volume average particle size was 0.14 μm.
[Preparation of aqueous medium 1]
A water-based medium 1 was prepared by mixing 990 parts of water, 83 parts of resin particle dispersion 1, 37 parts of a 48.5 mass% aqueous solution of sodium dodecyldiphenyl ether disulfonate Eleminol MON-7 (manufactured by Sanyo Kasei Co., Ltd.) and 90 parts of ethyl acetate. Got

[Production of toner particles]
1200 parts of water, cyan pigment (manufactured by Dainichiseika Co., Ltd.: Pigment Blue 15:3) 5
40 parts and 1200 parts of the amorphous resin A1 were mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) and then kneaded at 150° C. for 30 minutes using a two-roll mill. Next, after cooling by rolling, it was pulverized using a palpelizer to obtain a masterbatch 1.
In a container equipped with a stir bar and a thermometer, 378 parts of amorphous resin A1, 50 parts of Fischer-Tropsch wax having a melting point of 90° C., 20 parts of resin composition C4, 3,5-di-t-butylsalicylic acid. 2 parts of an aluminum compound and 947 parts of ethyl acetate were added, the temperature was raised to 80° C., the temperature was maintained for 5 hours, and then the temperature was cooled to 30° C. in 1 hour. Next, 500 parts of masterbatch 1 and 500 parts of ethyl acetate were added and mixed for 1 hour to obtain a raw material liquid 1.
1324 parts of the raw material liquid 1 was transferred to a container, and using a bead mill Ultra Visco Mill (manufactured by AIMEX Co., Ltd.), the liquid feeding speed was 1 kg/h, the peripheral speed of the disk was 6 m/s, and the particle diameter was 0.5 mm. 80% by volume of zirconia beads were filled and three passes were performed. Next, 1042.3 parts of a 65 mass% ethyl acetate solution of the amorphous resin A1 was added, and one pass was performed under the above conditions to obtain a dispersion liquid 1. Dispersion 1 had a solid content concentration of 50% by mass at 130° C. for 30 minutes.
200 parts of crystalline polyester B12 and 400 parts of ethyl acetate were placed in a 2 L container, heated to 75° C., and then rapidly cooled at 27° C./min in an ice water bath. Next, 500 ml of glass beads having a particle size of 3 mm was added, and the mixture was ground for 10 hours using a batch type sand mill device (manufactured by Campehapio Co.) to obtain a crystalline polyester dispersion liquid 1.
664 parts of dispersion 1, 73.9 parts of crystalline polyester dispersion 1, 4.6 parts of ketimine 1 were placed in a container and mixed for 1 minute at 5000 rpm using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.). After that, 1200 parts of the aqueous medium 1 was added, and the mixture was mixed for 20 minutes at 13000 rpm using a TK homomixer (made by Tokushu Kika Co., Ltd.) to obtain an emulsified slurry 1.

The emulsified slurry 1 was put into a container equipped with a stirrer and a thermometer, the solvent was removed at 30° C. for 8 hours, and the mixture was aged at 45° C. for 4 hours to obtain a dispersion slurry 1. 100 parts of Dispersion Slurry 1 were filtered under reduced pressure. Next, the following operations (1) to (4) were performed twice to obtain a filter cake 1.
(1) Ion-exchanged water (100 parts) was added to the filter cake, and the mixture was mixed with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at 12000 rpm for 10 minutes and then filtered.
(2) 100 parts of a 10 mass% sodium hydroxide aqueous solution was added to the filter cake, and the mixture was mixed at 12000 rpm for 30 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.), and then filtered under reduced pressure. (3) 100 parts of 10 mass% hydrochloric acid was added to the filter cake, and the mixture was mixed at 12000 rpm for 10 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) and then filtered.
(4) 300 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed at 12000 rpm for 10 minutes using a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) and then filtered.
The filter cake 1 was dried at 45° C. for 48 hours using a circulating air drier, and then sieved with a mesh having an opening of 75 μm to obtain toner particles.
To 100 parts by mass of the obtained toner particles, 1.0 part by mass of silica fine particles having a primary average particle size of 13.0 nm was added, and the peripheral speed was 45 m/with a Henschel mixer (FM75 type, manufactured by Mitsui Miike Kakoki Co., Ltd.). After mixing for 5 minutes, the toner 20 was obtained by passing through an ultrasonic vibrating screen having an opening of 54 μm. Table 3 shows the particle size and circularity of the toner 20.

<Production Example of Magnetic Core Particles>
Process 1 (weighing/mixing process):
Fe ₂ O ₃ 60.2% by mass
MnCO ₃ 33.9 mass%
Mg(OH) ₂ 4.8 mass%
SrCO ₃ 1.1% by mass
The ferrite raw material was weighed so that Then, it was pulverized and mixed for 2 hours with a dry ball mill using zirconia (φ10 mm) balls.
Process 2 (preliminary baking process):
After crushing and mixing, a calcined ferrite was produced by firing at 1000° C. for 3 hours in the atmosphere using a burner type firing furnace. The composition of ferrite is as follows.
(MnO) in a (MgO) b (SrO) c (Fe 2 O 3) d above formula, a = 0.39, b = 0.11 , c = 0.01, d = 0.50

Process 3 (crushing process):
After crushing to about 0.5 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using balls of zirconia (φ10 mm), and crushed for 2 hours with a wet ball mill.
The slurry was pulverized with a wet bead mill using zirconia beads (φ1.0 mm) for 4 hours to obtain a ferrite slurry.
Process 4 (granulation process):
2.0 parts by mass of polyvinyl alcohol was added to 100 parts by mass of calcined ferrite as a binder in the ferrite slurry, and granulated into spherical particles of about 36 μm with a spray dryer (manufacturer: Okawara Kakohki).
Step 5 (main firing step):
In order to control the firing atmosphere, firing was performed in an electric furnace in a nitrogen atmosphere (oxygen concentration of 1.00 vol% or less) at 1150° C. for 4 hours.
Process 6 (selection process):
After crushing the agglomerated particles, coarse particles were removed by sieving with a sieve having an opening of 250 μm to obtain magnetic core particles 1.

<Production example of coat resin>
Cyclohexyl methacrylate monomer 26.8 parts by weight Methyl methacrylate monomer 0.2 parts by weight Methyl methacrylate macromonomer 8.4 parts by weight (macromonomer having methacryloyl group at one end and having a weight average molecular weight of 5000)
Toluene 31.3 parts by mass Methyl ethyl ketone 31.3 parts by mass Add the above materials to a four-necked separable flask equipped with a reflux condenser, a thermometer, a nitrogen introducing tube and a stirrer, and introduce nitrogen gas sufficiently. The atmosphere was nitrogen. Then, the mixture was heated to 80° C., 2.0 parts by mass of azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was filtered off and dried in vacuum to obtain a coat resin.

<Example of magnetic carrier production>
Coat resin 20.0% by mass
Toluene 80.0% by mass
The above materials were dispersed and mixed by a bead mill to obtain a resin liquid.
100 parts by mass of the magnetic core particles were charged into a Nauta mixer, and further, the resin liquid was charged into the Nauta mixer as a resin component in an amount of 2.0 parts by mass. The mixture was heated to a temperature of 70° C. under reduced pressure, mixed at 100 rpm, and solvent removal and coating operations were performed for 4 hours. Then, the obtained sample was transferred to a Julia mixer, heat-treated at 100° C. for 2 hours in a nitrogen atmosphere, and then classified with a sieve having an opening of 70 μm to obtain a magnetic carrier 1. The volume distribution-based 50% particle diameter (D50) of the resulting magnetic carrier 1 was 38.2 μm.

  The toners 1 to 25 and the magnetic carrier 1 described above were mixed with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) for 0.5 s-1 at a rotation time of 5 min so that the toner concentration would be 8.0% by mass. And mixed to obtain two-component developers 1 to 25.

<Example 1>
As an image forming apparatus, a Canon digital commercial printing printer image RUNNER ADVANCE C9075 PRO remodeling machine is used, and the two-component developer 1 is put into the developing device at the cyan position and/or the magenta position, and the toner amount on the paper is desired. The following image was formed and evaluated as described below. The modification points were such that the fixing temperature, the process speed, the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power can be freely set. For image output evaluation, an FFh image (solid image) with a desired image ratio was output. FFh is a value in which 256 gradations are displayed in hexadecimal notation, 00h is the first gradation of 256 gradations (white background portion), and FFh is the 256th gradation of 256 gradations (solid portion). ..
Evaluations were made based on the following evaluation methods, and the results are shown in Table 5.

[Low temperature fixability evaluation]
Paper: CS-680 (68.0 g/m ² ) (Canon Marketing Japan Inc.)
Amount of applied toner on paper: 1.20 mg/cm ²
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: An image of 10 cm ² is placed in the center of the A4 paper. Fixing test environment: low temperature and low humidity environment: temperature 15° C./humidity 10% RH (hereinafter “L/L”)
Fixing temperature: 170℃
Process speed: 450 mm/sec
The evaluation image was output and the low temperature fixability was evaluated. The value of the image density reduction rate was used as an evaluation index of low temperature fixability. The image density reduction rate was obtained by first measuring the image density of the central portion using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, a load of 4.9 kPa (50 g/cm ² ) was applied to the portion where the image density was measured, and the fixed image was rubbed (5 reciprocations) with sillbon paper, and the image density was measured again. Then, the reduction rate (%) of the image density before and after the rubbing was measured.
(Evaluation criteria)
A: Concentration decrease rate less than 2.0% (excellent)
B: Density reduction rate of 2.0% or more and less than 5.0% (good)
C: Density reduction rate of 5.0% or more and less than 15.0% (level that does not cause a problem in the present invention)
D: Density reduction rate of 15.0% or more (unacceptable level in the present invention)

[Environmental stability]
The image densities of the 5000th solid image were measured under low-temperature low-humidity environment and high-temperature high-humidity environment (temperature 30° C./humidity 80% RH), and the density difference between them was calculated. This density difference was used as an index of the environmental stability of the toner. The image density was measured by the above-mentioned X-Rite color reflection densitometer.
(Evaluation criteria)
A: Concentration difference less than 0.10 (excellent)
B: Concentration difference of 0.10 or more and less than 0.15 (good)
C: Concentration difference of 0.15 or more and less than 0.25 (a level that does not pose a problem in the present invention)
D: Density difference of 0.25 or more (unacceptable level in the present invention)

[Storability]
5 g of the toner was put in a 100 cc poly cup and left in a temperature and humidity variable type thermostat (55° C. 41%) for 48 hours, and after the standing, the cohesiveness of the toner was evaluated. The cohesiveness was evaluated by using the powder tester PT-X manufactured by Hosokawa Micron Co., Ltd. as an evaluation index based on the residual rate of the toner remaining when the powder was shaken with a mesh having an opening of 20 μm for 10 seconds at an amplitude of 0.5 mm.
(Evaluation criteria)
A: Residual rate is less than 2.0% (very excellent)
B: Residual rate of 2.0% or more and less than 10.0% (good)
C: Residual rate of 10.0% or more and less than 15.0% (at a level where there is no problem in the present invention)
D: Residual rate 15.0% or more (not acceptable in the present invention)

<Examples 2 to 20 and Comparative Examples 1 to 5>
Evaluation was performed in the same manner as in Example 1 except that the two-component developers 2 to 25 were used. The evaluation results are shown in Table 5.

Claims (8)

In a toner having toner particles containing an amorphous resin, a resin composition, and a crystalline polyester resin,
The resin composition contains a polymer in which a styrene acrylic polymer is graft-polymerized on a polyolefin,
The crystalline polyester resin is a urethane-modified crystalline polyester resin,
The content of the crystalline polyester resin, based on the total of the non-crystalline resin and the crystalline polyester resin state, and are 1% by weight to 20% by weight,
The toner the toner is characterized in toner der Rukoto melt-kneading pulverization.   The crystalline polyester resin has a carboxylic acid unit, an alcohol unit and an isocyanate unit,
  The toner according to claim 1, wherein the content of the isocyanate unit is 1.0 mol% or more and 10.0 mol% or less based on the total number of moles of the unit.   The toner according to claim 2, wherein the isocyanate unit is a unit derived from a linear aliphatic diisocyanate.   In a toner having toner particles containing an amorphous resin, a resin composition, and a crystalline polyester resin,
  The resin composition contains a polymer in which a styrene acrylic polymer is graft-polymerized on a polyolefin,
  The crystalline polyester resin is a urethane-modified crystalline polyester resin,
  The content of the crystalline polyester resin is 1% by mass or more and 20% by mass or less based on the total amount of the amorphous resin and the crystalline polyester resin,
  The crystalline polyester resin has a carboxylic acid unit, an alcohol unit and an isocyanate unit,
  Based on the total number of moles of the unit, the content of the isocyanate unit is 1.0 mol% or more and 10.0 mol% or less,
  The toner, wherein the isocyanate unit is a unit derived from a linear aliphatic diisocyanate. The toner according to claim 2, wherein the isocyanate unit is a unit derived from a linear aliphatic diisocyanate having 4 to 8 carbon atoms. The urethane-modified crystalline polyester resin has a crystalline polyester moiety containing the alcohol unit and the carboxylic acid unit,
The crystalline polyester moiety is a condensation product of an alcohol component containing an aliphatic diol having 6 to 18 carbon atoms as a main component and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms as a main component. The toner according to claim 2, which is a polymer. The resin composition has a monomer unit having a functional group containing a nitrogen atom,
The content of the monomer unit having a functional group containing a nitrogen atom is 10.0 mol% or more and 50.0 mol% or less based on the total number of moles of all the monomer units constituting the resin composition. The toner according to any one of 1. A method for producing a toner, comprising a step of melt-kneading an amorphous resin, a resin composition, and a crystalline polyester resin, and pulverizing the obtained kneaded product,
The resin composition contains a polymer in which a styrene acrylic polymer is graft-polymerized on a polyolefin,
The crystalline polyester resin is a urethane-modified crystalline polyester resin,
The method for producing a toner, wherein the content of the crystalline polyester resin is 1% by mass or more and 20% by mass or less based on the total amount of the amorphous resin and the crystalline polyester resin.