JP2018156074A - Toner binder and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To have excellent low temperature fixability, glossiness and hot offset resistance, and toner fluidity, heat storage stability, charge stability, crushability, image strength, bending resistance and document offset property, moisture heat storage resistance and durability. A toner binder containing a crystalline resin (A), an amorphous polyvinyl resin (B) having an ester group, and an amorphous polyester resin (C). , A toner binder characterized by satisfying the following relational expression (1). Q2 / Q1> 0.50 (1) [In the formula, Q1 is the endothermic amount based on the endothermic peak derived from the crystalline resin (A) in the first heating process measured by the differential scanning calorimeter (DSC). [J / g] and Q2 represent the endothermic amount [J / g] based on the endothermic peak derived from the crystalline resin (A) in the second heating process. ] [Selection diagram] None

Description

  The present invention relates to a toner binder and a toner.

In recent years, with the development of electrophotographic systems, the demand for electrophotographic apparatuses such as copiers and laser printers is rapidly increasing, and the demands for their performance are also increasing.
Conventionally, for electrophotography, a latent image based on image information is formed on a latent image carrier such as an electrophotographic photosensitive member, the latent image is developed with a corresponding color toner, and then the toner image is transferred onto a transfer material. There are known methods and apparatuses that obtain an image by heating and fixing a toner image on a transfer material after repeating an image forming process such as transferring to a toner.

  In order to pass through these processes without problems, the toner must first maintain a stable charge amount, and then it must have good fixability to paper. In addition, since the apparatus includes a heating body in the fixing unit, the temperature rises in the apparatus, and thus the toner is required not to block in the apparatus.

Further, there is a strong demand for improvement in low-temperature fixability of toner from the viewpoint of energy saving in that the electrophotographic apparatus is reduced in size, speeded up, and promotes higher image quality and energy consumption in the fixing process is reduced.
Recently, many types of paper such as recycled paper with large surface irregularities and coated paper with a smooth surface are used as a transfer material. In order to cope with the surface properties of these transfer materials, a fixing device having a wide nip width such as a soft roller or a belt roller is preferably used. However, when the nip width is widened, the contact area between the toner and the fixing roller increases, and a so-called high temperature offset phenomenon occurs in which the molten toner adheres to the fixing roller. Therefore, it is assumed that offset resistance is required.

As a method for satisfying the above, a technique for incorporating amorphous polyester into amorphous polyester has been proposed (Patent Document 1).
Such a method can secure low-temperature fixability and glossiness of the toner, but has insufficient hot-offset resistance, toner fluidity, and heat-resistant storage stability, which is stability during high-temperature storage, and charging stability and pulverization. There is also a problem that the grindability at the time is lowered.
A method of coating with a shell layer obtained by using an emulsion aggregation method has also been proposed (Patent Document 2), but the crystalline resin becomes compatible with the toner binder of the core, and reprecipitation of crystals does not occur in a short time. Since it is sufficient, the image strength after fixing and the bending resistance are still insufficient.
Further, the above method has insufficient moisture and heat storage stability, which is stable at high humidity, and the durability of the toner is lowered, and the design of the copying machine / printer is limited. Furthermore, there is a problem that the cost as a toner is high.
On the other hand, there is a method in which a crystalline resin is added to an amorphous polyvinyl resin and crystal precipitation is promoted by utilizing incompatibility with the crystalline resin (Patent Document 3). The durability is improved, and the wet heat and heat storage stability is also good. However, since crystalline polyester and polyvinyl resin have poor compatibility, sufficient low-temperature fixability cannot be obtained, and gloss and charge stability of a printed image are insufficient.

JP 2005-308995 A JP 2006-251564 A JP 2011-197659 A

  The present invention includes low-temperature fixability and glossiness, hot offset resistance, toner fluidity, heat-resistant storage stability, charge stability, pulverization property, image strength, folding resistance, document offset property, wet heat storage resistance and durability. It is an object to provide a toner binder and a toner excellent in the above.

As a result of intensive studies to solve these problems, the present inventors have reached the present invention.
That is, the present invention provides a toner binder containing a crystalline resin (A), an amorphous polyvinyl resin (B) having an ester group, and an amorphous polyester resin (C), wherein the following relational expression (1) is satisfied. A toner binder characterized by satisfying; a toner containing the toner binder.
Q2 / Q1> 0.50 (1)
[In the formula, Q1 is a crystalline resin in the first temperature rising process of the toner binder measured by a differential scanning calorimeter (DSC) that is heated from 0 ° C. to 150 ° C. under the condition of 10 ° C./min ( The endothermic amount [J / g], Q2 based on the endothermic peak derived from A) is measured from 150 ° C. after measuring Q1 in the first temperature rising process of the toner binder measured by a differential scanning calorimeter (DSC). An endothermic amount based on an endothermic peak derived from the crystalline resin (A) in the second temperature raising process in which the temperature is raised from 0 ° C. to 10 ° C. per minute and then raised again from 0 ° C. to 150 ° C. at 10 ° C. per minute. [J / g] is represented. ]

  According to the present invention, low-temperature fixability and glossiness, hot offset resistance, toner fluidity, heat-resistant storage stability, charge stability, pulverization, image strength, folding resistance, document offset resistance, wet heat resistance and durability It is possible to provide an excellent toner binder and toner.

The toner binder of the present invention contains a crystalline resin (A), an amorphous polyvinyl resin (B) having an ester group, and an amorphous polyester resin (C).
Further, it is necessary to satisfy the following relational expression (1) from the viewpoints of toner fluidity, heat-resistant storage stability, charging stability, grindability, image strength, and document offset.

Q2 / Q1> 0.50 (1)
[In the formula, Q1 is a crystalline resin in the first temperature rising process of the toner binder measured by a differential scanning calorimeter (DSC) that is heated from 0 ° C. to 150 ° C. under the condition of 10 ° C./min ( The endothermic amount [J / g], Q2 based on the endothermic peak derived from A) is measured from 150 ° C. after measuring Q1 in the first temperature rising process of the toner binder measured by a differential scanning calorimeter (DSC). An endothermic amount based on an endothermic peak derived from the crystalline resin (A) in the second temperature raising process in which the temperature is raised from 0 ° C. to 10 ° C. per minute and then raised again from 0 ° C. to 150 ° C. at 10 ° C. per minute. [J / g] is represented. ]

In the toner and toner binder of the present invention, the first temperature rising process measured by a differential scanning calorimeter (DSC) corresponds to the heat fixing process, and the second temperature rising process is the heat of the obtained fixed image. It can be said that it corresponds to stability.
That is, when the relational expression (1) is satisfied, in the thermal fixing process corresponding to the first temperature raising process, a part of the crystalline resin (A) is amorphous polyvinyl resin (B) or amorphous polyester resin (C ) And the toner is plasticized so that it can be fixed at a low temperature. However, after cooling, the crystalline resin (A) is recrystallized to reduce the Tg and the toner binder. Viscosity can be eliminated and the thermal stability of the fixed image can be improved.
Further, from the same phenomenon, it is possible to suppress a decrease in Tg of the toner binder after melt-kneading, and the toner can be manufactured without performing a special process as in Patent Document 1.

Therefore, by satisfying the relational expression (1), it is possible to achieve both the heat resistant storage stability and the low-temperature fixability at a high level, and the toner fluidity, heat storage stability, charging stability, toner binder. The pulverization property, image strength, and document offset property are improved. Q2 / Q1 is an index of the easiness of precipitation of the crystals (A) in the toner binder during cooling after heat fixing. The larger the value, the easier (A) crystals are precipitated during cooling, and the thermal stability of the fixed image. Can be increased. It preferably satisfies the relational expression (1-1), more preferably satisfies the relational expression (1-2), and most preferably satisfies the relational expression (1-3).
Q2 / Q1 ≧ 0.55 (1-1)
Q2 / Q1 ≧ 0.60 (1-2)
Q2 / Q1 ≧ 0.65 (1-3)
In order to increase Q2 / Q1, the weight average molecular weight of the crystalline resin (A) or the amorphous polyester resin (C) is increased, and the ratio of the crystalline resin (A) in the toner binder is increased. Residual water content, monomer, organic solvent and surface activity increase the difference between SP _C which is the solubility parameter (SP value) of resin (C) and SP _A which is the solubility parameter of crystalline resin (A) It can be controlled by reducing the amount of the agent.

When the endothermic amount of the toner binder of the present invention is repeatedly measured with a differential scanning calorimeter (DSC) under the above conditions of temperature rise, cooling and temperature rise, an endothermic peak derived from the crystalline resin (A) is shown.
Therefore, the endothermic amount Q1 is based on the endothermic peak in the first temperature raising process, and the endothermic amount Q2 is based on the endothermic peak in the second temperature raising process.

  As the temperature raising / cooling conditions for the measurement by DSC, the temperature is raised from 0 ° C. to 150 ° C. under the condition of 10 ° C./min (first temperature raising process). Subsequently, it cools to 0 degreeC on the conditions of 10 degreeC / min (1st cooling process). Further, the temperature is raised to 150 ° C. under the condition of 10 ° C./min (second temperature raising process).

When there are two or more endothermic peaks derived from the crystalline resin (A), the endothermic amount is calculated by adding together the endothermic peak areas corresponding to Q1 and Q2 in the DSC chart.
When the endothermic peak derived from the crystalline resin (A) overlaps with the endothermic peak not derived from the crystalline resin (A), the endothermic peak not derived from the crystalline resin (A) is subtracted. Of the raw materials further blended into the toner binder, a crystalline raw material (crystalline substance alone) such as wax may exhibit an endothermic peak. In such a case, from the sum of the endothermic peak areas, the heat of fusion (Q _w0 ) of the crystalline substance that is not derived from the crystalline resin (A) and not derived from the crystalline resin (A) in the toner binder. The value (Q _w ) calculated from the content (q _w ) of the crystalline substance alone as the following formula (Q _w ) as the heat of fusion of the crystalline substance alone not derived from the crystalline resin (A), and the sum of the endothermic peak areas It can be calculated by subtracting from.

Q _W = Q _W0 × q _W / 100

The heat of fusion (Q _W0 ) of a single crystalline substance not derived from the crystalline resin (A) and the content (q _W ) of a single crystalline substance not derived from the crystalline resin (A) in the toner binder are, for example, It may be calculated from the analysis result of the raw material of the toner to be produced and its composition ratio, and when this is not known, the composition of the toner is analyzed by isolating and analyzing the constituent material by solvent extraction of the toner. It may be calculated after clarifying the constituent ratio of the constituent substances.

  The endothermic amount Q2 (J / g) derived from the crystalline resin (A) in the second temperature raising process is preferably 0.5 to 30 J / g, more preferably 1 to 25 J / g, and still more preferably 2 to 20 J. / G. From the viewpoint of low-temperature fixability and gloss, the endothermic amount derived from the crystalline resin (A) is preferably 0.5 J / g or more, and preferably 30 J / g or less from the viewpoint of durability, document offset property and image strength. The endothermic amount derived from the crystalline resin (A) in the temperature raising process is measured by DSC.

“Crystallinity” in the present invention refers to a resin having a clear endothermic peak in the first heating step of the DSC measurement.
The endothermic peak top temperature Ta (° C.) derived from the crystalline resin (A) is preferably 40 to 100 ° C., more preferably 50 to 90 ° C., and particularly preferably 55 to 85 ° C. Ta is preferably 40 ° C. or higher from the viewpoint of heat resistant storage stability, wet heat storage resistance, toner durability, and charging stability of the toner, and 100 ° C. or lower is preferable from the viewpoint of low-temperature fixability and gloss.
The peak top temperature refers to the temperature at the deepest portion of the recess of the endothermic peak of the DSC chart.
And when there are two or more endothermic peaks derived from the crystalline resin (A), at least one of them should be in this range.
When it is desired to increase the endothermic peak top temperature Ta (° C.), a chain aliphatic diol, a linear alkanedicarboxylic acid, a linear alkenedicarboxylic acid and / or a linear alkyl group which are constituent monomers described later It can be controlled by increasing the number of carbon atoms of the alkyl (meth) acrylate having.

The type of the crystalline resin (A) of the present invention is not particularly limited as long as it has a clear endothermic peak in the first temperature rising process of the DSC measurement described above. For example, a crystalline polyester resin, Examples thereof include resins such as a crystalline polyurethane resin, a crystalline polyurea resin, a crystalline polyamide resin, and a crystalline polyvinyl resin.
(A) may use 1 type and may use 2 or more types together.

  Among the above crystalline resins (A), the crystalline polyvinyl resin and the crystalline polyester resin can easily control the compatibility with the amorphous polyvinyl resin (B) and the amorphous polyester resin (C) having an ester group. This is preferable.

  Preferred examples of the crystalline polyvinyl resin include polymers having a monomer having a polymerizable double bond and an ester group as essential constituent monomers. One type of monomer may be used, or two or more types may be used in combination.

Specific examples of the monomer having a polymerizable double bond and an ester group include esterified products of vinyl alcohol and aliphatic monocarboxylic acid (such as vinyl acetate, vinyl propionate and vinyl butyrate), allyl alcohol, and the like. Esterified products with dicarboxylic acid (diallyl phthalate, diallyl adipate, etc.), esterified products with 2-methylallyl alcohol and aliphatic monocarboxylic acid (isopropenyl acetate, etc.), vinyl methacrylate, vinyl alcohol and aromatic monocarboxylic acid Esterified products (vinyl benzoate, methyl-4-vinyl benzoate, etc.), esterified products of alicyclic alcohol and methacrylic acid (cyclohexyl methacrylate, etc.), esterified products of aromatic (aliphatic) alcohol and (meth) acrylic acid (benzyl) (Meth) acrylate, Phenyl (meth) acrylate, etc.), vinyl methoxyacetate, ethyl-α-ethoxy acrylate, alkyl (meth) acrylate having a straight or branched alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate , Propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate, stearyl (meth) acrylate And behenyl acrylate, etc.], dialkyl fumarate (two alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups are Straight chain having 2 to 8 carbon atoms, Branched or alicyclic groups), poly (meth) allyloxyalkanes (diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane and tetrametaaryl Monomers having a polyalkylene glycol chain, a polymerizable double bond and an ester group [polyethylene glycol [Mn = 300] mono (meth) acrylate, polypropylene glycol (Mn = 500) monoacrylate, methyl, etc. Alcohol EO 10 mol adduct (meth) acrylate and lauryl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene Glycoldi Meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and polyethylene glycol di (meth) acrylate, etc.] and the like.
Of these monomers having a polymerizable double bond and an ester group, alkyl (meth) acrylates having a linear alkyl group having 1 to 50 carbon atoms are preferred from the viewpoints of crystallinity, low-temperature fixability and heat-resistant storage stability. Further, an alkyl (meth) acrylate having a linear alkyl group having 18 to 36 carbon atoms is more preferable, and stearyl (meth) acrylate and behenyl (meth) acrylate are most preferable.
The proportion of the monomer having a polymerizable double bond and an ester group is preferably 30% by weight or more from the viewpoint of crystallinity, based on the total weight of monomers constituting the crystalline polyvinyl resin, More preferably, it is 60 weight% or more, Most preferably, it is 90 weight% or more.

  Crystalline polyvinyl resin is a monomer having a polymerizable double bond in addition to a monomer having a polymerizable double bond and an ester group, and a monomer having a polymerizable double bond and an ester group. Monomers (such as styrene), monomers having a carboxyl group and a polymerizable double bond, and salts thereof (such as methacrylic acid and acrylic acid, and salts thereof (alkali metal salts, ammonium salts, amine salts, and quaternary ammonium). Salts, etc.), monomers having a sulfo group and a polymerizable double bond and salts thereof, monomers having a phosphono group and a polymerizable double bond, and salts thereof, hydroxyl groups and a polymerizable double bond A monomer having a bond, a nitrogen-containing monomer having a polymerizable double bond (such as acrylonitrile), a monomer having 6 to 18 carbon atoms having an epoxy group and a polymerizable double bond, and a halogen element Polymerizability Monomers having 2 to 16 carbon atoms having a heavy bond, ethers having a polymerizable double bond (such as ethyl vinyl ether), ketones having a polymerizable double bond, and sulfur-containing compounds having a polymerizable double bond, etc. Can be used as a constituent monomer. The ratio of the monomer excluding the monomer having a polymerizable double bond and an ester group is based on the total weight of monomers constituting the crystalline polyvinyl resin, from the viewpoint of crystallinity and compatibility. Preferably it is 0-70 weight%, More preferably, it is 0-40 weight%, Most preferably, it is 0-10 weight%.

  Examples of the crystalline polyester resin include a polyester resin having a diol component (x) and a dicarboxylic acid component (y) as essential constituent monomers, and a trivalent or higher alcohol component or trivalent as necessary. The above polycarboxylic acid components may be used in combination.

  Examples of the diol of the diol component (x) include those other than the diol (x ′) having a functional group to be described later (those having no functional group other than two hydroxyl groups). Chain aliphatic diol {linear aliphatic diol (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-tetradecanediol 1,18-octadecanediol and 1,20-eicosanediol), branched chain aliphatic diol (1,2-propanediol, etc.) C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polytetramethylene ether glycol, etc.)}; C4-C36 alicyclic diol (1,4-cyclohexanedimethanol and hydrogenation) Bisphenol A and the like; alkylene oxide of the above alicyclic diol (hereinafter, “alkylene oxide” may be abbreviated as AO) [ethylene oxide (hereinafter, “ethylene oxide” may be abbreviated as EO), propylene Oxides (hereinafter, “propylene oxide” is abbreviated as PO) and butylene oxide (hereinafter, “butylene oxide” is abbreviated as BO), etc.] adducts (preferably 1-30 added moles, etc.); bisphenols (bisphenols) A, Sphenol F, bisphenol S, etc.) AO (EO, PO, BO, etc.) adducts (preferably 2-30 added moles, etc.); polylactone diol (poly ε-caprolactone diol, etc.); polybutadiene diol, etc. . As a diol component (x), 1 type may be used and these 2 or more types may be used together.

  Among these diols, chain aliphatic diols are preferable from the viewpoint of crystallinity. The number of carbon atoms is preferably 2 to 36, and more preferably 2 to 20. Further, from the same viewpoint, a linear aliphatic diol is preferable to a branched aliphatic diol.

  Examples of the linear aliphatic diol preferably include those having 2 to 36 carbon atoms, and more preferably those having 2 to 20 carbon atoms. Specific examples include ethylene glycol and 1,3-propanediol. 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, Examples include 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,20-eicosanediol. Among these, from the viewpoint of crystallinity, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol and 1,1 12-dodecanediol is preferred.

  From the viewpoint of crystallinity, low-temperature fixability and heat-resistant storage stability, the content of the linear aliphatic diol is based on the total number of moles of the diol component (x) used as the monomer constituting the crystalline polyester resin. , 80 mol% or more, preferably 90 mol% or more.

  As the polyol having 3 to 8 or more valences used in combination with the diol component (x) as necessary, a polyhydric aliphatic alcohol having 3 to 8 or more carbon atoms having 3 to 36 carbon atoms (alkane polyol and its molecule or Intermolecular dehydrates (eg glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan and polyglycerin etc.); sugars and derivatives thereof (eg sucrose and methylglucoside etc.); trisphenols (trisphenol PA) Etc.) AO adduct (preferably 2-30 mol added); AO adduct (preferably 2-30 mol added) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol (hydroxyethyl (meth)) Acrylate and other vinyl monomers Such as copolymer); and the like. As a 3-8 valence or more polyol, 1 type may be used and 2 or more types may be used together.

  Among these, from the viewpoint of hot offset resistance, preferred are 3 to 8 or higher polyhydric aliphatic alcohols and AO adducts of novolac resins, and more preferred are AO adducts of novolak resins.

In addition to the diol component (x), the crystalline polyester resin comprises two hydroxyl groups, a carboxylic acid (salt) group, a sulfonic acid (salt) group, a sulfamic acid (salt) group, and a phosphoric acid (salt) group. A diol (x ′) having at least one group selected from the group (hereinafter sometimes abbreviated as “diol having a functional group”) may be used as a constituent monomer. As the diol (x ′) having the functional group, one type may be used, or two or more types may be used in combination.
In the present invention, the expression “acid (salt)” means “acid or acid salt”.

  Examples of the diol having a carboxylic acid (salt) group include tartaric acid (salt), 2,2-bis (hydroxymethyl) propanoic acid (salt), 2,2-bis (hydroxymethyl) butanoic acid (salt), and 3- [ Bis (2-hydroxyethyl) amino] propanoic acid (salt) and the like.

  Examples of the diol having a sulfonic acid (salt) group include 2,2-bis (hydroxymethyl) ethanesulfonic acid (salt), 2- [bis (2-hydroxyethyl) amino] ethanesulfonic acid (salt), and 5-sulfo. -Isophthalic acid-1,3-bis (2-hydroxyethyl) ester (salt) etc. are mentioned.

  Examples of the diol having a sulfamic acid (salt) group include N, N-bis (2-hydroxyethyl) sulfamic acid (salt), N, N-bis (3-hydroxypropyl) sulfamic acid (salt), and N, N- Examples thereof include bis (4-hydroxybutyl) sulfamic acid (salt) and N, N-bis (2-hydroxypropyl) sulfamic acid (salt).

Examples of the diol having a phosphoric acid (salt) group include bis (2-hydroxyethyl) phosphate (salt).
The salts that make up the acid salts include ammonium salts, amine salts (methylamine salts, dimethylamine salts, trimethylamine salts, ethylamine salts, diethylamine salts, triethylamine salts, propylamine salts, dipropylamine salts, tripropylamine salts, butylamines. Salt, dibutylamine salt, tributylamine salt, monoethanolamine salt, diethanolamine salt, triethanolamine salt, N-methylethanolamine salt, N-ethylethanolamine salt, N, N-dimethylethanolamine salt, N, N- Diethylethanolamine salt, hydroxylamine salt, N, N-diethylhydroxylamine salt, morpholine salt, etc.), quaternary ammonium salt [tetramethylammonium salt, tetraethylammonium salt and trimethyl (2-hydroxyethyl) Ammonium salts] and alkali metal salts (sodium salts and potassium salts, etc.).

  Of the diols (x ′) having a functional group, preferred are a diol having a carboxylic acid (salt) group and a diol having a sulfonic acid (salt) group from the viewpoint of charge stability and heat resistant storage stability of the toner.

  Examples of the dicarboxylic acid of the dicarboxylic acid component (y) constituting the crystalline polyester resin include alkane dicarboxylic acids having 2 to 50 carbon atoms (including carbon of the carbonyl group) (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecane) Dicarboxylic acids, octadecanedicarboxylic acids and decylsuccinic acids); alkene dicarboxylic acids having 4 to 50 carbon atoms (alkenyl succinic acids such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, maleic acid, fumaric acid and Citraconic acid etc.); C6-C40 alicyclic dicarboxylic acid [dimer acid (dimerized linoleic acid), etc.]; C8-C36 aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, t- Butyl isophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'-biphenyl dicar Etc. phosphate) and the like. As dicarboxylic acid component (y), 1 type may be used and these 2 or more types may be used together.

Among these dicarboxylic acids, alkane dicarboxylic acids and alkene dicarboxylic acids are preferred from the viewpoints of crystallinity, low-temperature fixability and heat-resistant storage stability, and linear alkane dicarboxylic acids and linear alkene dicarboxylic acids (adipic acid, sebacin) Acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, maleic acid, fumaric acid and the like) are particularly preferable. The copolymerization amount of the linear alkane dicarboxylic acid and the linear alkene dicarboxylic acid is based on the total number of moles of the dicarboxylic acid component (y) constituting the crystalline polyester resin. 80 mol% or more is preferable from the viewpoint of heat-resistant storage stability.
Also preferred are those obtained by copolymerizing an alkane dicarboxylic acid and / or an alkene dicarboxylic acid together with an aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, t-butylisophthalic acid and their lower alkyl esters). The copolymerization amount of the aromatic dicarboxylic acid is 20 mol% or less from the viewpoint of crystallinity, low-temperature fixability and heat-resistant storage stability, based on the total number of moles of the dicarboxylic acid component (y) constituting the crystalline polyester resin. Is preferred.

  In the production of the crystalline polyester resin, the tricarboxylic or higher polycarboxylic acid component used as necessary includes polycarboxylic acids having 3 to 6 or higher valences. Examples of polycarboxylic acids having 3 to 6 or more valences include, for example, aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid) and aliphatic tricarboxylic acids having 6 to 36 carbon atoms. (Hexane tricarboxylic acid etc.) etc. are mentioned.

  In addition, as dicarboxylic acid or polycarboxylic acid having 3 to 6 or more valences, acid anhydrides as described above, or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) May be used.

As the crystalline polyurethane resin, the crystalline polyester resin and the diisocyanate (v) are used as constituent monomers, and the crystalline polyester resin, the diol component (x) and the diisocyanate (v) are configured. The thing made into a monomer etc. are mentioned.
A crystalline polyurethane resin having a crystalline polyester resin and diisocyanate (v) as constituent monomers can be obtained by reacting the crystalline polyester resin and diisocyanate (v). The crystalline polyurethane resin comprising the crystalline polyester resin, the diol component (x) and the diisocyanate (v) as constituent monomers is obtained by reacting the crystalline polyester resin, the diol component (x) and the diisocyanate (v). Can be obtained.

  In addition to the diol component (x), the diol (x ′) having the functional group as a structural unit improves the charging stability and heat resistant storage stability of the toner.

  As the diisocyanate (v), an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, a modified product of these diisocyanates (urethane group, Carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified product) and mixtures of two or more thereof.

  Examples of the aromatic diisocyanate having 6 to 20 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, m- or p-xylylene diene. Isocyanates (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI) and crude diaminophenylmethane diisocyanate (crude MDI) Etc.

Examples of the aliphatic diisocyanate having 2 to 18 carbon atoms include a chain aliphatic diisocyanate having 2 to 18 carbon atoms and a cyclic aliphatic diisocyanate having 3 to 18 carbon atoms.
Examples of the chain aliphatic diisocyanate having 2 to 18 carbon atoms include linear aliphatic diisocyanates (ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, etc.), branched aliphatic diisocyanates (2, 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl- 2,6-diisocyanatohexanoate etc.) and mixtures thereof.

  Examples of the cycloaliphatic diisocyanate having 3 to 18 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis ( 2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate and mixtures thereof.

  As the modified product of diisocyanate, a modified product containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group, a uretdione group, a uretoimine group, an isocyanurate group and / or an oxazolidone group is used. Urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI, and mixtures thereof (for example, a mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)).

  Of these diisocyanates (v), from the viewpoint of hot offset resistance and bending resistance, preferred are aromatic diisocyanates having 6 to 15 carbon atoms and aliphatic diisocyanates having 4 to 15 carbon atoms, and more preferred. Are TDI, MDI, HDI, hydrogenated MDI and IPDI.

  From the viewpoint of compatibility with the amorphous polyester resin (C), the crystalline polyurethane resin is preferably 50% by weight or more of the crystalline polyester resin used as a monomer constituting the crystalline polyurethane resin.

  Examples of the crystalline polyurea resin include those containing the crystalline polyester resin, diamine (z) and diisocyanate (v) as constituent monomers. Such a crystalline polyurea resin can be obtained by reacting a crystalline polyester resin, a diamine (z) and a diisocyanate (v).

Examples of the diamine (z) include aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms.
Examples of the aliphatic diamine having 2 to 18 carbon atoms include a chain aliphatic diamine and a cyclic aliphatic diamine.

Examples of chain aliphatic diamines include alkylene diamines having 2 to 12 carbon atoms (such as ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine and hexamethylene diamine) and polyalkylenes (preferably having 2 to 6 carbon atoms) polyamines [diethylene triamines. , Iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like.
Cycloaliphatic polyamines include alicyclic diamines having 4 to 15 carbon atoms {1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4'-methylene dicyclohexane diamine (hydrogenated methylene dianiline) and 3 , 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like} and a heterocyclic diamine having 4 to 15 carbon atoms [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, etc.] and the like.

  The aromatic diamine having 6 to 20 carbon atoms is an aromatic having an unsubstituted aromatic diamine or an alkyl group (an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n- or isopropyl group, and a butyl group). Examples include diamines.

  Examples of the unsubstituted aromatic diamine include 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, diaminodiphenylsulfone, benzidine, thiodianiline, bis (3 , 4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, naphthylenediamine and mixtures thereof.

  The aromatic diamine having an alkyl group (alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n- or isopropyl group and butyl group) includes 2,4- or 2,6-tolylenediamine, crude Tolylenediamine, diethyltolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 4,4′-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2 , 4-diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl -2,5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl -2,4-diaminobenzene, 1,3,5-triisopropyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl -2,6-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6 -Dibutyl-1,5-diaminonaphthalene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetraisopropylbenzidine, 3,3 ', 5,5'-tetramethyl -4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraisopropyl-4, '-Diaminodiphenylmethane, 3,3', 5,5'-tetrabutyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,5-diisopropyl- 3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3', 5 5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraisopropyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4 ′ -Diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenyl sulfone and mixtures thereof Can be mentioned.

  Among these diamines (z), from the viewpoints of hot offset resistance and bending resistance, alkylene diamines having 2 to 12 carbon atoms, alicyclic diamines having 4 to 15 carbon atoms, and 6 to 20 carbon atoms are preferable. More preferred are ethylene diamine, hexamethylene diamine, isophorone diamine and 2,4′- or 4,4′-diphenylmethane diamine.

  As diisocyanate (v), the same thing as a crystalline polyurethane resin is mentioned, A preferable thing is also the same.

  From the viewpoint of compatibility with the amorphous polyester resin (C), the crystalline polyurea resin is preferably 50% by weight or more of the crystalline polyester resin used as the monomer constituting the crystalline polyurea resin.

  Examples of the crystalline polyamide resin include those having the crystalline polyester resin, the diamine (z), and the dicarboxylic acid component (y) as constituent monomers. Such a crystalline polyamide resin can be obtained by reacting the crystalline polyester resin, the diamine (z) and the dicarboxylic acid component (y).

  Examples of the diamine (z) include those similar to the crystalline polyurethane resin, and preferable ones are also the same. Examples of the dicarboxylic acid component (y) include those similar to the crystalline polyester resin, and preferred ones are also the same.

  From the viewpoint of compatibility with the amorphous polyester resin (C), the crystalline polyamide resin is preferably 50% by weight or more of the crystalline polyester resin used as the monomer constituting the crystalline polyamide resin.

The solubility parameter (SP _A ) of the crystalline resin (A) is 8.0 to 11.0 (cal / cm ³ ) ^1/2 from the viewpoint of easiness of precipitation of the crystals (A) in the toner binder. Is more preferable, 8.5 to 10.0 is further preferable, and 8.8 to 9.7 is most preferable.

The solubility parameter (SP _A ) of the crystalline resin (A) was determined by the method by Fedors [Polym. Eng. Sci. 14 (2) 152, (1974)].

The crystalline resin (A) solubility parameter (SP _A ) preferably satisfies the following relational expression (4) when the solubility parameter of the amorphous polyester resin (C) is SP _C from the viewpoint of compatibility. By satisfying both of the relational expressions (5), the crystalline resin (A) is easily plasticized when heated, and the low-temperature fixability and glossiness are improved.

| SP _A -SP _C | <2.3 (4)
In the above formula, SP _A is the solubility parameter [(cal / cm ³ ) ^1/2 ] of the crystalline resin (A), and SP _C is the solubility parameter [(cal / cm ³ ) ¹ of the amorphous polyester resin (C). ^{/ 2} ]. The unit is (cal / cm ³ ) ^1/2 .

SP _C of the amorphous polyester resin (C), the method according to Fedors similar to the solubility parameter of the crystalline resin _{(A) (SP A) [} Polym. Eng. Sci. 14 (2) 152, (1974)].

As the relational expression (4), the relational expression (4-1) is more preferably satisfied from the viewpoint of the compatibility between the crystalline resin (A) and the amorphous polyester resin (C), and more preferably the relational expression. It satisfies (4-2).
0.1 ≦ | SP _A −SP _C | ≦ 2.2 (4-1)
0.1 ≦ | SP _A −SP _C | ≦ 1.8 (4-2)
When it is desired to reduce | SP _A −SP _C |, for example, when the crystalline resin (A) is not changed, SP _C which is the solubility parameter (SP value) of the amorphous polyester resin (C) is decreased (SP _{When A} is smaller than SP _C ), when the amorphous polyester resin (C) is not changed, the SP _A of the crystalline resin (A) is increased (when SP _A is smaller than SP _C ). Further, as a method for increasing the SP _A of the crystalline resin (A), for example, a chain aliphatic diol which is a constituent monomer, a linear alkane dicarboxylic acid, a linear alkene dicarboxylic acid and / or a direct monomer are used. Control by reducing the number of carbon atoms of the alkyl (meth) acrylate having a chain alkyl group may be mentioned.

Further, the crystalline resin (A) is a resin in which at least two or more types of segments are chemically bonded, and the crystalline segment (a1) that is compatible with the amorphous polyester resin (C) is amorphous. What has a segment (a2) incompatible with a polyester resin (C) is preferable. In the present specification, the crystalline segment (a1) that is compatible with the amorphous polyester resin (C) is also simply referred to as a segment (a1) or a crystalline segment (a1). The segment (a2) that is incompatible with the amorphous polyester resin (C) is also simply referred to as segment (a2).
In the present invention, “not compatible” with the amorphous polyester resin (C) means that 10 parts by weight of the compound serving as each segment is mixed with 90 parts by weight of the amorphous polyester resin (C) at room temperature. When the mixture is visually observed, the whole or part of the mixture is turbid. Conversely, “compatible” with the amorphous polyester resin (C) means that the entire mixture is not turbid.
In the present invention, mixing of the amorphous polyester resin (C) and the compound to be a segment when confirming the compatibility is carried out by mixing 90 parts of the amorphous polyester resin (C) and 10 parts of the compound to be a segment with tetrahydrofuran 50. It was carried out by dissolving the solvent in the part and then removing the solvent.

  Such a segment (a1) is not particularly limited as long as it shows crystallinity and is compatible with the amorphous polyester resin (C). For example, the following crystalline polyester (a11), Examples include a structure composed of a compound such as crystalline polyurethane (a12), crystalline polyurea (a13), and crystalline polyamide (a14). As a segment (a1), the structure comprised from such a compound is preferable.

Crystalline polyester (a11)
The crystalline polyester (a11) that can be used as the crystalline segment (a1) is not particularly limited as long as it is compatible with the amorphous polyester resin (C).

  Preferable crystalline polyester (a11) includes the same ones as the above-mentioned crystalline polyester resin, and preferable ones are also the same.

Crystalline polyurethane (a12)
The crystalline polyurethane (a12) that can be used as the crystalline segment (a1) is not particularly limited as long as it is compatible with the amorphous polyester resin (C).

  Examples of the crystalline polyurethane (a12) include the crystalline polyurethane resins described above, and preferred ones are also the same.

Crystalline polyurea (a13)
The crystalline polyurea (a13) that can be used as the crystalline segment (a1) is not particularly limited as long as it is compatible with the amorphous polyester resin (C).

  Examples of the crystalline polyurea (a13) include the crystalline polyurea resins described above, and preferred ones are also the same.

Crystalline polyamide (a14)
The crystalline polyamide (a14) that can be used as the crystalline segment (a1) is not particularly limited as long as it is compatible with the amorphous polyester resin (C).

  Examples of the crystalline polyamide (a14) include the crystalline polyamide resins described above, and preferred ones are also the same.

  Of the crystalline segments (a1) that are compatible with the amorphous polyester resin (C), the crystalline polyester (a11), the crystalline polyurethane (a12), and the crystalline polyurea ( a13), and more preferred are crystalline polyester (a11) and crystalline polyurethane (a12). As a segment (a1), the structure comprised from such a compound is preferable.

  As the segment (a2) contained in the crystalline resin (A) together with the crystalline segment (a1) that is compatible with the amorphous polyester resin (C), a compound that is not compatible with the amorphous polyester resin (C) If it is the structure comprised from, it will not specifically limit. Examples of the compound incompatible with the amorphous polyester resin (C) include alkyl monoalcohol (preferably having 18 to 42 carbon atoms) and alkyl monocarboxylic acid (preferably having 18 to 42 carbon atoms), preferably carbon. Examples thereof include linear alkyl monoalcohol having 18 to 42 and linear alkyl monocarboxylic acid having 18 to 42 carbon atoms. The segment (a2) is preferably a structure composed of such a compound. As linear alkyl monoalcohol having 18 to 42 carbon atoms, for example, behenyl alcohol and stearyl alcohol are preferable.

In the preferred crystalline resin (A) of the present invention, at least the segment (a1) and the segment (a2) are preferably chemically bonded in the same molecule. Moreover, it is preferable that crystalline resin (A) has 1 or more types chosen from the group which consists of an ester bond, a urethane bond, a urea bond, and an amide bond.
Further, in addition to the combination of one type of segment (a1) and one type of segment (a2), it may include three or more types of segments, and segment (a1) and segment (a2) may be directly chemically bonded. Alternatively, the segments (a1) and the segments (a3) other than the segment (a2) may be combined.
Examples of the segment (a3) include an amorphous segment that is compatible with the amorphous polyester resin (C).

  Accordingly, in the case of including three or more types of segments, for example, a combination of one type of segment (a1), one type of segment (a2), and one type of segment (a3), two types of segments (a1) and 1 A combination of seed segment (a2), a combination of one kind of segment (a1) and two kinds of segments (a2), and the like can be mentioned. Here, as an example of two or more types of segments, there is a case where the molecular weight and other physical properties are different even if the type of chemical structure (for example, polyester) is the same.

  The chemical bond between (a1) and (a2) is preferably one or more kinds of bonds selected from the group consisting of an ester bond, a urethane bond, a urea bond and an amide bond from the viewpoint of low-temperature fixability. Ester bonds and urethane bonds are more preferred.

As described above, the crystalline resin (A) is a resin in which at least two types of segments are chemically bonded, and is not compatible with the crystalline segment (a1) compatible with the amorphous polyester resin (C). It preferably has a segment (a2). The weight ratio (a1) / (a2) between the crystalline segment (a1) and the incompatible segment (a2) is preferably 70/30 to 99.9 / 0.1, more preferably from the viewpoint of low-temperature fixability. Is 90/10 to 99/1.
At that time, assuming that the solubility parameter of the amorphous polyester resin (C) is SP _C , the solubility parameter of the segment (a1) is SP _a1 , and the solubility parameter of the segment (a2) is SP _a2 , the segment (a1) and the segment ( It is preferable from the viewpoint of compatibility that a2) satisfies both the following relational expressions (2) and (3). By satisfying both of the relational expressions (2) and (3), the crystalline resin (A) is easily plasticized when heated and recrystallized when cooled. Low temperature fixability, glossiness, toner fluidity, Heat resistant storage stability, image strength after fixing, and bending resistance are improved.

| SP _a1 −SP _C | <1.8 (2)
| SP _a2 −SP _C | ≧ 1.8 (3)
In the above formula, SP _a1 is the solubility parameter [(cal / cm ³ ) ^1/2 ] of the segment (a1), SP _a2 is the solubility parameter [(cal / cm ³ ) ^1/2 ] of the segment (a2), SP _C Represents the solubility parameter [(cal / cm ³ ) ^1/2 ] of the amorphous polyester resin (C). The unit is (cal / cm ³ ) ^1/2 .
The solubility parameter (hereinafter sometimes referred to as SP value) of the segment (a1) and the segment (a2) is obtained from the SP value of the monomers constituting each segment and their ratio.

The SP values (SP _a1, SP _a2 , SP _C ) of the crystalline segment (a1), the segment (a2), and the amorphous polyester resin (C) are determined by the method of Fedors [Polym. Eng. Sci. 14 (2) 152, (1974)].

As the relational expression (2), the relational expression (2-1) is more preferably satisfied from the viewpoint of the compatibility between the amorphous polyester resin (C) and the segment (a1), and the relational expression (2) is more preferable. -2) is satisfied.
0.1 ≦ | SP _a1 −SP _C | ≦ 1.7 (2-1)
0.1 ≦ | SP _a1 −SP _C | ≦ 1.5 (2-2)
Similarly, as the relational expression (3), the relational expression (3-1) is preferably satisfied from the viewpoint of compatibility between the amorphous polyester resin (C) and the segment (a2), and more preferably the relational expression. It satisfies (3-2).
4.0 ≧ | SP _a2 −SP _C | ≧ 1.8 (3-1)
3.5 · | SP _a2 −SP _C | ≧ 1.8 (3-2)
When it is desired to reduce | SP _a1 −SP _C |, for example, when the crystalline segment (a1) is not changed, SP _C which is the solubility parameter (SP value) of the amorphous polyester resin (C) is decreased (SP _{When a1} is smaller than SP _C ), when the amorphous polyester resin (C) is not changed, SP _a1 of the crystalline segment (a1) is increased (when SP _a1 is smaller than SP _C ). If it is desired to reduce | SP _a2 -SP _C |, if the segment (a2) is not changed, SP _C which is the solubility parameter (SP value) of the amorphous polyester resin (C) is reduced (SP _a2 is SP). If _C is less than), if you do not want to change the amorphous polyester resin (C) to increase the _{SP a2} of segment (a2) _{(SP a2} can be achieved with SP If _C is less than) the like.

The weight average molecular weight (Mw) of the crystalline resin (A) of the present invention is preferably 3,000 to 50,000, more preferably 3,500 to 40,000, particularly preferably 4,000 to 30,000. It is.
50,000 or less is preferable from the viewpoint of low-temperature fixability, and 3,000 or more is preferable from the viewpoint of heat-resistant storage stability.

The molecular weight distribution, number average molecular weight (Mn) and weight average molecular weight (Mw) of the crystalline resin (A), the amorphous polyvinyl resin (B) having an ester group and the amorphous polyester resin (C) in the present invention are: It can be measured under the following conditions using gel permeation chromatography (GPC).
Apparatus (example): “HLC-8120” [manufactured by Tosoh Corporation]
Column (example): “TSK GEL GMH6” [manufactured by Tosoh Corporation] Measurement temperature: 40 ° C.
Sample solution: 0.25% by weight tetrahydrofuran solution (insoluble matter filtered off with glass filter)
Solution injection volume: 100 μl
Detection device: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400) , 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

From the viewpoint of heat-resistant storage stability, the crystalline resin (A) preferably has a content of components having a molecular weight of 1,500 or less in (A) of 12% by weight or less based on the weight of (A). More preferably, it is 8 weight% or less, More preferably, it is 7 weight% or less.
The content of components having a molecular weight of 1,500 or less in (A) is the molecular weight relative to the total area of the molecular weight distribution curve in (A) after obtaining the molecular weight distribution curve in (A) under the above GPC measurement conditions. The molecular weight in the distribution curve can be calculated from the area ratio of the portion having a molecular weight of 1,500 or less. However, calculation is performed excluding system peaks.

The acid value of the crystalline resin (A) is preferably from 0.01 to 30 mgKOH / g, more preferably from 0.01 to 20 mgKOH / g, still more preferably from the viewpoint of heat-resistant storage stability and charge stability. 01-15 mg KOH / g. Especially preferably, it is 0.1-10 mgKOH / g, Most preferably, it is 0.1-5 mgKOH / g.
In the present invention, the acid value can be measured by a method defined in JIS K0070.

It is preferable that the xylene-insoluble content of the crystalline resin (A) is 0.1 to 6% by mass. More preferably, it is 0.1-5 mass%, Most preferably, it is 0.1-4 mass%.
This is because when the toner is prepared by a suspension polymerization method, it becomes easy to uniformly dissolve the crystalline resin in the monomer constituting the amorphous polyvinyl resin (B). This is because the heat resistant storage stability is improved.

The measuring method of the xylene insoluble content of the crystalline resin (A) is as follows.
For sample preparation, 1.00 g of crystalline resin (A) was dissolved or dispersed in 100 g of xylene at a temperature equal to or higher than the endothermic peak top temperature Ta (° C.), and cooled to 25 ° C., and then centrifuged using a centrifuge. After removing the supernatant liquid, drying under reduced pressure (170 ° C., 2 hours), measuring the weight of xylene-insoluble matter (measured to 4 decimal places), and calculating xylene-insoluble content of (A) by the following formula To do.
Xylene-insoluble matter (% by weight) of crystalline resin (A) = (mass of xylene-insoluble matter (g) /1.00) × 100 The conditions for centrifugation are as follows.
<Centrifuge separation conditions>
Centrifuge: H-19F (manufactured by Kokusan Co., Ltd.)
Rotation speed: 4000rpm
Rotation time: 20 minutes

The amorphous polyvinyl resin (B) having an ester group in the present invention is an amorphous polyvinyl resin excluding the crystalline polyvinyl resin, and “polymerizable two” exemplified as a monomer that can be used for the crystalline polyvinyl resin. Examples thereof include amorphous polyvinyl resins having a monomer having a heavy bond and an ester group as an essential constituent monomer. Further, “amorphous” of the amorphous polyvinyl resin (B) means that there is no clear endothermic peak in the first temperature rising process of DSC measurement. By containing the amorphous polyvinyl resin (B), the fluidity, wet heat storage resistance, grindability and durability of the toner are improved.
From the viewpoint of compatibility with the crystalline resin (A) and low-temperature fixability, (B) is preferably a (meth) acrylate having a linear or branched alkyl group having 1 to 50 carbon atoms as an essential constituent monomer. And more preferably selected from the group consisting of (meth) acrylates having a linear alkyl group having 1 to 12 carbon atoms and (meth) acrylates having a branched alkyl group having 3 to 24 carbon atoms. Amorphous polyvinyl resin having at least one (meth) acrylate as an essential constituent monomer, particularly preferably a group consisting of methyl (meth) acrylate, butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate It is an amorphous polyvinyl resin having at least one selected from the essential constituent monomers.

  The amorphous polyvinyl resin (B) is a monomer having a polymerizable double bond and an ester group in the constituting monomer from the viewpoint of compatibility with the crystalline resin (A) and low-temperature fixability. The weight ratio is preferably 0.1 to 40% by weight, more preferably 1 to 20% by weight, based on the total weight of the monomers constituting (B).

The amorphous polyvinyl resin (B) having an ester group includes a polymerizable double resin exemplified as a constituent monomer of the crystalline polyvinyl resin in addition to “monomer having a polymerizable double bond and an ester group”. Hydrocarbon monomer having a bond (for example, styrene), monomer having a carboxyl group and a polymerizable double bond, and salts thereof (for example, methacrylic acid and acrylic acid and salts thereof (alkali metal salt, ammonium salt) , Amine salts and quaternary ammonium salts, etc.), monomers having a sulfo group and a polymerizable double bond, and salts thereof, monomers having a phosphono group and a polymerizable double bond, and salts thereof, Monomer having a hydroxyl group and a polymerizable double bond, a nitrogen-containing monomer having a polymerizable double bond (for example, acrylonitrile), a carbon number of 6 to 18 having an epoxy group and a polymerizable double bond Monomers, monomers having 2 to 16 carbon atoms having a halogen element and a polymerizable double bond, ethers having a polymerizable double bond (such as ethyl vinyl ether) and ketones having a polymerizable double bond and polymerization An amorphous vinyl resin containing a sulfur-containing compound having an ionic double bond as a constituent monomer is also preferred.
Among the above, from the viewpoint of compatibility with the crystalline resin (A), charge stability and heat resistant storage stability, it is more preferable to polymerize with an aromatic hydrocarbon monomer having a polymerizable double bond and a carboxyl group. Monomer having an ionic double bond, more preferably styrene and (meth) acrylic acid. Amorphous polyvinyl resin (B) is the above-mentioned single unit excluding the monomer having a polymerizable double bond and an ester group in the constituting monomer from the viewpoints of heat-resistant storage stability, wet heat-resistant storage and pulverization. The weight ratio of the monomer is preferably 60 to 99.9% by weight, more preferably 80 to 99% by weight, based on the total weight of the monomers constituting (B).
The above monomers constituting (B) may be used alone or in combination of two or more.

  The Mw of the amorphous polyvinyl resin (B) having an ester group is preferably 3,000 to 2,500,000, more preferably 3 from the viewpoints of low-temperature fixability, heat-resistant storage stability, wet heat-resistant storage stability and durability. 500 to 2,000,000, particularly preferably 4,000 to 1,800,000.

  In the molecular weight distribution obtained by gel permeation chromatography, the amorphous polyvinyl resin (B) having an ester group in the present invention is at least 1 in the region having a molecular weight of 3,000 to 60,000 from the viewpoint of low-temperature fixability of the toner. Those having two peaks are preferred.

In addition, the amorphous polyvinyl resin (B) having an ester group may be used alone or in combination of two or more. In the molecular weight distribution obtained by gel permeation chromatography, low temperature fixability, heat resistant storage stability, moisture heat storage resistance. From the standpoint of achieving both compatibility and durability, it is preferable that each has at least one peak in a region having a molecular weight of 3,000 to 60,000 and a region having a molecular weight of 100,000 to 2.5 million.
More preferred are those having at least one peak in the 3,500 to 40,000 region and 120,000 to 2 million region, respectively, and particularly preferred are the 4,000 to 20,000 region. , Each having at least one peak in the region of 140,000 to 1.8 million.

The amorphous polyvinyl resin (B) having an ester group is a resin (LB) having at least one peak in a region having a molecular weight of 3,000 to 60,000 in the molecular weight distribution obtained by gel permeation chromatography, It may be a resin (HB) mixture having at least one peak in a region having a molecular weight of 100,000 to 2.5 million.
When (B) is a mixture of (LB) and (HB), (LB) and (HB) may be combined at once, or (LB) and (HB) may be combined and mixed. Good.
Examples of the method of mixing (LB) and (HB) include powder mixing, melt kneading, and dissolution mixing.

  The Mw of (LB) is preferably from 3,000 to 60,000, more preferably from 3,500 to 40,000, particularly preferably from 4,000 to 20,000, from the viewpoint of low-temperature fixability of the toner. is there.

  The Mw of (HB) is preferably 100,000 to 2,500,000, more preferably 120,000 to 2,000,000, and particularly preferably 140,000 to 200,000 from the viewpoints of heat resistant storage stability, wet heat storage resistance and durability improvement of the toner. 1.8 million.

  The acid value of the amorphous polyvinyl resin (B) having an ester group is preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, and particularly preferably from the viewpoint of heat resistance and heat and heat resistance of the toner. 30 mgKOH / g or less, most preferably 20 mgKOH / g or less.

  The glass transition temperature (hereinafter abbreviated as Tg) of the amorphous polyvinyl resin (B) having an ester group is preferably 40 to 110 ° C., more preferably 40 to 100 ° C., particularly from the viewpoint of low-temperature fixability of the toner. Preferably it is 40-90 degreeC.

  In addition, Tg is measured by the method (DSC method) prescribed | regulated to ASTMD3418-82 using DSC.

The amorphous polyvinyl resin (B) having an ester group can be obtained by a known polymerization method such as solution polymerization, bulk polymerization, suspension polymerization and emulsion polymerization using the monomer and the radical polymerization initiator. .
Among these polymerization methods, preferred from the viewpoint of molecular weight control are solution polymerization, suspension polymerization, bulk polymerization, and combinations thereof.

Examples of the radical polymerization initiator include azo polymerization initiators (for example, azobisisobutyronitrile, azobisvaleronitrile, and azobiscyanovaleric acid), and organic peroxide polymerization initiators (for example, benzoyl peroxide, di-t -Butyl peroxide, t-butyl peroxybenzoate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane] and the like.
Of these, di-t-butyl peroxide and 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane are preferred.

  The amount of the radical polymerization initiator used is preferably 0.01 to 10% by weight, more preferably 0.02 to 8% by weight, particularly preferably 0.05 to 6% by weight, based on the total weight of the monomers. .

Examples of organic solvents that can be used for the synthesis of the amorphous polyvinyl resin (B) of the present invention include aromatic hydrocarbon solvents (toluene, xylene, ethylbenzene, tetralin, etc.); aliphatic hydrocarbon solvents (n-hexane, n-heptane, n-decane, mineral spirits, cyclohexane, etc.); halogen solvents (methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene, perchloroethylene, etc.); ester solvents (ethyl acetate) Butyl acetate, methyl 2-hydroxyisobutyrate, methyl lactate, ethyl lactate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, methyl pyruvate and ethyl pyruvate); ether solvents (diethyl ether, tetrahydrofuran, dioxane, Oxolane, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether, etc.); ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone) Alcohol solvents (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, 2,2,3,3-tetrafluoropropanol and trifluoro Ethanol, etc.); amide solvents (dimethylformamide, dimethylacetamide, etc.); sulfoxide solvents (dimethyl) Sulfoxide, etc.); heterocyclic compounds based solvents (N- methylpyrrolidone) and include mixed solvent of two or more thereof.
Among these, preferred are aromatic hydrocarbon solvents from the viewpoint of operability, and more preferred are xylene, toluene and ethylbenzene.

  Moreover, when performing suspension polymerization, it can superpose | polymerize in water using inorganic acid salt dispersing agents (calcium carbonate, calcium phosphate, etc.), organic dispersing agents (polyvinyl alcohol, methylcellulose, etc.), etc.

  When styrene monomer is used after suspension polymerization, the content of styrene monomer in the obtained toner is preferably 100 ppm or less, based on the weight of the toner, from the viewpoint of heat-resistant storage, wet heat-resistant storage and durability. More preferably 50 ppm or less, particularly preferably 25 ppm or less, most preferably 5 ppm or less. The monomer content in the toner can be measured by gas chromatography.

An example of measurement conditions for measuring the monomer content and the styrene monomer content in the toner by gas chromatography is shown below.
Model: “GC2010” [manufactured by Shimadzu Corporation]
Column: “DB-5” (5 wt% phenylmethylpolysiloxane, inner diameter 0.25 mm, length 30 m) [manufactured by Shimadzu Corporation]
Eluent: Dimethylformamide Flow rate: 40.5 ml / min
Detector temperature: 250 ° C
Injection volume: 1 μl

In the present invention, the content of the volatile organic compound (hereinafter abbreviated as VOC) in the toner is preferably 500 ppm or less based on the weight of the toner from the viewpoints of heat resistant storage stability, wet heat storage resistance and durability. More preferably, it is 300 ppm or less, particularly preferably 200 ppm or less, and most preferably 100 ppm or less. The content of VOC in the toner can be measured by gas chromatography.
A constant amount of toner is heated at 130 ° C. for a certain period of time, the generated VOC gas is collected, and the content of VOC in (Z) is measured by gas chromatography. An example of measurement conditions is shown below.
Model: “GC2010” [manufactured by Shimadzu Corporation]
Column: “DB-5” (5 wt% phenylmethylpolysiloxane, inner diameter 0.25 mm, length 30 m) [manufactured by Shimadzu Corporation]
Flow rate: 40.5 ml / min
Detector temperature: 250 ° C
Injection volume: 1 μl

The SP value of the amorphous polyvinyl resin (B) having an ester group is preferably 9.5 to 11.5 (cal / cm ³ ) ^1/2 from the viewpoint of low-temperature fixability, and more preferably 9. 5 to 11.0 (cal / cm ³ ) ^1/2 , particularly preferably 10.0 to 11.0 (cal / cm ³ ) ^1/2 .

The absolute value of the difference in SP value between the crystalline resin (A) and the amorphous polyvinyl resin (B) having an ester group is preferably 1.8 (cal / cm ³ ) ^1/2 or less from the viewpoint of low-temperature fixability. More preferably, it is 1.6 or less, and particularly preferably 0.2 or more and 1.4 or less.

The storage elastic modulus G ′ (120) at 120 ° C. of the amorphous polyvinyl resin (B) is preferably 1 × 10 ³ to 1 × 10 ⁶ Pa, more preferably 3 × 10 ³ from the viewpoint of low-temperature fixability. ˜5 × 10 ⁵ Pa, particularly preferably 5 × 10 ³ to 1 × 10 ⁵ Pa.

  The toner binder of the present invention contains an amorphous polyester resin (C). The “amorphous resin” in the present invention refers to a resin that does not have a clear endothermic peak in the first temperature rising process of DSC measurement.

  Examples of the amorphous polyester resin (C) in the present invention include a polyester resin having an alcohol component (X) and a carboxylic acid component (Y) as essential constituent monomers.

  Examples of the alcohol component (X) include an unsaturated alcohol component (X1) and a saturated alcohol component (X2). 1 type may be used for alcohol component (X) and it may use 2 or more types together.

  Examples of the unsaturated alcohol (X1) include unsaturated monoalcohols having 2 to 30 carbon atoms, unsaturated diols having 2 to 30 carbon atoms, specifically 2-propen-1-ol and oleyl alcohol. , 2-hydroxyethyl methacrylate and ricinoleyl alcohol.

  Examples of the saturated alcohol component (X2) include monool (X21), diol (X22), and polyol (X23) having a valence of 3 to 8 or more.

As monool (X21), a C1-C30 linear or branched alkyl alcohol (Methanol, ethanol, isopropanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, etc.) etc. are mentioned, for example.
Among these monools, preferred are linear alkyl alcohols having 8 to 24 carbon atoms, and more preferred are dodecyl alcohol, myristyl alcohol, stearyl alcohol and behenyl alcohol.
These may be used alone or in combination of two or more.

Examples of the diol (X22) include alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol. 3-methyl-1,5-pentanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol, etc.) (X221); alkylene ether glycol having 4 to 36 carbon atoms (diethylene glycol, Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.) (X222); C6-C36 alicyclic diol (1,4-cyclohexanedimethanol and hydrogenated bisphenol) A etc.) (X223); (Poly) oxyalkylene adduct of the above alicyclic diol (preferably the number of added moles = 1-30) (X224); Alkylene oxide adducts of bisphenols (preferably 2-30 added moles)] (X225); and the like.
Of these diols (X22), aromatic diols (X225) are preferable and alkylene oxide adducts of bisphenols are more preferable from the viewpoints of low-temperature fixability and heat-resistant storage stability.
In the alkylene oxide, the alkylene group preferably has 2 to 4 carbon atoms (ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3-, 1,3- or iso-butylene oxide. And tetrahydrofuran.

  An alkylene oxide adduct of bisphenols is generally obtained by adding alkylene oxide (hereinafter, “alkylene oxide” may be abbreviated as AO) to bisphenols. Examples of bisphenols include those represented by the following general formula (5).

HO-Ar-P-Ar-OH (5)
[In the formula, P represents an alkylene group having 1 to 3 carbon atoms, —SO ₂ —, —O—, —S—, or a direct bond; Ar represents a hydrogen atom other than the portion to which the hydroxyl group and P are bonded is a halogen atom. A phenylene group which may be substituted with an atom or an alkyl group having 1 to 30 carbon atoms is represented. ]

  Specific examples of bisphenols include bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6- Dimethyl bisphenol A and 2,2'-diethyl bisphenol F are mentioned, These can also use 2 or more types together.

  The alkylene oxide added to these bisphenols is preferably an alkylene oxide having 2 to 4 carbon atoms. Specifically, ethylene oxide (hereinafter, “ethylene oxide” may be abbreviated as EO), propylene oxide. (Hereinafter, “propylene oxide” may be abbreviated as PO.), 1,2-, 2,3-, 1,3- or iso-butylene oxide, tetrahydrofuran, and combinations of two or more thereof. .

Among these, EO and / or PO are preferable from the viewpoint of heat-resistant storage stability and low-temperature fixability. The number of added moles of AO is preferably 2 to 30 moles, more preferably 2 to 10 moles from the viewpoints of heat resistant storage stability and low temperature fixability.
Among the alkylene oxide adducts of bisphenols, EO and / or PO adducts of bisphenol A (preferably having an average addition mole number of 2 to 4, more preferably 2 to 3) are preferable from the viewpoint of toner fixing properties. is there.

  As the polyol (X23) having a valence of 3 to 8 or more, an aliphatic polyhydric alcohol (X231) having a valence of 3 to 8 or more having 3 to 36 carbon atoms, a saccharide and a derivative thereof (x32 ), (Poly) oxyalkylene ethers of aliphatic polyhydric alcohols (preferably 1 to 30 as the number of oxyalkylene units) (X233), polyoxyalkylene ethers of trisphenols (such as trisphenol PA) (of oxyalkylene units) The number is preferably 2 to 30) (X234), novolak resins (phenol novolak, cresol novolak, etc. are included, and the average degree of polymerization is preferably 3 to 60), and the number of oxyalkylene units is preferably 2 -30) (X235) etc. are mentioned.

  Examples of the aliphatic polyhydric alcohol (X231) having a valence of 3 to 8 or more having 3 to 36 carbon atoms include alkane polyols and intramolecular or intermolecular dehydrates such as glycerin, trimethylolethane, Examples include trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol.

  Examples of the saccharide and its derivative (X232) include sucrose and methyl glucoside.

  Among the saturated alcohol components (X2), those preferable from the viewpoint of achieving both low temperature fixability and hot offset resistance are alkylene glycols having 2 to 36 carbon atoms (X221), alkylene oxide adducts of bisphenols (number of AO units). Preferably 2 to 30) (X225), 3 to 8 or more aliphatic polyhydric alcohols (X231) having 3 to 36 carbon atoms, and polyoxyalkylene ethers of novolak resins (preferably as the number of oxyalkylene units) 2-30) (X235).

More preferable from the viewpoint of heat-resistant storage stability are alkylene glycols having 2 to 10 carbon atoms, alkylene oxide adducts of bisphenols (preferably 2 to 5 as the number of AO units), 3 to 4 valent aliphatic polyhydric alcohols. And a polyoxyalkylene ether of a novolac resin (preferably 2 to 30 as the number of oxyalkylene units).
Particularly preferred are alkylene glycols having 2 to 6 carbon atoms, trivalent aliphatic polyhydric alcohols and alkylene oxide adducts of bisphenol A (preferably 2 to 5 as the number of AO units), most preferably ethylene glycol. , Propylene glycol, 3-methyl-1,5-pentanediol, trimethylolpropane and bisphenol A alkylene oxide adduct (preferably 2 to 3 as the number of AO units).

From the viewpoint of amorphousness, an alkylene oxide adduct of bisphenols (preferably 2 to 5 as the number of AO units) is further preferred, and an alkylene oxide adduct of bisphenol A (preferably 2 to AO units is preferred). 3).
The alcohol component (X) preferably contains 10 mol% or more of an alkylene oxide adduct of bisphenols based on the total number of moles of the alcohol component (X) in the monomer constituting (C), 30 More preferably, it is contained in an amount of at least mol%, and most preferably at least 50 mol%.

  Examples of the carboxylic acid component (Y) include an unsaturated carboxylic acid component (Y1) and a saturated carboxylic acid component (Y2). As the carboxylic acid component (Y), one type may be used, or two or more types may be used in combination.

  Examples of the unsaturated carboxylic acid component (Y1) include unsaturated monocarboxylic acid (Y11), unsaturated dicarboxylic acid (Y12), and anhydrides and lower alkyl esters of these acids.

  As unsaturated monocarboxylic acid (Y11), C2-C30 unsaturated monocarboxylic acid is mentioned, for example, Specifically, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, 3-butenoic acid, Angelica Acid, tiglic acid, 4-pentenoic acid, 2-ethyl-2-butenoic acid, 10-undecenoic acid, 2,4-hexadienoic acid, myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, elaidic acid, vaccenic acid, Examples thereof include gadoleic acid, eicosenoic acid, erucic acid, and nervonic acid.

  Examples of the unsaturated dicarboxylic acid (Y12) include alkene dicarboxylic acids having 4 to 50 carbon atoms. Specifically, alkenyl succinic acids such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itacone. Examples include acid and glutaconic acid.

Of these unsaturated carboxylic acids (Y1), preferred are alkenyl succinic acid such as acrylic acid, methacrylic acid and dodecenyl succinic acid, maleic acid and fumaric acid from the viewpoint of compatibility between low-temperature fixability, hot offset resistance and durability. It is an acid.
More preferred are acrylic acid, methacrylic acid, maleic acid, fumaric acid and combinations thereof. Likewise preferred are anhydrides and lower alkyl esters of these acids.

  Examples of the saturated carboxylic acid component (Y2) include aromatic carboxylic acid (Y21) and aliphatic carboxylic acid (Y22). One type of saturated carboxylic acid component (Y2) may be used, or two or more types may be used in combination.

Examples of the aromatic carboxylic acid (Y21) include aromatic monocarboxylic acids having 7 to 37 carbon atoms (benzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.), and those having 8 to 36 carbon atoms. Aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.), trivalent or higher aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and the like.
Examples of the aliphatic carboxylic acid (Y22) include aliphatic monocarboxylic acids having 2 to 50 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid. Acid, myristic acid, palmitic acid, margaric acid, stearic acid and behenic acid), aliphatic dicarboxylic acids having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, repargic acid, sebacic acid, etc.), C6-C36 aliphatic tricarboxylic acid (hexane tricarboxylic acid etc.) etc. are mentioned.

  The saturated carboxylic acid component (Y2) may be an anhydride of these carboxylic acids or a lower alkyl (carbon number 1 to 4) ester (such as methyl ester, ethyl ester, or isopropyl ester).

Among these saturated carboxylic acid components (Y2), those which are preferable from the viewpoint of achieving both low-temperature fixability and hot offset resistance are aromatic monocarboxylic acids having 7 to 37 carbon atoms and aliphatic dicarboxylic acids having 2 to 50 carbon atoms. An acid, an aromatic dicarboxylic acid having 8 to 20 carbon atoms, and an aromatic polycarboxylic acid having 9 to 20 carbon atoms and having 3 or more valences.
More preferable from the viewpoint of heat-resistant storage stability and charging stability, adipic acid, alkyl succinic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, and combinations thereof. Particularly preferred are adipic acid, terephthalic acid, trimellitic acid, and combinations thereof. Moreover, anhydrides and lower alkyl esters of these acids may be used.

  The amorphous polyester resin (C) preferably comprises two or more carboxylic acid components (Y) from the viewpoint of amorphousness, more preferably three or more carboxylic acid components (Y). .

The amorphous polyester resin (C) is a total mole of the alcohol component (X-1) containing 80 mol% or more of the aromatic diol and the carboxylic acid component (Y) based on the total number of moles of the alcohol component (X). It is a polyester resin having a carboxylic acid component (Y-1) containing 80 mol% or more of an aromatic dicarboxylic acid based on the number as a constituent monomer, charging stability, heat resistant storage stability, low temperature fixability, glossiness From the viewpoint of image strength and bending resistance, it is preferable.
This makes it easier to uniformly dissolve the amorphous polyester resin (C) in the monomer constituting the amorphous polyvinyl resin (B) (especially styrene monomer), increasing the uniformity of the toner, and charging stability and heat resistance. This is because storability and image transportability are improved. It is particularly effective when the toner is prepared by suspension polymerization.

The absolute value of the difference in SP value between the amorphous polyester resin (C) and the amorphous polyvinyl resin (B) having an ester group is preferably 1.8 from the viewpoints of charging stability, heat resistant storage stability and image transportability. (Cal / cm ³ ) ^1/2 or less, more preferably 1.2 (cal / cm ³ ) ^1/2 or less, particularly preferably 0.2 (cal / cm ³ ) ^1/2 or more and 1.0 ( cal / cm ³ ) ^1/2 or less.

  Specific examples of the aromatic diol include polyoxyalkylene ethers of the above-described bisphenols (number of AO units 2 to 30) (X225). Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, and combinations thereof.

In the present invention, each polyester can be produced in the same manner as a general polyester.
For example, the reaction can be carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280 ° C, more preferably 160 to 250 ° C, and particularly preferably 170 to 235 ° C. The reaction time is preferably 30 minutes or more, particularly preferably 2 to 40 hours, from the viewpoint of reliably performing the polycondensation reaction.

At this time, an esterification catalyst can be used as needed.
Examples of the esterification catalyst include a tin-containing catalyst (for example, dibutyltin oxide), antimony trioxide, and a titanium-containing catalyst [for example, titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, Japanese Patent Application Laid-Open No. 2006-243715. Catalysts described in the publication {titanium dihydroxybis (triethanolamate), titanium monohydroxytris (triethanolamate), titanylbis (triethanolaminate) and their intramolecular polycondensates, etc.}, and JP2007- No. 11307 catalyst (titanium tributoxyterephthalate, titanium triisopropoxyterephthalate, titanium diisopropoxyditerephthalate, etc.)], zirconium-containing catalyst (for example, zirconyl acetate), and acetic acid Lead and the like. Among these, a titanium-containing catalyst is preferable. It is also effective to reduce the pressure in order to improve the reaction rate at the end of the reaction.

  Further, a stabilizer may be added for the purpose of obtaining polyester polymerization stability. Examples of the stabilizer include hydroquinone, methyl hydroquinone and hindered phenol compounds.

  The charging ratio of the alcohol component (X) and the carboxylic acid component (Y) is preferably 2/1 to 1/2, more preferably 1.5 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 1-1.1.3, particularly preferably 1.4 / 1 to 1 / 1.2.

The content of the crystalline resin (A) in the toner is 5 to 80% by weight based on the total weight of the crystalline resin (A), the amorphous polyvinyl resin (B), and the amorphous polyester resin (C). It is preferable that
5% by weight or more is preferable from the viewpoint of low-temperature fixability, and 80% by weight or less is preferable from the viewpoint of heat-resistant storage stability.

The content of the amorphous polyvinyl resin (B) in the toner is 5 to 93 based on the total weight of the crystalline resin (A), the amorphous polyvinyl resin (B), and the amorphous polyester resin (C). It is preferable that it is weight%.
5% by weight or more is preferable from the viewpoint of heat-resistant storage stability, and 93% by weight or less is preferable from the viewpoint of low-temperature fixability.

The content of the amorphous polyester resin (C) in the toner is 2 to 20 based on the total weight of the crystalline resin (A), the amorphous polyvinyl resin (B), and the amorphous polyester resin (C). It is preferable that it is weight%.
It is preferably 2% by weight or more from the viewpoint of image strength, bending resistance and document offset property, and preferably 20% by weight or less from the viewpoint of gloss.

  In the present invention, when it is desired to control the hot offset resistance and durability of the toner, particularly when the amorphous polyester resin (C) is controlled by having a crosslinked structure, the amorphous polyester resin (C) is a main chain. A polyester resin having a branch (crosslinking point) therein is preferable. That is, the amorphous polyester resin (C) is preferably a polyester resin in which the polyester resin (C0) is crosslinked by a carbon-carbon bond.

  Specifically, it is a polyester resin obtained by a crosslinking reaction, and the form of the crosslinking reaction is not particularly limited. For example, an unsaturated double bond is introduced into the main chain or side chain of the polyester resin, a radical addition reaction, Examples of the reaction include a reaction by a cation addition reaction or an anion addition reaction to generate an intermolecular carbon-carbon bond.

  Moreover, as a crosslinking reaction, reaction which produces | generates an ester bond by the condensation reaction of the polycarboxylic acid of 3-6 valence or more at the time of polyester resin synthesis | combination, and the polyol of 3-6 valence or more valence. Also mentioned.

  Furthermore, examples of the crosslinking reaction include polyaddition reaction between a polyvalent epoxy group, a polyvalent isocyanate group, a polyvalent carbodiimide group, a polyvalent aziridine group, a polyvalent oxazoline group-containing compound and a polyester resin.

Among these, a method of generating an intermolecular carbon-carbon bond by a radical addition reaction, a cation addition reaction, an anion addition reaction, or the like is preferable from the viewpoint of grindability and low-temperature fixability.
Specifically, the polyester resin (C0) is a polyester resin having a carbon-carbon double bond, and a carbon-carbon double bond derived from (C0) is subjected to a cross-linking reaction to at least partially cross-link carbon. -The method of producing | generating a carbon bond is mentioned, It is a preferable method.

Further, in the amorphous polyester (C) of the present invention, the polyester resin having a carbon-carbon double bond is obtained by superimposing a component containing an unsaturated carboxylic acid component (Y1) and / or an unsaturated alcohol component (X1). A polyester resin obtained by condensation is preferred.
Furthermore, the polyester resin having a carbon-carbon double bond constitutes a saturated alcohol component (X2) and a saturated carboxylic acid component (Y2) in addition to the unsaturated carboxylic acid component (Y1) and the unsaturated alcohol component (X1). It may be included as a raw material.
Moreover, these components may be polycondensed individually by 1 type, and multiple types may be polycondensed.
In the present specification, aromatic ring bonding is not considered in determining whether the component is an unsaturated carboxylic acid component (Y1) or a saturated carboxylic acid component (Y2). That is, a compound other than the aromatic ring portion is an unsaturated carboxylic acid component is determined as an unsaturated carboxylic acid component (Y1), and a compound other than the aromatic ring portion is a saturated carboxylic acid component is determined as a saturated carboxylic acid component (Y2). To do.
Similarly, a bond of an aromatic ring is not considered in determining whether it is an unsaturated alcohol component (X1) or a saturated alcohol component (X1). That is, the compound other than the aromatic ring portion is an unsaturated alcohol is determined as the unsaturated alcohol component (X1), and the compound other than the aromatic ring portion is a saturated alcohol is determined as the saturated alcohol component (X2).

  In the present invention, the polyester resin (C0) is a resin containing a polyester resin (C1) having a glass transition temperature of −40 ° C. or higher and lower than 55 ° C. and / or a polyester resin (C2) having a glass transition temperature of 55 ° C. or higher and 85 ° C. or lower. Is preferred.

The glass transition temperature of the polyester resin (C1) is preferably −40 ° C. or higher and lower than 55 ° C. from the viewpoint of low-temperature fixability.
The glass transition temperature of the polyester resin (C1) is more preferably −30 to 50 ° C., particularly preferably −20 to 40 ° C., and most preferably −10 to 35 ° C.
In addition, glass transition temperature (Tg) can be measured by the method (DSC method) prescribed | regulated to ASTM D3418-82, for example using Seiko Instruments Co., Ltd. DSC20 and SSC / 580.

The glass transition temperature of the polyester resin (C2) is preferably 55 ° C. or higher and lower than 85 ° C. from the viewpoints of heat resistant storage stability, wet heat storage resistance, fluidity, image strength, bending resistance, and document offset properties.
The glass transition temperature of the polyester resin (C2) is more preferably 57 to 80 ° C, particularly preferably 60 to 75 ° C, and most preferably 63 to 73 ° C.

Examples of the method for producing the amorphous polyester resin (C) include the following methods.
First, a carboxylic acid component and an alcohol component (including an unsaturated carboxylic acid component (Y1) and / or an unsaturated alcohol component (X1) as a constituent raw material) are subjected to a condensation reaction as a constituent raw material, and a carbon-carbon double bond in the molecule A polyester resin (C0) having is obtained. Next, the radical reaction initiator (c) is allowed to act on the polyester resin (C0), and the radical generated from the radical reaction initiator (c) is used to produce an unsaturated carboxylic acid component ( The carbon-carbon double bonds resulting from Y1) and / or the unsaturated alcohol component (X1) are bonded together by a crosslinking reaction. Thereby, an amorphous polyester resin (C) can be manufactured. This method is preferable in that the crosslinking reaction can be made uniform in a short time.

  The radical reaction initiator (c) used for the crosslinking reaction of the polyester resin (C0) is not particularly limited, and an azo compound, a diazo compound (c1), or an organic peroxide (c2) is used. (C) may use 1 type and may use 2 or more types together.

  The azo compound or diazo compound (c1) is not particularly limited, and examples thereof include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,2′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

  The organic peroxide (c2) is not particularly limited, and examples thereof include benzoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α-bis (t-butyl). Peroxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t- Butylperoxyhexine-3, acetyl peroxide, isobutyryl peroxide, octanonor peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t -Butylperoxyisobutyrate, t-butylperoxyneodecanoate, cumylperoxyne Odecanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butyl Examples include peroxyisopropyl monocarbonate and t-butyl peroxyacetate.

Among these, the organic peroxide (c2) is preferable because it has high initiator efficiency and does not produce toxic byproducts such as cyanide.
Furthermore, since the crosslinking reaction proceeds efficiently and the amount used is small, a reaction initiator having a high hydrogen abstraction ability is particularly preferred, and benzoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, Dicumyl peroxide, α, α-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide, A radical reaction initiator having a high hydrogen abstraction ability such as t-butyl peroxylaurate is particularly preferred.

Although the usage-amount of a radical reaction initiator (c) is not restrict | limited in particular, 0.1-50 weight part is with respect to 100 weight part of unsaturated carboxylic acid component (Y1) and / or unsaturated alcohol component (X1). preferable.
When the amount of the radical reaction initiator (c) used is 0.1 parts by weight or more, the crosslinking reaction tends to proceed, and when it is 50 parts by weight or less, the odor tends to be good. The amount used is more preferably 30 parts by weight or less, still more preferably 20 parts by weight or less, and particularly preferably 10 parts by weight or less.

  Moreover, it is preferable to manufacture the amorphous polyvinyl resin (B) in the presence of the amorphous polyester resin (C0). When the amorphous polyvinyl resin (B) is obtained by solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization using a radical polymerization initiator, if (C0) is added in advance, the carbon-carbon bis derived from (C0). A part of (C) produced by the double bond is bonded to the amorphous polyvinyl resin (B), and the low-temperature fixability, hot offset resistance and durability of the toner are preferable.

The glass transition point (Tg) of the amorphous polyester resin (C) is determined from the viewpoints of low-temperature fixability, glossiness, toner fluidity, heat-resistant storage stability, image strength after fixing, folding resistance and document offset property. -40-85 degreeC is preferable, More preferably, it is -20-80 degreeC, Most preferably, it is 0-75 degreeC.
In addition, Tg is measured by the method (DSC method) prescribed | regulated to ASTMD3418-82 using DSC.

The Mw of the amorphous polyester resin (C) is 2, from the viewpoint of low-temperature fixability, glossiness, toner fluidity, heat resistant storage stability, grindability, image strength after fixing, bending resistance and document offset. 000 to 200,000 is preferable, more preferably 2,500 to 100,000, and particularly preferably 3,000 to 60,000.
Mw and Mn of the resin (B) are obtained by GPC in the same manner as the crystalline resin (A) described above.

The acid value of the amorphous polyester resin (C) is low temperature fixability, fluidity of glossy toner, heat resistant storage stability, charge stability, pulverization, image strength after fixing, folding resistance and document offset. Therefore, 30 mgKOH / g or less is preferable, more preferably 20 mgKOH / g or less, and still more preferably 15 mgKOH / g or less. Especially preferably, it is 10 mgKOH / g or less, Most preferably, it is 5 mgKOH / g or less.
In the present invention, the acid value can be measured by a method defined in JIS K0070.

  The softening point (Tm) measured by the flow tester of the amorphous polyester resin (C) is preferably 80 to 170 ° C, more preferably 85 to 165 ° C, and particularly preferably 90 to 160 ° C.

The softening point (Tm) is measured by the following method.
Using a Koka flow tester {for example, CFT-500D manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a 1 g measurement sample at a temperature rising rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent (flow value)” and “temperature”, and set the temperature corresponding to 1/2 of the maximum plunger descent It reads from a graph and makes this value (temperature when half of a measurement sample flows out) be a softening point [Tm].

  Two or more types of amorphous polyester resins (C) having different Tm may be used in combination, and a combination of those having a Tm of 80 to 110 ° C and those of 110 to 170 ° C is preferable.

The toner of the present invention contains the toner binder of the present invention.
The toner of the present invention may contain a resin other than the crystalline resin (A), the amorphous polyvinyl resin (B) having an ester group, and the amorphous polyester resin (C).

Examples of the resin other than the crystalline resin (A) and the amorphous polyvinyl resin (B) having an ester group and the amorphous polyester resin (C) include a polyolefin resin (E1) having a softening point of 100 to 170 ° C. A resin dispersant (E3) having a structure in which a vinyl monomer (E2) having an SP value of 10.6 to 12.6 and a vinyl monomer constituting (E2) is grafted on (E1) (E3) ) And the like.
Addition of the resin dispersant (E) is preferable from the viewpoint of uniformly dispersing the crystalline resin (A) in the toner and improving low-temperature fixability, grindability, and charging stability.

  The content of the resin dispersant (E) in the toner is 1 to 20% by weight based on the total weight of the crystalline resin (A), the amorphous polyvinyl resin (B), and the amorphous polyester resin (C). It is preferable that

The toner of the present invention may contain the toner binder of the present invention, but may contain a colorant. The colorant preferably contains one or more selected from the group consisting of a black colorant, a blue colorant, a red colorant and a yellow colorant. As the colorant, all of dyes and pigments used as toner colorants can be used.
Specifically, carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, solvent yellow (21, 77, 114, etc.), pigment yellow (12, 14, 17, 83, etc.), Indian first orange, Irgasin Red, Paranitonianiline Red, Toluidine Red, Solvent Red (17, 49, 128, 5, 13, 22 and 48.2, etc.), Disperse Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B lake, methyl violet B lake, phthalocyanine blue, solvent blue (25, 94, 60, 15.3, etc.), pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayaset YG, o Tetrazole brown B and oil pink OP, and the like. Further, if necessary, magnetic powder (a powder of ferromagnetic metal such as iron, cobalt and nickel, a compound such as magnetite, hematite and ferrite) can be added to serve as a colorant.

  The content of the colorant is preferably 0 to 60% by weight, more preferably 0.1 to 55% by weight, and particularly preferably 0.5 to 50% by weight based on the weight of the toner.

The toner of the present invention can contain a release agent, a charge control agent, a fluidizing agent and the like in addition to the toner binder and the colorant.
Release agents include natural waxes (such as beeswax, carnauba wax, and montan wax), petroleum waxes (such as paraffin wax, microcrystalline wax, and petrolatum), and synthetic waxes (polyethylene wax, polypropylene wax, oxidized polyethylene wax, and oxidized polypropylene). Wax, etc.) and synthetic ester wax (fatty acid ester synthesized from a fatty acid having 10 to 30 carbon atoms and an alcohol having 10 to 30 carbon atoms), etc., and one kind selected from the group consisting of these release agents It is preferable to contain the above.

  The maximum temperature (Tr) of the endothermic peak of the release agent is preferably 40 to 90 ° C., more preferably 45 to 85 ° C., and particularly preferably 50 to 80 ° C. from the viewpoint of low-temperature fixability and gloss.

Kinematic viscosity at 100 ° C. of the releasing agent is preferably from the viewpoint of low-temperature fixing property and glossiness was 3 to 20 mm ² / s, more preferably 4~19mm ² / s, particularly preferably 5~18mm ² / s It is.

  The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and particularly preferably 1 to 2% by weight based on the weight of the toner from the viewpoint of low-temperature fixability and glossiness. 10% by weight.

  As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes , Salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, metal complexes of salicylic acid alkyl derivatives, cetyltrimethylammonium bromide, and the like.

  The content of the charge control agent is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, and particularly preferably 0.5 to 7% based on the weight of the toner from the viewpoint of charge stability. .5% by weight.

  Examples of the fluidizing agent include silica, titania, alumina, fatty acid metal salts, silicone resin particles, and fluororesin particles, and two or more of them may be used in combination.

  The content of the fluidizing agent is preferably 0.2 to 5.0% by weight, more preferably 0.3 to 4.0% by weight, particularly preferably from the viewpoint of fluidity, based on the weight of the toner. Is 0.4 to 3.0% by weight.

  The toner is mixed with carrier particles [iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite (surface coated with acrylic resin, silicone resin, etc.), etc.] as necessary, and an electric latent image is mixed. It can be used as a developer. Further, instead of carrier particles, an electric latent image can be formed by rubbing with a charging blade or the like, and the electric latent image can be formed on a support (paper, polyester film, etc.) by a known heat roll fixing method. ).

The volume average particle diameter of the toner is preferably 1 to 15 μm, more preferably 2 to 10 μm, and particularly preferably 3 to 7 μm from the viewpoint of low-temperature fixability and gloss.
The volume average particle diameter of the toner can be measured using a Coulter counter “Multisizer IV” (manufactured by Beckman Coulter, Inc.).

The method for producing the toner is not particularly limited, and the suspension weight described in a known kneading and pulverizing method, Japanese Patent Publication No. 36-10231, Japanese Patent Publication No. 59-53856, Japanese Patent Publication No. 59-61842. Combined methods, emulsion polymerization methods represented by soap-free polymerization methods in which monomers are directly polymerized in the presence of water-soluble polymerization initiators to produce toner, interfacial polymerization methods such as microcapsule production methods, insite Polymerization method, coacervation method, association for aggregating at least one kind of fine particles as disclosed in JP-A-62-106473 and JP-A-63-186253 to obtain a desired particle size It may be obtained by a polymerization method, a dispersion polymerization method characterized by monodispersion, a dissolution suspension method in which necessary resins are dissolved in a water-insoluble organic solvent, and then converted into a toner in water. Near It may be prepared by a method of dispersing in the form of carbon dioxide.
At that time, the crystalline resin (A), the amorphous polyvinyl resin (B) and / or the monomer constituting the amorphous polyvinyl resin (B) and the amorphous polyester resin (C) are mixed. It is preferable to maintain the temperature of the manufacturing process after this mixing process below the maximum temperature (Ta) of the endothermic peak of the crystalline resin (A). By controlling the temperature so that it becomes the above temperature after this mixing step, (A) and (B) can be allowed to exist in a phase separated state in the toner, which is preferable from the viewpoint of heat resistant storage stability. .

  For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry blended, and then melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. Further, by further classifying, the volume average particle diameter (D50) is preferably 5 to 20 μm and then mixed with a fluidizing agent.

  For example, when a toner is obtained by a dissolution suspension method, components constituting the toner other than the fluidizing agent such as (A), (B), (C), a colorant and a release agent are dissolved or dissolved in an organic solvent. After dispersing into an oil phase, the oil phase is mixed with an aqueous phase containing a surfactant to form fine particles. Further, the organic solvent is removed from the mixture of the oil phase and the aqueous phase, and then the toner After separating and classifying the particles, finally, a fluidizing agent can be mixed to produce.

When the dissolution suspension method is carried out in the present invention, the crystalline resin (A) is in a state of being dispersed in an organic solvent, and the form thereof is realized, for example, by the following series of steps.
Crystalline resin (A) and ethyl acetate are put into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, and heated and dissolved under stirring. Thereafter, it is cooled to crystallize the crystalline resin (A) in the form of fine particles, and this is wet-pulverized by a pulverizer such as Ultraviscomil to obtain the dispersion liquid (A).

  By mixing the dispersion liquid (A) and (B) and (C) dissolved in an organic solvent, (A) is mixed with (B) and (C) as a solid to form a toner. Then, it is preferable that it is not compatible with (B) and (C).

  Further, instead of dispersing in an organic solvent as in the dissolution suspension method, it may be produced by a method of dispersing in carbon dioxide in a supercritical state (for example, described in JP-A-2007-277511).

The toner of the present invention is not limited to the toner in which the crystalline resin (A) is converted into a toner via a dispersion, and a method of depositing the molten (A) in the toner. The thing obtained by is also included.
For example, the polymerization reaction of the monomer constituting (B) is performed in the state where (A) and (C) or (C0) is melted or dissolved in the monomer constituting the amorphous polyvinyl resin (B). In the method, the polymerization reaction temperature is maintained below the maximum temperature (Ta) of the endothermic peak of (A), so that (A) and (C) precipitate with the progress of the polymerization of (B), and further after polymerization Regarding the process, by controlling the temperature under the same temperature condition, a phase-separated toner can be produced, which is preferable from the viewpoint of heat-resistant storage stability.

The solid content concentration and volatile content of the toner particles and the like of the present invention are determined by the following method.
About 2.00 g of a sample such as toner particles is weighed and dried at 120 ° C. for 1 hour. Take out the sample after drying, measure the weight to the second decimal place, calculate the solid content concentration from (weight of sample after drying / weight of sample before drying) × 100, {(weight of sample before drying− The volatile content is calculated from (weight of sample after drying) / weight of sample before drying} × 100.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

<Production Example 1> [Synthesis of Crystalline Resin (A-1)]
[Synthesis of Crystalline Segment (a1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 696 parts by weight of sebacic acid, 424 parts by weight of 1,6-hexanediol and 0.5 part by weight of tetrabutoxy titanate as a condensation catalyst were placed at 170 ° C. The reaction was carried out for 8 hours while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction is performed for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction is further performed under a reduced pressure of 0.5 to 2.5 kPa. When it became below, it took out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline segment (a1). The SP _a1 of the crystalline segment (a1) was 9.9.

[Segment (a2)]
As the segment (a2), behenyl alcohol was used. SP _a2 is 9.3.

  In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 12 parts by weight of sebacic acid, 920 parts by weight of the crystalline segment (a1) and 80 parts by weight of the segment (a2), and tetrabutoxy titanate as a condensation catalyst were added in an amount of 0. 5 parts was added and reacted at 220 ° C. under reduced pressure of 0.5 to 2.5 kPa for 10 hours to obtain a crystalline resin (A-1).

<Production Example 2> [Synthesis of Crystalline Resin (A-2)]
The autoclave was charged with 150 parts by weight of xylene and replaced with nitrogen, and then heated to 185 ° C. Next, a mixed solution of 1000 parts by weight of behenyl acrylate, 2.3 parts by weight of di-t-butyl peroxide and 1000 parts by weight of xylene is added dropwise at the same temperature over 3 hours, and further maintained at the same temperature for 1 hour. Thus, a xylene solution of the crystalline resin (A-2) was obtained. Next, the obtained xylene solution was cooled to 170 ° C. while removing xylene at 1 kPa or less. After confirming that xylene in the resin was 1,000 ppm by gas chromatography, a crystalline resin (A-2) was obtained.

<Production Example 3> [Synthesis of Crystalline Resin (A-3)]
The autoclave was charged with 150 parts by weight of xylene and replaced with nitrogen, and then heated to 185 ° C. Next, a mixed solution of 600 parts by weight of behenyl acrylate, 400 parts by weight of styrene, 2.3 parts by weight of di-t-butyl peroxide and 1000 parts by weight of xylene was dropped at the same temperature over 3 hours. Holding at temperature for 1 hour, a xylene solution of crystalline resin (A-3) was obtained. Next, the obtained xylene solution was cooled to 170 ° C. while removing xylene at 1 kPa or less. After confirming that xylene in the resin was 1,000 ppm by gas chromatography, a crystalline resin (A-3) was obtained.

<Production Example 4> [Synthesis of Crystalline Resin (A-4)]
The autoclave was charged with 550 parts by weight of xylene and replaced with nitrogen, and then heated to 140 ° C. Next, a mixed solution of 640 parts by weight of behenyl acrylate, 14.7 parts by weight of methacrylic acid, 174 parts by weight of styrene, 174 parts by weight of acrylonitrile, 6.3 parts by weight of di-t-butyl peroxide and 450 parts by weight of xylene at the same temperature. The solution was added dropwise at the same temperature over 3 hours, held at the same temperature for 1 hour, and then heated to 170 ° C. to obtain a xylene solution of the crystalline resin (A-4). Next, xylene was removed at 1 kPa or less in the obtained xylene solution, and it was confirmed by gas chromatography that xylene in the resin was 1,000 ppm. Thus, a crystalline resin (A-4) was obtained.

<Production Example 5> [Synthesis of Crystalline Resin (A-5)]
[Synthesis of Crystalline Segment (a1-2)]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, 687 parts by weight of sebacic acid, 412 parts by weight of 1,6-hexanediol and 2.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were placed at 200 ° C. The reaction was carried out for 4 hours while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 4 hours while distilling off the water produced under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 0.5 to 2.5 kPa. It was taken out when it became. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline segment (a1-2). The SP _a1 of the crystalline segment (a1-2) was 10.0.

[Segment (a2)]
As the segment (a2), behenyl alcohol was used. SP _a2 is 9.3.

  978 parts by weight of crystalline segment (a1-2) and 22 parts by weight of segment (a2) and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. The resultant was reacted at 220 ° C. under reduced pressure of 0.5 to 2.5 kPa for 10 hours to obtain a crystalline resin (A-5).

<Production Example 6> [Synthesis of Crystalline Resin (A-6)]
The autoclave was charged with 550 parts by weight of xylene and replaced with nitrogen, and then heated to 170 ° C. Next, a mixed solution of 600 parts by weight of behenyl acrylate, 200 parts by weight of styrene, 200 parts by weight of acrylonitrile, 3.1 parts by weight of di-t-butyl peroxide and 400 parts by weight of xylene at the same temperature was added over 3 hours at the same temperature. The solution was added dropwise and further kept at the same temperature for 1 hour to obtain a xylene solution of crystalline resin (A-6). Next, in the obtained xylene solution, xylene was removed at 1 kPa or less, and it was confirmed by gas chromatography that xylene in the resin was 1,000 ppm. Thus, a crystalline resin (A-6) was obtained.

  Table 1 shows physical property values of the crystalline resins (A-1) to (A-6).

<Production Example 7> [Synthesis of Amorphous Polyvinyl Resin (B-1)]
The autoclave was charged with 80 parts by weight of xylene and replaced with nitrogen, and then heated to 185 ° C. Subsequently, a mixed solution of 90 parts by weight of styrene, 8 parts by weight of n-butyl acrylate, 2 parts by weight of acrylic acid, 0.23 parts by weight of di-t-butyl peroxide and 35 parts by weight of xylene at the same temperature was mixed with 3 parts at the same temperature. The solution was added dropwise over time, and further maintained at the same temperature for 1 hour to obtain a xylene solution of an amorphous polyvinyl resin (B-1). Next, the obtained xylene solution was cooled to 170 ° C. while removing xylene at 1 kPa or less. It was confirmed by gas chromatography that xylene in the resin was 1,000 ppm and unreacted monomers were 1,000 ppm or less, and an amorphous polyvinyl resin (B-1) was obtained.

<Production Example 8> [Synthesis of Amorphous Polyvinyl Resin (B-2)]
The autoclave was charged with 50 parts by weight of xylene and replaced with nitrogen, and then heated to 190 ° C. Next, a mixed solution of 83 parts by weight of styrene, 17 parts by weight of n-butyl acrylate, 3 parts by weight of di-t-butyl peroxide and 18.2 parts by weight of xylene at the same temperature was dropped over 3 hours at the same temperature, Furthermore, it hold | maintained at the same temperature for 30 minutes, and the xylene solution of the amorphous polyvinyl resin (B-2) was obtained. Next, the obtained xylene solution was cooled to 170 ° C. while removing xylene at 1 kPa or less. It was confirmed by gas chromatography that xylene in the resin was 1,000 ppm and unreacted monomers were 1,000 ppm or less, and an amorphous polyvinyl resin (B-2) was obtained.

  Table 2 shows physical property values of the amorphous polyvinyl resins (B-1) and (B-2).

<Production Example 9> [Synthesis of Amorphous Polyester Resin (C-1)]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 752 parts by weight of bisphenol A / PO2 molar adduct, 313 parts by weight of terephthalic acid, 1 part by weight of fumaric acid, 1 part by weight of trimellitic anhydride, condensation catalyst Titanium diisopropoxy bistriethanolaminate (2.5 parts by weight) was added as follows, and the reaction was carried out for 4 hours while distilling off the generated water at 230 ° C. under a nitrogen stream, and the reaction was conducted under a reduced pressure of 0.5 to 2.5 kPa. After reacting for a period of time, it was taken out to obtain an amorphous polyester resin (C-1).

<Production Example 10> [Synthesis of Amorphous Polyester Resin (C-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 727 parts by weight of bisphenol A · EO 2 molar adduct, 26 parts by weight of trimethylolpropane, 132 parts by weight of terephthalic acid, 142 parts by weight of adipic acid, 48 parts of fumaric acid While adding 2.5 parts by weight of titanium diisopropoxybistriethanolamate as a condensation catalyst and 1 part by weight of tert-butylcatechol as a polymerization inhibitor while distilling off the water produced at 180 ° C. in a nitrogen stream. The reaction was performed for 4 hours. Furthermore, after making it react under reduced pressure of 0.5-2.5 kPa for 10 hours, it took out, and the amorphous polyester resin (C-2) was obtained.

<Production Example 11> [Synthesis of Amorphous Polyester Resin (C0-1)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 770 parts by weight of bisphenol A / EO 2 mole adduct, 110 parts by weight of terephthalic acid, 118 parts by weight of adipic acid, 38 parts by weight of fumaric acid, titanium as a condensation catalyst 2.5 parts by weight of diisopropoxybistriethanolamate and 1 part by weight of tert-butylcatechol as a polymerization inhibitor were added and reacted at 180 ° C. for 4 hours while distilling off the generated water. Furthermore, after making it react under reduced pressure of 0.5-2.5 kPa for 8 hours, it took out and obtained the amorphous polyester resin (C0-1).

<Production Example 12> [Synthesis of Amorphous Polyester Resin (C0-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 148 parts by weight of bisphenol A / PO2 molar adduct, 630 parts by weight of bisphenol A / PO2 molar adduct, 279 parts by weight of terephthalic acid, 1 part by weight of fumaric acid Then, 2.5 parts by weight of titanium diisopropoxybistriethanolamate was added as a condensation catalyst and reacted at 235 ° C. under a nitrogen stream for 4 hours while distilling off the generated water, thereby producing an amorphous polyester resin (C0-2). )

  Table 3 shows physical property values of the amorphous polyester resins (C-1), (C-2), (C0-1), and (C0-2).

<Production Example 13> [Production of crystalline resin dispersion (AD-1)]
Into a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, 15 parts by weight of the resin (A-1) produced in Production Example 1 and 15 parts by weight of ethyl acetate were added and the temperature was raised to 65 ° C. with stirring. Warm, stir at the same temperature for 30 minutes, cool to 10 ° C. over 1 hour to crystallize the crystalline resin into fine particles, wet pulverize with Ultra Viscomil (manufactured by IMEX), (AD-1) was obtained. The volume average particle diameter of (A-1) in (AD-1) was 0.5 μm, and the solid content concentration was 50% by weight.

<Production Example 14> [Production of Amorphous Polyvinyl Resin Solution (BS-1)]
Into a reaction vessel equipped with a stirrer, 50 parts by weight of amorphous polyvinyl resin (B-1) and 50 parts by weight of ethyl acetate were added and stirred to dissolve the resin uniformly. BS-1) was obtained.

<Production Example 15> [Production of Amorphous Polyester Resin Solution (CS-1)]
Into a reaction vessel equipped with a stirrer, 50 parts by weight of amorphous polyester resin (C-1) and 50 parts by weight of ethyl acetate were added and stirred to dissolve the resin uniformly. CS-1) was obtained.

<Production Example 16> [Production of Amorphous Polyester Resin Solution (CS-2)]
Into a reaction vessel equipped with a stirrer, 50 parts by weight of amorphous polyester resin (C-2) and 50 parts by weight of ethyl acetate were added and stirred to dissolve the resin uniformly. CS-2) was obtained.

<Production Example 17> [Production of release agent dispersion]
Paraffin wax (petroleum wax) “HNP-9” [Tr: 73 ° C., kinematic viscosity at 100 ° C .: 7 mm ² / s, Nippon Seiki, in a reaction vessel equipped with a stirrer, heating / cooling device, cooling tube and thermometer Made by Co., Ltd.] 10 parts by weight and 15 parts by weight of ethyl acetate were added, heated to 78 ° C. with stirring, stirred for 30 minutes at the same temperature, cooled to 30 ° C. over 1 hour, and paraffin wax in the form of fine particles Then, it was wet pulverized with Ultra Visco Mill (manufactured by Imex) to obtain a release agent dispersion. The obtained release agent dispersion had a volume average particle size of 0.25 μm and a solid content concentration of 50% by weight.

Example 1 [Production of Toner (T-1)]
5 parts by weight of crystalline resin (A-1), 72 parts by weight of amorphous polyvinyl resin (B-1), 10 parts by weight of amorphous polyester resin (C-1), and carbon black MA-100 [Mitsubishi as a colorant Chemical Co., Ltd.] 6 parts by weight and 6 parts by weight of paraffin wax (petroleum wax) “HNP-9” as a release agent were added to form a toner by the following method. First, after premixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] to obtain a volume average particle diameter. Toner particles having (D50) of 8 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain toner (T-1) of the present invention.

Example 2 [Production of Toner (T-2)]
5 parts by weight of crystalline resin (A-1), 72 parts by weight of amorphous polyvinyl resin (B-1), 10 parts by weight of amorphous polyester resin (C-2), and carbon black MA-100 [Mitsubishi as a colorant Chemical Co., Ltd.] 6 parts by weight and 6 parts by weight of paraffin wax (petroleum wax) “HNP-9” as a release agent were added to form a toner by the following method. First, after premixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] to obtain a volume average particle diameter. Toner particles having (D50) of 8 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain a toner (T-2) of the present invention.

Example 3 [Production of Toner (T-3)]
To 1000 parts by weight of ion-exchanged water in the reaction vessel, 14 parts by weight of sodium phosphate and 4.5 parts by weight of 10% by weight hydrochloric acid were added and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (Primix Co., Ltd.), while stirring at 12,000 rpm, a solution of calcium chloride in which 7.8 parts by weight of calcium chloride is dissolved in 10 parts by weight of ion-exchanged water is added to the dispersion stability. An aqueous medium containing the agent was prepared.

Next, in a separate container: 65 parts by weight of styrene 6 parts by weight of n-butyl acrylate 1 part by weight of acrylic acid 5 parts by weight of crystalline resin (A-1) 10 parts by weight of amorphous polyester resin (C-1) Part / Colorant Carbon Black MA-100 6 parts by weight Release agent Paraffin wax “HNP-9” 6 parts by weight was added, the above material was kept at 66 ° C., and a TK homomixer (manufactured by Primics Co., Ltd.) was added. And uniformly dissolved and dispersed at 500 rpm. To this, a polymerization initiator t-butyl peroxylaurate (manufactured by NOF Corporation, trade name “Perbutyl L”, molecular weight: 272, 10 hour half-life temperature: 98.3 ° C., active oxygen content: 5.24 %) 3.0 parts by weight were dissolved to prepare a polymerizable monomer composition.

  The polymerizable monomer composition was put into the aqueous medium in the reaction vessel, stirred at 10,000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N 2 purge, and granulated at pH 5.8. Then, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours and further to 90 ° C. and reacted for 6 hours to synthesize (B-1) in the presence of (A-1) and (C-1). Went.

After completion of the polymerization reaction, the reaction vessel is cooled to 62 ° C. for 1 hour, held at 62 ° C. for 1 hour, the reaction vessel is rapidly cooled to room temperature, and then 10% by weight hydrochloric acid is added to adjust the pH to 2 while stirring for 2 hours. The dispersion stabilizer was dissolved to obtain an aqueous dispersion of toner particles. The aqueous dispersion of toner particles was filtered off, washed with 2000 parts by weight or more of ion-exchanged water, and filtered. The obtained cake was returned to 1000 parts by weight of ion-exchanged water, stirred for 2 hours with 10 wt% hydrochloric acid added and adjusted to pH = 1 or less, washed and filtered. In the same manner as above, it was further washed with 2000 parts by weight or more of ion-exchanged water, filtered, sufficiently ventilated, dried under reduced pressure, and classified with an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] Toner particles having a volume average particle diameter (D50) of 5 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain the toner (T-3) of the present invention.

Example 4 [Production of Toner (T-4)]
To 1000 parts by weight of ion-exchanged water in the reaction vessel, 14 parts by weight of sodium phosphate and 4.5 parts by weight of 10% by weight hydrochloric acid were added and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (Primix Co., Ltd.), while stirring at 12,000 rpm, a solution of calcium chloride in which 7.8 parts by weight of calcium chloride is dissolved in 10 parts by weight of ion-exchanged water is added to the dispersion stability. An aqueous medium containing the agent was prepared.

Next, in a separate container: 65 parts by weight of styrene 6 parts by weight of n-butyl acrylate 1 part by weight of acrylic acid 5 parts by weight of crystalline resin (A-1) 10 parts by weight of amorphous polyester resin (C-2) Part / Colorant Carbon Black MA-100 6 parts by weight Release agent Paraffin wax “HNP-9” 6 parts by weight (where (C-2) is used as a polyester resin (C0) having a carbon-carbon double bond) .)
Was added, and the above material was kept at 66 ° C., and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Primics Co., Ltd.). To this, a polymerization initiator t-butyl peroxylaurate (manufactured by NOF Corporation, trade name “Perbutyl L”, molecular weight: 272, 10 hour half-life temperature: 98.3 ° C., active oxygen content: 5.24%) 3.0 parts by weight was dissolved to prepare a polymerizable monomer composition.

  The polymerizable monomer composition was put into the aqueous medium in the reaction vessel, stirred at 10,000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N 2 purge, and granulated at pH 5.8. Then, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours and further to 90 ° C., and reacted for 6 hours. In the presence of (A-1), the crosslinking reaction of (C-2) and (B-1 ) Was synthesized.

After completion of the polymerization reaction, the reaction vessel is cooled to 62 ° C. for 1 hour, held at 62 ° C. for 1 hour, the reaction vessel is rapidly cooled to room temperature, and then 10% by weight hydrochloric acid is added to adjust the pH to 2 while stirring for 2 hours. The dispersion stabilizer was dissolved to obtain an aqueous dispersion of toner particles. The aqueous dispersion of toner particles was filtered off, washed with 2000 parts by weight or more of ion-exchanged water, and filtered. The obtained cake was returned to 1000 parts by weight of ion-exchanged water, stirred for 2 hours with 10 wt% hydrochloric acid added and adjusted to pH = 1 or less, washed and filtered. In the same manner as above, it was further washed with 2000 parts by weight or more of ion-exchanged water, filtered, sufficiently ventilated, dried under reduced pressure, and classified with an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] Toner particles having a volume average particle diameter (D50) of 5 μm were obtained.
Next, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent are mixed in a sample mill, and the polyester resin (C0) is crosslinked by a carbon-carbon bond. A toner (T-4) of the present invention containing (C) was obtained.

<Examples 5 and 6> [Production of Toners (T-5) and (T-6)]
Using the dispersion liquid (AD-1), solutions (BS-1), (CS-1), (CS-2), and the release agent dispersion liquid obtained in Production Examples 13 to 17, a crystalline resin (A -1), amorphous polyvinyl resin (B-1), amorphous polyester resin (C-1), (C-2), and the solid content of the release agent dispersion liquid are the parts by weight shown in Table 4, respectively. The toner was prepared by the following method.

  In a beaker, 95 parts by weight of ion-exchanged water, 1 part by weight of sodium carboxymethylcellulose, 50.0% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate “Eleminol MON-7” [manufactured by Sanyo Chemical Industries, Ltd.] 16.8 parts by weight and 8.9 parts by weight of ethyl acetate was added and stirred to dissolve uniformly. Next, the temperature was raised to 25 ° C., and while stirring the TK auto homomixer at 10,000 rpm at the same temperature, 4.5 parts by weight of the crystalline resin dispersion, 64.8 parts by weight of the amorphous polyvinyl resin solution, amorphous 9.0 parts by weight of a polyester resin solution, 2.7 parts by weight of a colorant, and 5.4 parts by weight of a release agent dispersion were added and stirred for 2 minutes. Subsequently, this dispersion was transferred to a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, and ethyl acetate was distilled off at 30 ° C. until the concentration of ethyl acetate was 0.5% by weight or less. An aqueous resin dispersion of toner particles was obtained. Subsequently, it was washed and separated by filtration, and dried at 40 ° C. for 18 hours to make the volatile content 0.5% by weight or less. The toner of the present invention having 49.5 parts by weight of the obtained toner particles and 0.5 parts by weight of a fluidizing agent colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) and having a volume average particle diameter (D50) of 5 μm. (T-5) and (T-6) were obtained.

Example 7 [Production of Toner (T-7)]
5 parts by weight of crystalline resin (A-2), 72 parts by weight of amorphous polyvinyl resin (B-1), 10 parts by weight of amorphous polyester resin (C-1), and carbon black MA-100 [Mitsubishi as a colorant Chemical Co., Ltd.] 6 parts by weight and 6 parts by weight of paraffin wax (petroleum wax) “HNP-9” as a release agent were added to form a toner by the following method. First, after premixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] to obtain a volume average particle diameter. Toner particles having (D50) of 8 μm were obtained.
Next, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain toner (T-7) of the present invention.

<Example 8> [Production of toner (T-8)]
To 1000 parts by weight of ion-exchanged water in the reaction vessel, 14 parts by weight of sodium phosphate and 4.5 parts by weight of 10% by weight hydrochloric acid were added and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (Primix Co., Ltd.), while stirring at 12,000 rpm, a solution of calcium chloride in which 7.8 parts by weight of calcium chloride is dissolved in 10 parts by weight of ion-exchanged water is added to the dispersion stability. An aqueous medium containing the agent was prepared.

Next, in a separate container: 65 parts by weight of styrene 6 parts by weight of n-butyl acrylate 1 part by weight of acrylic acid 5 parts by weight of crystalline resin (A-3) 10 parts by weight of amorphous polyester resin (C-1) Part / Colorant Carbon Black MA-100 6 parts by weight Release agent Paraffin wax “HNP-9” 6 parts by weight was added, the above material was kept at 66 ° C., and a TK homomixer (manufactured by Primics Co., Ltd.) was added. And uniformly dissolved and dispersed at 500 rpm. To this, a polymerization initiator t-butyl peroxylaurate (manufactured by NOF Corporation, trade name “Perbutyl L”, molecular weight: 272, 10 hour half-life temperature: 98.3 ° C., active oxygen content: 5.24 %) 3.0 parts by weight were dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, stirred at 10000 rpm for 5 minutes with a TK homomixer under N ₂ purge at 65 ° C., and granulated at pH 5.8. . Then, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours and further to 90 ° C. and reacted for 6 hours to synthesize (B-1) in the presence of (A-3) and (C-1). Went.

After completion of the polymerization reaction, the reaction vessel is cooled to 62 ° C. for 1 hour, held at 62 ° C. for 1 hour, the reaction vessel is rapidly cooled to room temperature, and then 10% by weight hydrochloric acid is added to adjust the pH to 2 while stirring for 2 hours. The dispersion stabilizer was dissolved to obtain an aqueous dispersion of toner particles. The aqueous dispersion of toner particles was filtered off, washed with 2000 parts by weight or more of ion-exchanged water, and filtered. The obtained cake was returned to 1000 parts by weight of ion-exchanged water, stirred for 2 hours with 10 wt% hydrochloric acid added and adjusted to pH = 1 or less, washed and filtered. In the same manner as above, it was further washed with 2000 parts by weight or more of ion-exchanged water, filtered, sufficiently ventilated, dried under reduced pressure, and classified with an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] Toner particles having a volume average particle diameter (D50) of 5 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain toner (T-8) of the present invention.

<Example 9> [Production of toner (T-9)]
5 parts by weight of crystalline resin (A-4), 72 parts by weight of amorphous polyvinyl resin (B-1), 10 parts by weight of amorphous polyester resin (C-1), and carbon black MA-100 [Mitsubishi as a colorant Chemical Co., Ltd.] 6 parts by weight and 6 parts by weight of paraffin wax (petroleum wax) “HNP-9” as a release agent were added to form a toner by the following method. First, after premixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] to obtain a volume average particle diameter. Toner particles having (D50) of 8 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain toner (T-9) of the present invention.

Example 10 [Production of Toner (T-10)]
5 parts by weight of crystalline resin (A-5), 72 parts by weight of amorphous polyvinyl resin (B-1), 10 parts by weight of amorphous polyester resin (C-1), and carbon black MA-100 [Mitsubishi as a colorant Chemical Co., Ltd.] 6 parts by weight and 6 parts by weight of paraffin wax (petroleum wax) “HNP-9” as a release agent were added to form a toner by the following method. First, after premixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] to obtain a volume average particle diameter. Toner particles having (D50) of 8 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain toner (T-10) of the present invention.

Example 11 [Production of Toner (T-11)]
5 parts by weight of crystalline resin (A-6), 72 parts by weight of amorphous polyvinyl resin (B-1), 10 parts by weight of amorphous polyester resin (C-1), and carbon black MA-100 [Mitsubishi as a colorant Chemical Co., Ltd.] 6 parts by weight and 6 parts by weight of paraffin wax (petroleum wax) “HNP-9” as a release agent were added to form a toner by the following method. First, after premixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] to obtain a volume average particle diameter. Toner particles having (D50) of 8 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain the toner (T-11) of the present invention.

<Example 12> [Production of toner (T-12)]
5 parts by weight of crystalline resin (A-6), 72 parts by weight of amorphous polyvinyl resin (B-2), 10 parts by weight of amorphous polyester resin (C-1), and carbon black MA-100 [Mitsubishi as a colorant Chemical Co., Ltd.] 6 parts by weight and 6 parts by weight of paraffin wax (petroleum wax) “HNP-9” as a release agent were added to form a toner by the following method. First, after premixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] to obtain a volume average particle diameter. Toner particles having (D50) of 8 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain toner (T-12) of the present invention.

Example 13 [Production of Toner (T-13)]
72 parts by weight of amorphous polyvinyl resin (B-2) and 10 parts by weight of amorphous polyester resin (C0-1) were supplied to a twin-screw kneader (Kurimoto Iron Works, S5KRC kneader) at 52 kg / hr. As a radical reaction initiator, 2.0 parts of t-butylperoxyisopropyl monocarbonate was supplied at 1 kg / hour and kneaded and extruded at 160 ° C. for 6 minutes to carry out a crosslinking reaction. Next, 5 parts by weight of a resin obtained by a crosslinking reaction and a crystalline resin (A-6), 6 parts by weight of carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation] as a colorant, and paraffin wax (petroleum wax as a release agent) ) 6 parts by weight of "HNP-9" was added to make a toner by the following method.
First, after preliminarily mixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] to obtain a volume average particle diameter. Toner particles having (D50) of 8 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain a toner (T-13) of the present invention.

Example 14 [Production of Toner (T-14)]
72 parts by weight of amorphous polyvinyl resin (B-2) and 10 parts by weight of amorphous polyester resin (C0-2) were fed to a twin-screw kneader (Kurimoto Iron Works, S5KRC kneader) at 52 kg / hr. As a radical reaction initiator, 2.0 parts of t-butylperoxyisopropyl monocarbonate was supplied at 1 kg / hour and kneaded and extruded at 160 ° C. for 6 minutes to carry out a crosslinking reaction. Next, 5 parts by weight of a resin obtained by a crosslinking reaction and a crystalline resin (A-6), 6 parts by weight of carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation] as a colorant, and paraffin wax (petroleum wax as a release agent) ) 6 parts by weight of "HNP-9" was added to make a toner by the following method.
First, after preliminarily mixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] to obtain a volume average particle diameter. Toner particles having (D50) of 8 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain a toner (T-14) of the present invention.

Example 15 [Production of Toner (T-15)]
67 parts by weight of crystalline resin (A-6) and 15 parts by weight of amorphous polyester resin (C0-1) were supplied to a twin-screw kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) at a rate of 52 kg / hr. As an initiator, 2.0 parts of t-butylperoxyisopropyl monocarbonate was supplied at 1 kg / hour and kneaded and extruded at 160 ° C. for 6 minutes to carry out a crosslinking reaction. Next, 5 parts by weight of a resin obtained by a crosslinking reaction and amorphous polyvinyl resin (B-2), 6 parts by weight of carbon black MA-100 [manufactured by Mitsubishi Chemical Corporation] as a colorant, and paraffin wax (as a release agent) Petroleum wax) 6 parts by weight of “HNP-9” was added to form a toner by the following method.
First, after preliminarily mixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] to obtain a volume average particle diameter. Toner particles having (D50) of 8 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain toner (T-15) of the present invention.

<Example 16> [Production of toner (T-16)]
67 parts by weight of crystalline resin (A-6) and 10 parts by weight of amorphous polyester resin (C0-1) were supplied to a twin-screw kneader (Kurimoto Iron Works, S5KRC kneader) at 52 kg / hour, and simultaneously radical reaction As an initiator, 2.0 parts of t-butylperoxyisopropyl monocarbonate was supplied at 1 kg / hour and kneaded and extruded at 160 ° C. for 6 minutes to carry out a crosslinking reaction. Next, 10 parts by weight of the resin obtained by the crosslinking reaction and amorphous polyvinyl resin (B-2), 6 parts by weight of carbon black MA-100 [manufactured by Mitsubishi Chemical Co., Ltd.] as a colorant, and paraffin wax (as a release agent) Petroleum wax) 6 parts by weight of “HNP-9” was added to form a toner by the following method.
First, after preliminarily mixing using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], the mixture was kneaded using a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Next, the mixture was finely pulverized using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], and then classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.] to obtain a volume average particle diameter. Toner particles having (D50) of 8 μm were obtained.
Subsequently, 99 parts by weight of toner particles and 1 part by weight of colloidal silica (Aerosil R972: made by Nippon Aerosil) as a fluidizing agent were mixed in a sample mill to obtain the toner (T-16) of the present invention.

<Comparative Example 1> [Preparation of Comparative Toner (T′-1)]
Using the dispersion liquid (AD-1), solution (CS-1), and release agent dispersion liquid obtained in Production Examples 13 to 17, the crystalline resin (A-1) and the amorphous polyester resin (C- 1) The solid content of the release agent dispersion was weighed so as to have the parts by weight shown in Table 4, and a toner was prepared by the following method.

  In a beaker, 95 parts by weight of ion-exchanged water, 1 part by weight of sodium carboxymethylcellulose, 50.0% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate “Eleminol MON-7” [manufactured by Sanyo Chemical Industries, Ltd.] 16.8 parts by weight and 8.9 parts by weight of ethyl acetate was added and stirred to dissolve uniformly. Next, the temperature was raised to 25 ° C., and while stirring the TK auto homomixer at 10,000 rpm at the same temperature, 4.5 parts by weight of the crystalline resin dispersion, 73.8 parts by weight of the amorphous polyester resin solution, and Colorant 2 .7 parts by weight and 5.4 parts by weight of the release agent dispersion were added and stirred for 2 minutes. Next, this dispersion was transferred to a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, and ethyl acetate was distilled off at 30 ° C. until the concentration reached 0.5% by weight or less. An aqueous resin dispersion was obtained. Subsequently, it was washed and separated by filtration, and dried at 40 ° C. for 18 hours to make the volatile content 0.5% by weight or less. 49.5 parts by weight of the obtained toner particles and 0.5 parts by weight of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil) as a fluidizing agent are uniformly mixed, and a comparative toner having a volume average particle diameter (D50) of 5 μm ( T′-1) was obtained.

  For toners (T-1) to (T-16) and comparative toner (T′-1), low-temperature fixability, hot offset resistance, gloss, fluidity, heat-resistant storage stability, heat-and-moisture resistance storage resistance, The charging stability, pulverization property, image strength, bending resistance, document offset property and durability were evaluated. The results are shown in Table 4.

[1] Low-temperature fixability The toner is uniformly placed on the paper surface so as to be 0.6 mg / cm ² (At this time, the method of placing the powder on the paper surface uses a printer from which the heat fixing machine is removed. Other methods may be used as long as the powder can be placed uniformly). When this paper was passed through a pressure roller under conditions of a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 1 MPa, the temperature at which cold offset occurred was measured. The lower the temperature at which cold offset occurs, the better the low-temperature fixability.

[2] Hot offset resistance (hot offset generation temperature)
Fixation was evaluated using the same apparatus and method as for low-temperature fixability, and the presence or absence of hot offset on the fixed image was visually evaluated.
The temperature at which hot offset occurred after passing through the pressure roller was defined as hot offset resistance (° C.).

[3] Gloss Using an gloss meter (VG-1D) (manufactured by Nippon Denshoku Co., Ltd.) for an image fixed at 140 ° C., adjusting the light projection angle and the light reception angle to 60 °, and switching between S and S / 10 In accordance with S, 0 adjustment and a standard plate were used, and after setting the standard, the image was placed on a sample stage, and gloss was measured.
A higher gloss value means higher gloss.

[4] Fluidity The toner bulk density (g / 100 mL) was measured with a powder tester manufactured by Hosokawa Micron, and the fluidity was determined according to the following criteria. Δ or more (30 g / 100 mL or more) is a practical range.

[Criteria]
◎: 36 or more ○: 33 or more and less than 36 △: 30 or more and less than 33 ▲: 27 or more and less than 30 ×: Less than 27

[5] Heat-resistant storage stability The sample was allowed to stand in an atmosphere of 50 ° C. for 24 hours, the degree of blocking was judged visually, and the heat-resistant storage stability was evaluated according to the following criteria.
[Evaluation criteria]
◎: Blocking does not occur ○: Blocking occurs, but disperses easily with a little force △: Blocking occurs, but some blocking remains when force is applied ×: Blocking occurs and force is applied Does not disperse even when added

[6] Moisture and heat storage stability The sample was allowed to stand for 20 hours in an atmosphere of 40 ° C. and a relative humidity of 80%, the degree of blocking was judged visually, and the moisture and heat storage stability was evaluated according to the following criteria.
[Evaluation criteria]
◎: Blocking does not occur ○: Blocking occurs, but disperses easily with a little force △: Blocking occurs, but some blocking remains when force is applied ×: Blocking occurs and force is applied Does not disperse even when added

[7] Charge stability (1) 0.5 g of toner and 20 g of ferrite carrier (F-150, manufactured by Powdertech Co., Ltd.) are placed in a 50 ml glass bottle with a stopper, and this is placed at 23 ° C. and 50% relative humidity for 8 hours. Adjust humidity above.
(2) Blow-off powder with 20 μm stainless wire mesh set to 0.2 g of the mixed powder after stirring by stirring at 50 rpm × 20 minutes for 60 minutes with a tumbler shaker mixer (manufactured by Wheelie a Baschofen) The charge amount of the residual ferrite carrier is measured under the conditions of a blow pressure of 10 KPa and a suction pressure of 5 KPa, and the toner charge amount (μC / g) is measured by a conventional method. ) Is calculated.
“Charging amount of 60 minutes friction time / charging amount of 10 minutes friction time” was calculated and used as an index of charging stability.

[Criteria]
◎: 0.9 or more ○: 0.7 or more and less than 0.9

[8] Crushability A coarsely pulverized product (from 8.6 mesh pass to 30 mesh on) kneaded and cooled with a twin-screw kneader is used as a supersonic jet pulverizer, Labo Jet [manufactured by Nippon Pneumatic Industry Co., Ltd. ] Was pulverized under the following conditions.
Crushing pressure: 0.5 MPa
Grinding time: 10 minutes Adjuster ring: 15 mm
Size of louver: Medium Without classification, volume average particle size (μm) was measured with a Coulter counter “Multisizer IV” (manufactured by Beckman Coulter, Inc.), and pulverization was evaluated according to the following criteria.
In Examples 3 to 6, and 8 in which the pulverization process was not performed, the toner particles having a volume average particle diameter of less than 10 μm could be produced, and thus the evaluation was “◎”.

[Criteria]
◎: Less than 10 ○: 10 or more and less than 11 Δ: 11 or more and less than 12 ×: 12 or more

[9] Image strength The image fixed by the evaluation of low temperature fixability is subjected to a scratch test by applying a load of 10 g from right above a pencil fixed at an angle of 45 degrees according to JIS K5600. Image intensity was evaluated. Higher pencil hardness means better image strength.

[Criteria]
○: HB or more △: B
X: 2B or less

[10] Bending resistance The image fixed in the evaluation of the low-temperature fixing property is bent so that the image surface is on the inside, and rubbed twice with a load of 30 g.
The presence or absence of white streaks after the paper was spread and folded on the image was visually judged.

[Criteria]
○: No white streak
Δ: Slight white streak ×: White streak

[11] Document offset property Two sheets of A4 paper on which an image obtained by evaluation of low-temperature fixability is fixed are overlapped with each other on a fixing surface, and a weight of 420 g (0.68 g / cm ² ) is applied, and 65 ° C. And left for 10 minutes.
The document offset property was evaluated according to the following criteria for the state when the stacked papers were pulled apart.

[Criteria]
○: No resistance △: Sounds crispy but image does not peel off from paper ×: Image peels off from paper

[12] Durability Continuous copying was performed using a commercially available monochrome copying machine [AR5030, manufactured by Sharp Corporation] as a two-component developer, and durability was evaluated according to the following criteria.
[Evaluation criteria]
◎ No change in image quality after 10,000 copies, no fogging ○ Fog after 10,000 copies △: Fog after 6,000 copies ×: 2,000 Fog has occurred after copying

  The toners of Examples 1 to 16 obtained excellent results in any performance evaluation items. On the other hand, the toner of Comparative Example 1 that did not contain the amorphous polyvinyl resin (B) had poor hot offset resistance and durability.

The toner binder and toner of the present invention are excellent in low-temperature fixability, glossiness, and hot offset resistance, and have toner flowability, heat-resistant storage stability, charging stability, pulverization property, image strength, folding resistance, document offset property. Electrophotographic toner and electrostatic recording toner used for developing electrostatic images or magnetic latent images in electrophotography, electrostatic recording method, electrostatic printing method, etc. It is useful as an electrostatic printing toner.

Claims (16)

A toner binder containing a crystalline resin (A), an amorphous polyvinyl resin (B) having an ester group, and an amorphous polyester resin (C), wherein the toner binder satisfies the following relational expression (1): Toner binder.
Q2 / Q1> 0.50 (1)
[In the formula, Q1 is a crystalline resin in the first temperature rising process of the toner binder measured by a differential scanning calorimeter (DSC) that is heated from 0 ° C. to 150 ° C. under the condition of 10 ° C./min ( The endothermic amount [J / g], Q2 based on the endothermic peak derived from A) is measured from 150 ° C. after measuring Q1 in the first temperature rising process of the toner binder measured by a differential scanning calorimeter (DSC). An endothermic amount based on an endothermic peak derived from the crystalline resin (A) in the second temperature raising process in which the temperature is raised from 0 ° C. to 10 ° C. per minute and then raised again from 0 ° C. to 150 ° C. at 10 ° C. per minute. [J / g] is represented. ]   The endothermic amount Q2 based on an endothermic peak derived from the crystalline resin (A) in the second temperature rising process of the toner binder measured by a differential scanning calorimeter (DSC) is 0.5 to 30 J / g. The toner binder according to 1.   The toner binder according to claim 1, wherein the crystalline resin (A) is a crystalline polyvinyl resin and / or a crystalline polyester resin.   The toner binder according to any one of claims 1 to 3, wherein the maximum temperature (Ta) of the endothermic peak of the crystalline resin (A) is 40 to 100 ° C.   The toner binder according to claim 1, wherein the acid value of the crystalline resin (A) is 0.01 to 10 mg KOH / g.   The toner binder according to claim 1, wherein the crystalline resin (A) has a weight average molecular weight of 3,000 to 50,000.   The toner binder according to claim 1, wherein the content of the component having a molecular weight of 1,500 or less in the crystalline resin (A) is 8% by weight or less based on the weight of (A).   The toner binder according to claim 1, wherein the crystalline resin (A) has a xylene-insoluble content of 0.1 to 6.0% by mass.   The crystalline resin (A) is a resin in which at least two or more types of segments are chemically bonded, the crystalline segment (a1) compatible with the amorphous polyester resin (C), and the amorphous polyester resin The toner binder according to claim 1, which has a segment (a2) that is incompatible with (C). The toner binder according to claim 9, wherein the crystalline segment (a1) and the segment (a2) satisfy both the following relational expressions (2) and (3).
| SP _a1 −SP _C | <1.8 (2)
| SP _a2 −SP _C | ≧ 1.8 (3)
[However, SP _a1 is the solubility parameter [(cal / cm ³ ) ^1/2 ] of segment (a1), SP _a2 is the solubility parameter [(cal / cm ³ ) ^1/2 ] of segment (a2), and SP _C is The solubility parameter [(cal / cm ³ ) ^1/2 ] of the amorphous polyester resin (C) is represented. ]   The toner binder according to claim 1, wherein the amorphous polyester resin (C) is a polyester resin obtained by crosslinking the amorphous polyester resin (C 0) with a carbon-carbon bond.   The toner binder according to claim 11, wherein the amorphous polyester resin (C0) is a polyester resin having a carbon-carbon double bond.   The amorphous polyester resin (C0) is a polyester resin obtained by polycondensation of a component containing an unsaturated carboxylic acid component (Y1) and / or an unsaturated alcohol component (X1). Toner binder.   Amorphous polyester resin (C0) having a glass transition temperature of −40 ° C. to less than 55 ° C. and / or an amorphous polyester resin (C2) having a glass transition temperature of 55 ° C. to 85 ° C. The toner binder according to claim 11, wherein the toner binder is a resin containing a toner.   The amorphous polyester resin (C) is a polyester resin obtained by polycondensation of a component containing an alcohol component (X) and a carboxylic acid component (Y), and the alcohol component (X) contains an aromatic diol of 80 The toner binder according to claim 1, wherein the toner binder is contained in an amount of at least mol%, and the carboxylic acid component (Y) contains at least 80 mol% of an aromatic dicarboxylic acid. A toner containing the toner binder according to claim 1.