JP6530107B2 - Method of manufacturing toner - Google Patents

Description

  The present invention relates to a method for producing a toner used for developing a latent image formed in electrophotography, electrostatic recording, electrostatic printing and the like.

At present, from the viewpoint of energy saving, coexistence of heat-resistant storage stability, moisture-heat storage stability and low-temperature fixability is desired for toners for electrophotography. In order to solve this problem, there is proposed a method of achieving both the decrease in the fixing temperature and the heat resistant storage stability by incorporating the crystalline polyester in the amorphous polyester (Patent Document 1).
However, although this method gives good results for low temperature fixability and heat resistant storage stability, it has insufficient moisture and heat storage stability, and the toner durability is lowered, which limits the design of copiers and printers. There is. Furthermore, there is a problem that the cost as a toner is high.
In order to solve these problems, a technology is proposed in which a crystalline polyester resin is contained in a styrene-acrylic resin, which is relatively cheaper than polyester (Patent Document 2). By using a styrene-acrylic resin, the durability of the toner is improved, and good results are obtained in terms of moisture and heat storage stability. However, since the crystalline polyester and the styrene-acrylic resin have poor compatibility, sufficient low temperature fixability can not be obtained, and the gloss and charge stability of the printed image are also insufficient.

JP, 2006-091882, A Japanese Patent Application Laid-Open No. 2003-302791

An object of the present invention is to provide an inexpensive toner which can achieve both heat resistant storage stability, moisture and heat storage stability and low temperature fixability, and is excellent in toner durability, gloss and charge stability.

The inventors of the present invention arrived at the present invention as a result of intensive studies to develop a toner having both heat resistant storage stability, moisture resistant storage stability and low temperature fixability.
That is, the present invention is a method for producing a toner containing a colorant and a binder resin (TB), wherein the binder resin (TB) comprises a crystalline resin (A) and a styrenic monomer (b1) as a component. And 50 to 95% by weight of a styrene-acrylic resin (B), the endothermic peak top temperature Ta (.degree. C.) of the crystalline resin (A) is in the range of 50 to 100.degree . A method for producing a toner characterized by satisfying the relational expressions (1) and (2), which comprises the step of mixing a crystalline resin (A) and a styrene-acrylic resin (B) The temperature of the manufacturing process after the process is maintained at 25 to 40 ° C. , which is a method of manufacturing a toner.

Q ₁ / (Q ₀ × q / 100) ≧ 0.8 (1)
[Wherein, Q ₀ is a crystalline resin (in the first temperature rising process detected by differential scanning calorimetry when the temperature of the crystalline resin (A) is raised from 0 ° C. to 150 ° C. at 10 ° C./minute The endothermic energy [J / g] based on the endothermic peak of A) is represented. Q ₁ is an endothermic amount based on the endothermic peak derived from the crystalline resin (A) in the first temperature rising process which is detected when the temperature of the toner is raised from 0 ° C. to 150 ° C. at 10 ° C./min. Represents / g]. q represents the content (% by weight) of the crystalline resin (A) to the toner. ]

Q ₂ / Q ₁ ≦ 0.50 (2)
[Wherein, Q ₂ is measured at a temperature of 10 ° C./min from 150 ° C. to 0 ° C. after measuring Q _{1 in the first} temperature raising process of the toner, and then again 10 ° C./min from 0 ° C. to 150 ° C. The endothermic amount [J / g] based on the endothermic peak derived from the crystalline resin (A) in the second temperature raising process of raising the temperature by ° C. is shown. ]

  The toner of the present invention has both heat resistance storage stability, humidity resistance storage stability and low temperature fixing properties, and is excellent in toner durability, glossiness, charging stability and low price.

It is a flowchart of the experimental apparatus used for manufacture of the toner using the carbon dioxide of a liquid state or a supercritical state in this invention.

The toner of the present invention will be described below.
The toner of the present invention is a toner containing a coloring agent and a binder resin (TB), and the binder resin (TB) comprises a crystalline resin (A) and a styrenic monomer (b1) as a component. A styrene-acrylic resin (B) containing 50 to 95% by weight is contained. Furthermore, the following relational expressions (1) and (2) are satisfied.

Q ₁ / (Q ₀ × q / 100) ≧ 0.8 (1)

[In the relational expression (1), Q ₀ is in the first temperature rising process detected by differential scanning calorimetry when the temperature of the crystalline resin (A) is raised from 0 ° C. to 150 ° C. at 10 ° C./min. The endothermic amount [J / g] based on the endothermic peak of crystalline resin (A) is represented. Q ₁ is an endothermic amount based on the endothermic peak derived from the crystalline resin (A) in the first temperature rising process which is detected when the temperature of the toner is raised from 0 ° C. to 150 ° C. at 10 ° C./min. Represents / g]. q represents the content (% by weight) of the crystalline resin (A) to the toner. ]

Q ₂ / Q ₁ ≦ 0.50 (2)

In [equation (2), Q ₂ is, after measuring the Q ₁ in the first heating process of the toner, after cooling per minute 10 ° C. to 0 ℃ from 0.99 ° C., to 0.99 ° C. from 0 ℃ The endothermic amount [J / g] based on the endothermic peak derived from the crystalline resin (A) in the second temperature raising process of raising the temperature again at 10 ° C. per minute is shown. ]

When the crystalline resin (A) and the styrene-acrylic resin (B) are contained as the binder resin (TB), the toner is melted at the time of heat fixation, and (A) and (B) become compatible. As a result, (B) is plasticized, the glass transition temperature of the binder resin is lowered, and the melt viscosity is also lower than that of the styrene-acrylic resin (B) alone at the same temperature.
As a result, the melt viscosity as a toner also decreases, and therefore, it is possible to perform fixing at a lower temperature at the time of fixing.

The decrease in the melt viscosity of (B) due to the compatibility of (A) and (B) depends on the amount of compatibility of (A) with (B), and the larger the amount of compatibility, the melting is The viscosity can be reduced. Ideally, the total amount of (A) in the toner is preferably compatible with (B) at the time of fixing. Therefore, from the viewpoint of low temperature fixability, a combination of resins in which (A) and (B) are easily compatible is preferable.

On the other hand, in the toner before heating and melting, when (A) is compatible with (B), the glass transition temperature of (B) is lowered, so that the heat resistant storage stability of the toner is lowered.
Therefore, it is preferable that (A) and (B) in the toner be present in a phase separated state without being compatible with each other even before the heating and melting, even if they are a combination of resins compatible when heating and melting.

Specifically, as described above, in the toner of the present invention, (A) and (B), which are compatible when heated and melted, are present in a phase separated state in the toner before heated and melted, and thus the level is high. It is compatible with the contradictory performance of heat-resistant storage stability and low-temperature fixability. The present invention has been completed by realizing such a form.

By realizing such a form, the toner durability, the gloss and the charging stability are also improved.
Specifically, the compatibility of the toner before heating and melting with (A) and (B) is suppressed to suppress the softening of the toner and the nonuniformity of the toner composition, whereby the durability and the charging stability of the toner are respectively suppressed. Improve. Further, at the time of fixing, the melt viscosity of the toner can be lowered, so that an image with high gloss of the printed image can be realized.

The toner of the present invention can achieve both of the contradictory performances of the heat resistant storage stability at a high level and the low temperature fixability by satisfying the relational expression (1) and the relational expression (2).

Q ₁ / (Q ₀ × q / 100) ≧ 0.8 (1)
Q ₂ / Q ₁ ≦ 0.50 (2)

In the relational expression (1), Q ₀ is a crystal in the first temperature rising process detected by differential scanning calorimetry when the temperature of the crystalline resin (A) is increased from 0 ° C. to 150 ° C. at 10 ° C./min. Endothermic [J / g] based on the endothermic peak of the water-soluble resin (A).
Q ₁ is an endothermic amount based on the endothermic peak derived from the crystalline resin (A) in the first temperature rising process which is detected when the temperature of the toner is raised from 0 ° C. to 150 ° C. at 10 ° C./min. Represents / g].
q represents the content (% by weight) of the crystalline resin (A) to the toner.

Moreover, in relation (2), Q ₂ is, after measuring the Q ₁ in the first heating process of the toner, after cooling per minute 10 ° C. to 0 ℃ from 0.99 ° C., from 0 ℃ 0.99 The endothermic amount [J / g] based on the endothermic peak derived from the crystalline resin (A) in the second temperature raising process of raising the temperature again at 10 ° C. per minute to ° C. is shown.

That is, when the toner of the present invention is repeatedly heated and cooled and heated under the above conditions, an endothermic peak derived from the crystalline resin (A) is shown as measured by a differential scanning calorimeter (DSC).
Therefore, the heat absorption amount Q ₁ based on the endothermic peak in the _first temperature rising process and the heat absorption amount Q ₂ based on the endothermic peak in the second temperature rising process are set.

As temperature raising / cooling conditions at the time of measurement by DSC, the temperature is raised to 150 ° C. under the conditions of 0 ° C. to 10 ° C./minute (first temperature raising process). Subsequently, it cools to 0 degreeC on 10 degreeC / min conditions (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 endothermic peak areas corresponding to Q ₁ and Q ₂ 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 fraction not derived from the crystalline resin (A) is subtracted. Among the raw materials to be further blended in the toner binder, crystalline raw materials such as wax may exhibit an endothermic peak. In such a case, from the value obtained by summing the endothermic peak areas, the heat of fusion (Q _w0 ) of the crystalline substance alone not derived from the crystalline resin (A) and the substance not derived from the crystalline resin (A) in the toner The value (Q _w ) calculated by the following equation from the content (q _w ) of can be calculated by subtracting the heat of fusion of a substance not derived from the crystalline resin (A).

Q _w = Q _w0 × q _w / 100

The heat of fusion (Q _w0 ) of the substance not derived from the crystalline resin (A) and the content (q _w ) of the substance not derived from the crystalline resin (A) in the toner are, for example, raw materials of the manufactured toner It may be calculated from the analysis result and its composition ratio, or if it is unknown, it is calculated after the toner composition ratio is clarified by a method of analyzing this constituent material by solvent extraction of toner etc. You may.

The value of the left side of the relational expression (1) is usually 0.8 or more, preferably 0.85 or more, more preferably 0. 5 or more from the viewpoint of heat resistance storage stability of toner, humidity and heat storage stability, toner durability and charging stability. 90 or more.

The value of the left side of the relational expression (2) is usually 0.50 or less, preferably 0.3 or less, more preferably 0.2 or less, particularly preferably 0.1 or less, from the viewpoint of low temperature fixability and gloss of the toner preferably is that Q ₂ is not detected.

The binder resin (TB) of the present invention contains a crystalline resin (A) and a styrene-acrylic resin (B) containing 50 to 95% by weight of a styrenic monomer (b1) as a component.

The "crystalline" in the present invention refers to a resin having a clear endothermic peak in the first temperature raising process of the above-mentioned DSC measurement.
The endothermic peak top temperature Ta (° C.) derived from the crystalline resin (A) is preferably 50 to 100 ° C., more preferably 53 to 90 ° C., particularly preferably 55 to 85 ° C.
From the viewpoints of the heat resistant storage stability of the toner, the humidity and heat storage stability, the toner durability, and the charging stability, Ta is preferably 50 or more, and preferably 100 or less from the viewpoint of low temperature fixing property and gloss.
In addition, peak top temperature refers to the temperature of the deepest part of the recessed part of the endothermic peak of a DSC chart.
And when there exist two or more endothermic peaks derived from crystalline resin (A), at least one should just exist in this range.

The type of the crystalline resin (A) of the present invention is not particularly limited as long as it is a resin having a clear endothermic peak in the first temperature raising process of the above-described DSC measurement. (A1), crystalline polyurethane resin (A2), crystalline polyurea resin (A3), crystalline polyamide resin (A4), crystalline polyvinyl resin (A5), crystalline epoxy resin (A6), crystalline polyether resin ( And compounds such as A7).

Examples of the crystalline polyester resin (A1) include polyester resins synthesized from a diol component (x) and a dicarboxylic acid component (y), and a trivalent or higher alcohol component or a trivalent or higher polycarboxylic acid as necessary. An acid component may be used in combination.

Aliphatic diol, alkylene ether glycol having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.) as the diol of the diol component (x); carbon number 4-36 alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); alkylene oxides of the above-mentioned alicyclic diols (hereinafter, "alkylene oxide" is abbreviated as AO) [ethylene oxide (hereinafter , "Ethylene oxide" is abbreviated as EO, propylene oxide (hereinafter, "propylene oxide" is abbreviated as PO), butylene oxide (hereinafter, "butylene oxide" is abbreviated as BO), etc. Adducts (mol additions 1 to 30); AO (EO, PO, BO, etc.) adducts of bisphenols (bisphenol A, bisphenol F, bisphenol S etc.) adducts (mol additions 2 to 30); polylactone diol (poly) ε-caprolactone diol and the like); polybutadiene diol and the like. Two or more of these may be used in combination.

Among these diols, aliphatic diols are preferred from the viewpoint of crystallinity. The carbon number is in the range of 2 to 36, preferably in the range of 2 to 20. Furthermore, from the same viewpoint, linear aliphatic diols are preferable to branched aliphatic diols.

Examples of linear aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1 , 18-octadecanediol, 1,20-eicosanediol and the like. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol 1,12-dodecanediol are preferable.

From the viewpoint of crystallinity, the content of the linear aliphatic diol is preferably 80 mol% or more, more preferably 90 mol% or more of the diol component to be used.

  The trivalent to octavalent or higher polyol optionally used in combination with the diol component (x) is a trivalent to octavalent or higher polyhydric aliphatic alcohol having 3 to 36 carbon atoms (alkane polyol and its molecule or Intermolecular dehydrated products such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerins; saccharides and their derivatives such as sucrose and methylglucoside; trisphenols (such as trisphenol PA) AO adducts of (2 to 30 moles of addition); AO adducts of novolak resin (phenol novolac, cresol novolac, etc.) (2 to 30 moles of addition); acrylic polyol [hydroxyethyl (meth) acrylate and other vinyl compounds Copolymerization of monomers Etc.]; and the like.

  Among these, trihydric to trihydric or higher polyhydric aliphatic alcohols and AO adducts of novolak resins are preferable, and further preferable are AO adducts of novolac resins.

The crystalline polyester resin (A1) is selected from the group consisting of a carboxylic acid (salt) group, a sulfonic acid (salt) group, a sulfamic acid (salt) group and a phosphoric acid (salt) group in addition to the diol (x). It is also possible to use geor which has at least one kind of group as a constitutional unit.
In addition, the expression of "acid (salt)" in the present invention means "acid or acid salt".

Examples of diols 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- [3 Examples include bis (2-hydroxyethyl) amino] propanoic acid (salt) and the like.

Examples of diols 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), 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) and the like.
As salts constituting acid salts, ammonium salts, amine salts (methylamine salts, dimethylamine salts, trimethylamine salts, ethylamine salts, ethylamine salts, diethylamine salts, triethylamine salts, propylamine salts, dipropylamine salts, tripropylamine salts, butylamine Salts, dibutylamine salts, tributylamine salts, monoethanolamine salts, diethanolamine salts, triethanolamine salts, N-methylethanolamine salts, N-ethylethanolamine salts, N, N-dimethylethanolamine salts, N, N- Diethylethanolamine salt, hydroxylamine salt, N, N-diethylhydroxylamine salt and morpholine salt, etc., quaternary ammonium salt [tetramethylammonium salt, tetraethylammonium salt and trimethyl (2-hydroxyethyl) Ammonium salts, alkali metal salts (sodium salts and potassium salts, etc.).

Among the diols having functional groups, diols having a carboxylic acid (salt) group and diols having a sulfonic acid (salt) group (x ') are preferable from the viewpoint of chargeability of the toner and heat resistant storage stability.

As dicarboxylic acid of dicarboxylic acid component (y) which constitutes crystalline polyester resin (A1), alkanedicarboxylic acid (succinic acid, adipic acid, sebacic acid, azeline) of carbon number (including carbon of carbonyl group) 2-50 Acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc .; alkene dicarboxylic acid having 4 to 50 carbon atoms (dodecenylsuccinic acid, pentadecenylsuccinic acid, alkenylsuccinic acid such as octadecenylsuccinic acid, etc., maleic acid, Fumaric acid, citraconic acid, etc.); Alicyclic dicarboxylic acid having 6 to 40 carbon atoms (dimer acid (dimerized linoleic acid), etc.), aromatic dicarboxylic acid having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid , T-Butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyl Etc. dicarboxylic acid). Two or more of these may be used in combination.

Among these dicarboxylic acids, it is preferable from the viewpoint of crystallinity to use aliphatic dicarboxylic acids of alkane dicarboxylic acids and alkene dicarboxylic acids, and linear type dicarboxylic acids are particularly preferable.
Moreover, what co-polymerized aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, t-butyl isophthalic acid, and these lower alkyl esters) with aliphatic dicarboxylic acid is similarly preferable. As a copolymerization amount of aromatic dicarboxylic acid, 20 mol% or less is preferable.

  In addition, as a dicarboxylic acid or a polycarboxylic acid having 3 to 6 or more valences, acid anhydrides of the above or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) are used. It is also good.

The crystalline polyurethane (A2) usable as the crystalline resin (A) of the present invention is not particularly limited in its chemical structure as long as it is compatible with the styrene-acrylic resin (B).

As crystalline polyurethane (A2), what has said crystalline polyester (A1) and diisocyanate (v) as a structural unit, said crystalline polyester (A1), said diol component (x), and diisocyanate (v) And the like.

As diisocyanate (v), aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in NCO group. The same applies to the following.), Aliphatic diisocyanate having 2 to 18 carbon atoms, modified products of these diisocyanates (urethane group, A carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a uretimine group, an isocyanurate group, a modified product containing an oxazolidone group, etc.) and mixtures of two or more of these, etc. may be mentioned.

As aromatic diisocyanates, 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, m- or p-. Xylylene diisocyanate (XDI), α, α, α ', α'-tetramethyl xylylene diisocyanate (TMXDI), 2,4'- or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI {crude diaminophenylmethane [A condensation product of formaldehyde and an aromatic amine (aniline) or a mixture thereof, a mixture thereof, and the like can be mentioned.

Examples of aliphatic diisocyanates include linear aliphatic diisocyanates and cyclic aliphatic diisocyanates.
As linear aliphatic diisocyanates, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate And bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and mixtures thereof.

As cyclic aliphatic diisocyanates, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methyl cyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate and mixtures thereof, and the like.

As modified products of diisocyanate, modified products containing a urethane group, a carbodiimide group, an allophanate group, a urea group, a biuret group, a uretdione group, a uretimine group, an isocyanurate group and / or an oxazolidone group are used. Urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), urethane-modified TDI and mixtures thereof [eg, mixture of modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)], etc. may be mentioned.

Among these diisocyanates (v), 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. It is.

The crystalline polyurea (A3) is not particularly limited in its chemical structure as long as it is compatible with the binder resin (B).

Examples of the crystalline polyurea (A3) include those having the above-mentioned crystalline polyester resin (A1), diamine (z) and diisocyanate (v) as structural units.

As a diamine (z), a C2-C18 aliphatic diamine, a C6-C20 aromatic diamine, etc. are mentioned.
Examples of aliphatic diamines having 2 to 18 carbon atoms include linear aliphatic diamines and cyclic aliphatic diamines.

Examples of the chain aliphatic diamine include alkylene diamines having 2 to 12 carbon atoms (ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and polyalkylenes (2 to 6 carbon atoms) polyamines [diethylene triamine, imino Bispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and the like] and the like.
Examples of cyclic aliphatic polyamines include alicyclic diamines having 4 to 15 carbon atoms {1,3-diaminocyclohexane, isophoronediamine, mensenediamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline) and 3 , 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane etc.} and heterocyclic diamines having 4 to 15 carbon atoms [piperazine, N-aminoethyl piperazine, 1,4-diaminoethyl piperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine and the like] and the like.

As the aromatic diamine having 6 to 20 carbon atoms, aromatic diamine, 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), etc. Can be mentioned.

As the aromatic diamine, 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- or 4,4′-diphenylmethanediamine, diaminodiphenyl sulfone, benzidine, thiodianiline, bis (3,4 And -diaminophenyl) sulfone, 2, 6-diaminopyridine, m-aminobenzylamine, naphthalenediamine, and mixtures thereof.

As an aromatic diamine which has an alkyl group (C1-C4 alkyl groups such as methyl group, ethyl group, n- or isopropyl group and butyl group), 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 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-triethene -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 It can be mentioned.

The crystalline polyamide (A4) is not particularly limited in its chemical structure as long as it is compatible with the binder resin (B).

As crystalline polyamide (A4), what makes said crystalline polyester (A1), said diamine (z), and dicarboxylic acid (y) a structural unit etc. is mentioned.

The crystalline polyvinyl resin (A5) is not particularly limited in its chemical structure as long as it is compatible with the binder resin (B).

As crystalline polyvinyl resin (A5), the polymer which homopolymerized or copolymerized the ester which has a polymerizable double bond is mentioned.

Examples of the ester having a polymerizable double bond include vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth ) Acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxy acrylate, alkyl (meth) acrylate having 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 ) Acrylates and eicosyl (meth) acrylates etc.], dialkyl fumarate (2 alkyl groups are linear, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleates (2 The alkyl group in the group is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes (diaryloxyethane, triaryloxyethane, tetraaryloxyethane) , Etc., monomers having a polyalkylene glycol chain and a polymerizable double bond [polyethylene glycol [Mn = 300] mono (meth) acrylate, polypropylene, etc. Glycol (Mn = 500) monoacrylate, methyl alcohol EO 10 molar adduct (meth) acrylate and lau Ryl alcohol EO 30 moles adduct (meth) acrylate etc., poly (meth) acrylates [poly (meth) acrylates of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate etc.] and the like.

The crystalline polyvinyl resin (A5) is, in addition to an ester having a polymerizable double bond, a hydrocarbon monomer having a polymerizable double bond, a monomer having a carboxyl group and a polymerizable double bond, and salts thereof A monomer having a sulfo group and a polymerizable double bond and a salt thereof, a monomer having a phosphono group and a polymerizable double bond and a salt thereof, a monomer having a hydroxyl group and a polymerizable double bond, Nitrogen-containing monomers having a polymerizable double bond, monomers having 6 to 18 carbon atoms having an epoxy group and a polymerizable double bond, and monomers having 2 to 16 carbon atoms having a halogen element and a polymerizable double bond A monomer, an ether having a polymerizable double bond, a ketone having a polymerizable double bond, a sulfur-containing compound having a polymerizable double bond, and the like can be used as the constituent monomer.

  As the crystalline epoxy resin (A6), a ring-opening polymer of polyepoxide, a polyadduct of polyepoxide and an active hydrogen-containing compound [water, the above diol (x), dicarboxylic acid (y), diamine (z), etc.], etc. Can be mentioned.

  The polyepoxide is not particularly limited as long as it has two or more epoxy groups in the molecule. Among the polyepoxides, preferred are those having 2 to 6 epoxy groups in the molecule from the viewpoint of the mechanical properties of the cured product. The epoxy equivalent (molecular weight per epoxy group) of the polyepoxide is preferably 65 to 1,000, more preferably 90 to 500. If the epoxy equivalent is 1,000 or less, the cross-linked structure becomes dense and physical properties such as water resistance, chemical resistance and mechanical strength of the cured product are improved, while one having an epoxy equivalent of less than 65 is synthesized It is difficult.

  Examples of polyepoxides include aromatic polyepoxy compounds, heterocyclic polyepoxy compounds, alicyclic polyepoxy compounds and aliphatic polyepoxy compounds.

Examples of the crystalline polyether resin (A7) include crystalline polyoxyalkylene polyols and the like.
The method for producing the crystalline polyoxyalkylene polyol is not particularly limited, and any known method may be used.

For example, a method of ring-opening polymerization of a chiral polyoxyalkylene polyol with a catalyst used in polymerization of ordinary polyoxyalkylene polyols (Journal of the American Chemical Society, 1956, 78, 18, p. 4787-4792); ring-opening polymerization of an inexpensive racemic polyoxyalkylene polyol using a sterically bulky complex chemical structure as a catalyst.

As a method of using a special complex, a method of using a compound in which a lanthanoid complex and an organic aluminum are brought into contact as a catalyst (described in JP-A-11-12353) or a reaction of bimetal-μ-oxo alkoxide and a hydroxyl compound in advance Methods (described in JP-A-2001-521957) and the like.

In addition, as a method of obtaining a polyoxyalkylene polyol having a very high isotacticity, a method using a salen complex as a catalyst (Journal of the American Chemical Society, 2005, Vol. 127, No. 33, pp. 11566-11567) Description etc. are mentioned.

For example, when a chiral polyoxyalkylene polyol is used and glycol or water is used as an initiator during ring-opening polymerization, a polyoxyalkylene glycol having 50% or more isotacticity having a hydroxyl group at the end is obtained. Be
The end of the polyoxyalkylene glycol having an isotacticity of 50% or more may be, for example, one modified to become a carboxyl group. When the isotacticity is 50% or more, the polyoxyalkylene polyol usually has crystallinity.
Examples of the glycol include the diol (x1) and the like, and examples of the carboxylic acid used for carboxy modification include the dicarboxylic acid (y2) and the like.

Among the crystalline resins (A), preferred from the viewpoint of low-temperature fixability are crystalline polyester resin (A1), crystalline polyurethane resin (A2), crystalline polyurea resin (A3) and crystalline polyamide resin (A4) And more preferably a crystalline resin having at least one functional group selected from the group consisting of an ester group, a urethane group, a urea group and an amide group, and particularly preferably a crystal having an ester group. Resin.

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 35,000, and particularly preferably 4,000 to 25,000. It is.
It is preferably 50,000 or less from the viewpoint of low temperature fixability, and 3,000 or more from the viewpoint of heat resistant storage stability.

The molecular weight distribution and Mw of the crystalline resin (A) and the styrene-acrylic resin (B) in the present invention can be measured under the following conditions using gel permeation chromatography (GPC).
Device (example): "HLC-8120" (manufactured by Tosoh Corporation)
Column (example): "TSK GEL GMH6" (manufactured by Tosoh Corp.) 2 Measurement temperature: 40 ° C
Sample solution: 0.25% by weight of tetrahydrofuran solution (Insoluble content filtered off with a glass filter)
Solution injection volume: 100 μl
Detector: Refractive index detector Reference substance: 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 Corp.)

As the styrene-based monomer (b1), aromatic hydrocarbon having a polymerizable double bond: styrene; hydrocarbyl (alkyl having 1 to 30 carbon atoms, cycloalkyl, aralkyl and / or alkenyl) substitution product of styrene (for example, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene etc. And vinyl naphthalene and the like. Among these, from the viewpoint of compatibility with the crystalline resin (A), styrene, a hydrocarbyl-substituted product of styrene, and a combination thereof are preferable.

As an acrylic monomer (b2), alkyl groups such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate and the like Alkyl esters having 1 to 18 carbon atoms; alkyls having 1 to 18 carbons, such as hydroxyl ethyl (meth) acrylate; hydroxyl group-containing (meth) acrylates; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) Amino group-containing (meth) acrylates having 1 to 18 carbon atoms of alkyl group such as acrylates; acrylonitrile, methacrylonitrile, nitrile group-containing (meth) acrylic compounds having methyl group of 1 to 18 carbon atoms and methacrylonitrile; It can be mentioned, such as acrylic acid.
Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid, and mixtures of two or more of these are preferable.

The styrene-acrylic resin (B) contains 50 to 95% by weight of a styrene-based monomer (b1) as a component. If it is less than 50%, the compatibility with the crystalline resin (A) is poor, and the low temperature fixability is not sufficiently improved.

The styrene-acrylic resin (B) of the present invention comprises a monomer (b3) containing a carboxyl group and a monomer containing a sulfonic acid group in addition to the styrenic monomer (b1) and the acrylic monomer (b2) as constituent units. It is preferable to use b4), and (b3) and (b4) in combination. The styrene-acrylic resin having a carboxyl group-containing monomer (b3) or a sulfonic acid group-containing monomer (b4) as a structural unit has an acid value because it contains an acid group.

Styrene-acrylic resin (B) having a styrenic monomer (b1), an acrylic monomer (b2), a carboxyl group-containing monomer (b3) and / or a sulfonic acid group-containing monomer (b4) as a constitutional unit The acid value of) is preferably 5.0 to 40.0 mg KOH / g, more preferably 8.0 to 30.0 mg KOH / g, and particularly preferably 10.0 to 20.0 mg KOH / g.
It is mgKOH / g.
5.0 mg KOH / g or more is preferable from the viewpoint of low temperature fixability, and 40, 0 mg KOH / g or less is preferable from the viewpoint of heat resistant storage stability.

As a monomer (b3) containing a carboxyl group, unsaturated monocarboxylic acid (b31), unsaturated dicarboxylic acid (b31), etc. are mentioned.
As unsaturated monocarboxylic acid (b31), the notation of (meth) acrylic acid [“(meth) acrylic” means acrylic or methacrylic. ], Crotonic acid, isocrotonic acid and cinnamic acid.
Moreover, as unsaturated dicarboxylic acid (b31), maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and the like can be mentioned.
Furthermore, acid anhydrides of unsaturated dicarboxylic acids (for example, acid anhydrides such as maleic acid, fumaric acid and itaconic acid) and monoalkyl (C1-C10) esters (for example, monomethyl esters of maleic acid and monodecyl esters of maleic acid) Fumaric acid monoethyl ester, itaconic acid monobutyl ester, citraconic acid monodecyl ester, etc. can also be used.

Examples of the monomer (b4) containing a sulfonic acid group include alkene sulfonic acid having 2 to 14 carbon atoms, a styrene sulfonic acid, sulfo (hydroxy) alkyl (meth) acrylate having 5 to 18 carbon atoms, and 5 to 5 carbon atoms. And 18 sulfo (hydroxy) alkyl (meth) acrylamides, alkyl (3 to 18 carbon atoms) allyl sulfosuccinic acid and the like.

Styrene-acrylic resin (B) having a styrenic monomer (b1), an acrylic monomer (b2), a carboxyl group-containing monomer (b3) and / or a sulfonic acid group-containing monomer (b4) as a constitutional unit And the crystalline resin (A), the toner of the present invention preferably satisfies the following relational expression (3).

20 ≦ X ≦ 55 (3)
X = 0.61 x AV-0.64 x (| SP _B- SP _A- 0.5 |)-0.35 x (| E _B- E _A + 20 |)-0.50 x Mw / 10,000 + 18 .0

In formula, AV represents the acid value (mgKOH / g) of styrene-acrylic resin (B).
Moreover, SP _B is a styrene - solubility parameter of the acrylic resin (B) (SP value), SP _A represents a solubility parameter of the crystalline resin (A).
Further, E _B represents the ester group concentration (% by weight) of the styrene-acrylic resin (B), and E _A represents the ester group concentration (% by weight) of the crystalline resin (A).

In addition, the solubility parameter (SP value) in this invention is a method by Fedors [Polym. Eng. Sci. 14 (2) 152, (1974)].

The ester group concentration of the crystalline resin (A) and the styrene-acrylic resin (B) can be calculated from the number of ester groups [-C (= O) O-] in (A) or (B). Specifically, it is a value represented by the following formula (5).
Ester group concentration (unit:%) = [(N × 44) / number average molecular weight] × 100 (5)
Here, N is the average of the number of ester groups per molecule of (A) or (B), and 44 is the formula weight of the ester group [-C (= O) O-].
In calculating the actual ester group concentration, the method of calculating by calculating the monomer composition and the number of ester groups constituting (A) by nuclear magnetic resonance spectrum (NMR) etc., and the quantitative ratio of the raw materials used for the production of (A) There is a method of calculating by calculating the number of ester groups from

  The styrene-acrylic resin (B) has one or more molecular weight peaks in the molecular weight distribution obtained by GPC, in which case it has at least one peak in the region of 3,000 to 60,000. Is preferred.

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

The toner preferably satisfies the following relational expression (4).
10 ≦ Tg ₁ −Tg ₂ ≦ 30 (4)

In the formula (4), Tg ₁ represents a glass transition temperature (° C.) in the first temperature rising process which is detected by DSC when the temperature of the toner is raised from 10 ° C. to 150 ° C. at 10 ° C./min.
Further, Tg ₂ is measured at a temperature of 10 ° C./min from 150 ° C. to 0 ° C. after measuring Tg _{1 in the first} temperature raising process of the toner, and then raised again at 10 ° C./min from 0 ° C. to 150 ° C. It represents the glass transition temperature (° C.) in the second temperature raising process detected when the temperature is raised.

When the value of Tg ₁ -Tg ₂ is less than 10 ° C., the low temperature fixability of the toner is insufficient, and when it is more than 30 ° C., the phase separation state can not be maintained at the time of toner formation.

The content of the crystalline resin (A) in the toner is preferably 5 to 30% by weight based on the total weight of the crystalline resin (A) and the styrene-acrylic resin (B).
5% or more is preferable from the viewpoint of low-temperature fixability, and 30% or less is preferable from the viewpoint of heat resistant storage stability.

The styrene-acrylic resin (B) is prepared by solution polymerization, bulk polymerization, suspension polymerization and emulsification using the above monomers (b1) and (b2) and optionally (b3) and (b4) and a radical polymerization initiator. It can be obtained by a known polymerization method such as polymerization.
Among these polymerization methods, preferred from the viewpoint of molecular weight control are solution polymerization, suspension polymerization, bulk polymerization and combinations thereof.

As a radical polymerization initiator, an azo polymerization initiator (for example, azobisisobutyronitrile, azobisvaleronitrile, and azobiscyanovaleric acid), an organic peroxide polymerization initiator [for example, benzoyl peroxide, di-t -Butyl peroxide, t-butylperoxybenzoate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane] and the like.
Among 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, and particularly preferably 0.05 to 6% by weight, based on the total amount of monomers.

As an organic solvent which can be used for the synthesis of the styrene-acrylic resin (B) of the present invention, aromatic hydrocarbon solvents (toluene, xylene, ethylbenzene and tetralin etc.); aliphatic hydrocarbon solvents (n-hexane, n-heptane, n-decane, mineral spirits and cyclohexane etc .; halogen solvents (methyl chloride, methyl bromide, methyl iodide, methylene dichloride, carbon tetrachloride, trichloroethylene and perchlorethylene 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 etc; ether solvents (diethyl ether, tetrahydrofuran, dioxa , Dioxolane, 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 etc .; alcohol solvents (methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, benzyl alcohol, 2,2,3,3-tetrafluoropropanol and tri) Fluoroethanol etc .; amide solvents (such as dimethylformamide and dimethylacetamide); sulfoxide solvents (di Sulfoxide, etc.); heterocyclic compounds based solvents (N- methylpyrrolidone) and include mixed solvent of two or more thereof.
Among them, aromatic hydrocarbon solvents are preferable from the viewpoint of operability, more preferably xylene, toluene and ethylbenzene.

When suspension polymerization is performed, polymerization can be performed in water using an inorganic acid salt dispersant (such as calcium carbonate and calcium phosphate), an organic dispersant (such as polyvinyl alcohol and methyl cellulose), or the like.

The method for producing the toner is not particularly limited, and may be obtained by a known melt suspension method, polymerization method or the like, or may be produced by a method of dispersing in carbon dioxide in a supercritical state. .
At that time, the step of mixing the crystalline resin (A) and the monomer (b) constituting the styrene-acrylic resin (B) and / or the styrene-acrylic resin (B) is included, and this mixing step It is preferable to maintain the temperature of the subsequent production steps at or below the melting point Tm _A of the crystalline resin (A).
By performing temperature control after this mixing step, it is possible to cause (A) and (B) to exist in the toner in a phase separated state.

For example, in the case of obtaining the toner by the melt suspension method, the components constituting the toner other than the fluidizing agent such as (A), (B), the coloring agent, and the releasing agent are dissolved or dispersed in an organic solvent After the phase formation, fine particle formation is carried out by mixing this oil phase with an aqueous phase containing a surfactant, further removing the organic solvent from the mixture of the oil phase and the water phase, and then separating the toner particles, After classification, the fluidizing agent can be finally mixed and manufactured.

When the melt suspension method is carried out in the present invention, the crystalline resin (A) is in the state of being dispersed in an organic solvent, and the form thereof is realized, for example, as in the following series of steps.
The crystalline resin (A) and ethyl acetate are charged into a reaction vessel equipped with a stirring device, a heating and cooling device, a condenser and a thermometer, and the mixture is heated and dissolved under stirring. After cooling, the crystalline resin (A) is crystallized in the form of fine particles, and this is obtained by wet pulverization using, for example, a pulverizer such as an ultravisco mill.

Since (A) is converted to a solid as toner, it is preferable that the toner be incompatible with (B).

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

The crystalline resin (A) of the present invention is not limited to the introduction to the toner as the above-mentioned crystalline resin dispersion, but may be carried out by, for example, precipitating (A) in the molten state in the toner. It is.
For example, also in the method of carrying out the polymerization reaction in a state in which (A) is melted in the monomers (b1) to (b4) constituting the styrene-acrylic resin (B) as in the polymerization method, the polymerization reaction temperature is By maintaining the temperature below the melting point Tm _{A of} (A), (A) is precipitated as the polymerization proceeds, and the same temperature control is performed for the steps after the polymerization to produce a toner in a phase separated state. Can.

As a method of controlling the particle diameter of the toner, in the emulsion phase inversion method, the particle diameter can be controlled by a known method such as adding water at the time of phase inversion, using surfactant in combination, or stirring at phase inversion. .

The toner of the present invention contains a colorant, and as this colorant, it is preferable to contain 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 dyes, pigments and the like used as colorants for toner can be used.
Specifically, carbon black, iron black, sudan black SM, fast yellow G, benzidine yellow, solvent yellow (21, 77 and 114 etc.), pigment yellow (12, 14, 17 and 83 etc.), indofirst orange, Irgacin red, paranito aniline 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 and 15.3 etc.), pigment blue, brilliant green, phthalocyanine green, oil yellow GG, Kayase YG, o Tetrazole brown B and oil pink OP, and the like.
If necessary, magnetic powders (powders of ferromagnetic metals such as iron, cobalt and nickel, and compounds such as magnetite, hematite and ferrite) can be contained as well as the function 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 may contain a release agent, a charge control agent, a fluidizing agent, and the like in addition to the colorant.
Examples of mold release agents include natural waxes (such as beeswax, carnauba wax and montan wax), petroleum waxes (such as paraffin wax, microcrystalline wax and petrolatum), synthetic waxes (such as polyethylene wax, polypropylene wax, oxidized polyethylene wax and oxidized polypropylene) Waxes, etc., synthetic ester waxes (fatty acid esters synthesized from fatty acids having 10 to 30 carbon atoms and alcohols having 10 to 30 carbon atoms, etc.), and the like, and one type selected from the group consisting of these releasing 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., 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 fixability and gloss are 3 to 20 mm ² / s, more preferably 4~19mm ² / s, particularly preferably 5~18mm ² / s is there.

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 10% by weight, based on the weight of the toner.

As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, polymers containing quaternary ammonium bases, metal-containing azo dyes, copper phthalocyanine dyes And salicylic acid metal salts, boron complexes of benzyl acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, metal complexes of alkyl derivatives of salicylic acid, 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 7.5% by weight, based on the weight of the toner.

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

  From the viewpoint of heat resistant storage stability, durability and charge stability, it is preferable to use two or more types of fluidizing agents having different volume average particle sizes of primary particles in combination, in which case the volume average particle size of each primary particle is It is more preferable to contain the fluidizing agent 1 of 5 nm or more and less than 30 nm and the fluidizing agent 2 of 30 nm or more and 200 nm or less in volume average particle diameter of the primary particles in combination. Particularly preferred is a combination of a fluidizing agent 1 having a primary particle volume average particle size of 5 nm to less than 30 nm and a fluidizing agent 2 having a primary particle volume average particle size of 30 nm to 200 nm.

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 0.4 to 3% by weight based on the weight of the toner. It is .0% by weight.

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

The volume average particle size of the toner is preferably 1 to 15 μm, more preferably 2 to 10 μm, and particularly preferably 3 to 7 μm.
The volume average particle size of the toner can be measured using Coulter Counter "Multisizer III" (manufactured by Beckman Coulter, Inc.).

  EXAMPLES The present invention will be further described by way of examples, but the present invention is not limited thereto.

<Production Example 1> [Synthesis of Crystalline Resin (A-1)]
Ethylene glycol 284 parts by weight, adipic acid 650 parts by weight, titanium diisopropoxy bis triethanolaminate 2.5 parts by weight as a polymerization catalyst in a reaction vessel equipped with a stirrer, heating / cooling unit, thermometer, cooling pipe and nitrogen introduction pipe The reaction mixture is heated to 180 ° C., reacted at the same temperature for 4 hours while distilling off water generated under nitrogen stream, and then heated up to 220 ° C., then distilling off water generated under nitrogen stream While reacting for 4 hours. Furthermore, while distilling off water at a reduced pressure of 0.007 to 0.026 MPa at the same temperature, the reaction was performed until the acid value became 0.5 or less. Then, it cooled to 180 degreeC, 24.6 weight parts of trimellitic anhydrides were put into the reaction container, and it was made to react at 180 degreeC for 1 hour, and crystalline resin (A-1) was obtained.

<Production Example 2> [Synthesis of Crystalline Resin (A-2)]
A crystalline resin (A-2) was obtained in the same manner as in Production Example 1 except that ethylene glycol and adipic acid were replaced by 253 parts by weight of 1,4-butanediol and 617 parts by weight of dodecanedioic acid in Production Example 1 .

<Production Example 3> [Synthesis of Crystalline Resin (A-3)]
A crystalline resin (A-3) was obtained in the same manner as in Production Example 1 except that ethylene glycol and adipic acid were replaced by 408 parts by weight of 1,12-dodecanediol and 434 parts by weight of dodecanedioic acid in Production Example 1 .

<Production Example 4> [Synthesis of Crystalline Resin (A-4)]
A crystalline resin (A-4) was obtained in the same manner as in Production Example 1 except that ethylene glycol and adipic acid were replaced by 272 parts by weight of 1,6-hexanediol and 445 parts by weight of sebacic acid in Production Example 1.

The physical property values of the crystalline resins (A-1) to (A-4) are shown in Table 1.

<Production Example 5> [Synthesis of Styrene-Acrylic Resin (B-1)]
The autoclave was charged with 80 parts by weight of xylene, purged with nitrogen, and heated to 185 ° C. Then, at the same temperature, a mixture of 60 parts by weight of styrene, 15 parts by weight of n-butyl methacrylate, 23 parts by weight of methyl methacrylate, 2 parts by weight of acrylic acid, 0.23 parts by weight of di-t-butyl peroxide and 35 parts by weight of xylene The solution was dropped over 3 hours at the same temperature, and further kept at the same temperature for 1 hour to obtain a xylene solution of a styrene-acrylic resin (B-1). Next, the obtained xylene solution was heated to 170 ° C. while removing xylene at 1 kPa or less. It was confirmed by gas chromatography that the content of xylene in the resin was 1,000 ppm and the content of the monomer was 1,000 ppm or less to obtain a styrene-acrylic resin (B-1).

<Production Example 6> [Synthesis of Styrene-Acryl Resin (B-2)]
A styrene-acrylic resin (B was prepared in the same manner as in Production Example 5 except that 70 parts by weight of styrene, 15 parts by weight of n-butyl methacrylate, 13 parts by weight of methyl methacrylate and 2 parts by weight of acrylic acid were substituted. -2) was obtained.

<Production example 7> [Synthesis of styrene-acrylic resin (B-3)]
Production Example 5 except that 70 parts by weight of styrene, 15 parts by weight of n-butyl methacrylate, 13 parts by weight of methyl methacrylate, 2 parts by weight of acrylic acid, and 0.06 parts by weight of di-t-butyl peroxide Similar to 5, a styrene-acrylic resin (B-3) was obtained.

<Production Example 8> [Synthesis of Styrene-Acryl Resin (B-4)]
In the same manner as in Production Example 5 except that 50 parts by weight of styrene, 20 parts by weight of n-butyl methacrylate, 28 parts by weight of methyl methacrylate and 2 parts by weight of acrylic acid were substituted in Production Example 5, a styrene-acrylic resin (B -4) was obtained.

<Production Example 9> [Synthesis of Styrene-Acryl Resin (B-5)]
A styrene-acrylic resin (B-5) was obtained in the same manner as in Production Example 5 except that 90 parts by weight of styrene, 8 parts by weight of n-butyl methacrylate, and 2 parts by weight of acrylic acid were substituted.

<Production Example 10> [Synthesis of Styrene-Acryl Resin (B-6)]
A styrene-acrylic resin was prepared in the same manner as in Preparation Example 5 except that 70 parts by weight of styrene, 15 parts by weight of n-butyl methacrylate, 14.87 parts by weight of methyl methacrylate and 0.13 parts by weight of acrylic acid were substituted. System resin (B-6) was obtained.

<Production Example 11> [Synthesis of Styrene-Acryl Resin (B-7)]
A styrene-acrylic resin (B was prepared in the same manner as in Production Example 5 except that 70 parts by weight of styrene, 15 parts by weight of n-butyl methacrylate, 10 parts by weight of methyl methacrylate and 5 parts by weight of acrylic acid were substituted. -7) was obtained.

Production Example 12 Synthesis of Styrene-Acryl Resin (B-8)
A styrene-acrylic resin (B-8) was obtained in the same manner as in Production Example 5 except that 70 parts by weight of styrene, 15 parts by weight of n-butyl methacrylate, and 15 parts by weight of methyl methacrylate were substituted in Production Example 5. .

<Production example 13> [Synthesis of styrene-acrylic resin (B-9)]
A styrene-acrylic resin was prepared in the same manner as in Preparation Example 5 except that 70 parts by weight of styrene, 15 parts by weight of n-butyl methacrylate, 6.45 parts by weight of methyl methacrylate and 8.55 parts by weight of acrylic acid were substituted. System resin (B-9) was obtained.

<Comparative production example 1> [Synthesis of styrene-acrylic resin (B'-1)]
A styrene-acrylic resin (B was prepared in the same manner as in Production Example 5 except that 30 parts by weight of styrene, 20 parts by weight of n-butyl methacrylate, 48 parts by weight of methyl methacrylate and 2 parts by weight of acrylic acid were substituted. '-1) was obtained.

Physical properties of the styrene-acrylic resins (B-1) to (B-9) and (B'-1) are shown in Table 2.

<Production Examples 14 to 22 and Comparative Production Example 2>
50 parts by weight of each of the styrene-acrylic resins (B-1) to (B-9) and (B'-1) and 50 parts by weight of ethyl acetate are charged into a reaction vessel equipped with a stirrer and stirred. The resin was uniformly dissolved to obtain styrene-acrylic resin solutions (BS-1) to (BS-9) and (B'S-1).

<Production Example 23> [Production of Crystalline Resin Dispersion (AD-1)]
15 parts by weight of the resin (A-1) produced in Production Example 1 and 15 parts by weight of ethyl acetate were charged into a reaction vessel equipped with a stirrer, a heating / cooling device, a condenser and a thermometer, and the temperature was raised to 65 ° C. with stirring. The mixture is warmed, stirred at the same temperature for 30 minutes, cooled to 10 ° C. over 1 hour to crystallize the crystalline resin in the form of fine particles, and further wet-pulverized with an ultravisco mill (manufactured by IMEX) to obtain a crystalline resin dispersion (AD-1) was obtained. The volume average particle diameter of (AD-1) was 0.5 μm, and the solid content concentration was 50% by weight.

<Production Example 24> [Production of Crystalline Resin Dispersion (AD-2)]
A crystalline resin dispersion (AD-2) was obtained in the same manner as in Production Example 23 except that 15 parts by weight of the resin (A-1) was replaced with the resin (A-2) in Production Example 23. The volume average particle diameter of (AD-2) was 0.5 μm, and the solid concentration was 50% by weight.

<Production Example 25> [Production of Crystalline Resin Dispersion (AD-3)]
A crystalline resin dispersion (AD-3) was obtained in the same manner as in Production Example 23 except that 15 parts by weight of the resin (A-1) was replaced with the resin (A-3) in Production Example 23. The volume average particle diameter of (AD-3) was 0.5 μm, and the solid concentration was 50% by weight.

<Production Example 26> [Production of Crystalline Resin Dispersion (AD-4)]
A crystalline resin dispersion (AD-4) was obtained in the same manner as in Production Example 23 except that 15 parts by weight of the resin (A-1) was replaced with the resin (A-4) in Production Example 23. The volume average particle diameter of (AD-4) was 0.5 μm, and the solid concentration was 50% by weight.

<Production Example 27> [Production of Release Agent Dispersion]
Paraffin wax (petroleum wax) "HNP-9" [Tr: 73 ° C, kinematic viscosity at 100 ° C: 7 mm ² / s, Nippon Seiso Co., Ltd.] in a reaction vessel equipped with a stirrer, heating / cooling device, cooling pipe and thermometer 10 parts by weight, 15 parts by weight of ethyl acetate are added, the temperature is raised to 78 ° C. with stirring, the mixture is stirred for 30 minutes at the same temperature, and cooled to 30 ° C. over 1 hour to make paraffin wax into fine particles The resultant mixture was further crystallized with an ultravisco mill (manufactured by Imex Co., Ltd.) to obtain a release agent dispersion. The volume average particle diameter of the obtained release agent dispersion was 0.25 μm, and the solid content concentration was 50% by weight.

<Production Example 28> [Production of Resin Solution (C-1)]
90 parts by weight of (AD-1), 695 parts by weight of (BS-1), 27 parts by weight of a coloring agent, and 54 parts by weight of a releasing agent dispersion are added to a reaction vessel equipped with a stirrer and a thermometer and stirred The mixture was stirred at 40 ° C. for 60 minutes to obtain a resin solution (C-1).

Examples 1 to 10
Using the solutions (BS-1) to (BS-9), (B'S-1) and (AD-1) to (AD-4) obtained in Production Examples 14 to 26 and Comparative Production Example 2, The solid parts of the styrene-acrylic resins (B-1) to (B-9), the crystalline resins (A-1) to (A-4), and the releasing agent dispersion liquid are respectively the parts by weight shown in Table 3 The toner was weighed 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 is raised to 25 ° C., and 9.0 parts by weight of a crystalline resin dispersion, 2.7 parts by weight of a colorant, and a release agent dispersion 5, while stirring the TK autohomomixer at 10,000 rpm at the same temperature. 4 parts by weight and 69.5 parts by weight of a styrene-acrylic resin solution were added and stirred for 2 minutes. Next, this dispersion is transferred to a reaction vessel equipped with a stirrer, heating / cooling device, condenser and thermometer, and ethyl acetate is distilled off until the concentration becomes 0.5% by weight or less at 30 ° C. An aqueous resin dispersion was obtained. Then, it was washed, filtered off, 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 silica “Aerosil R 972” (volume average particle diameter of primary particles: 16 nm, manufactured by Nippon Aerosil) as fluidizing agent 1 are uniformly mixed, and the volume average is Toners (T-1) to (T-10) of the present invention having a particle diameter of 5 μm and comparative toners (T'-1) to (T'-3) were obtained.

Examples 11 to 13
49.5 parts by weight of the obtained toner particles, 0.25 parts by weight of silica "Aerosil R 972" (volume average particle diameter of primary particles: 16 nm, manufactured by Nippon Aerosil) as fluidizing agent 1, and silica "Aerosil R972" as fluidizing agent 2 Toner according to the present invention having a volume average particle diameter of 5 μm in the same manner as in Examples 1 to 10 except that 0.25 parts by weight of “RY50” (volume average particle diameter of primary particles: 40 nm, manufactured by Nippon Aerosil) is uniformly mixed. T-11) to (T-13) were obtained.

Example 14
In the experimental apparatus of FIG. 1, first, the valves V1 and V2 were closed, carbon dioxide (purity 99.99%) was introduced into the particle recovery tank T4 from a cylinder B2 using a pump P4, and adjusted to 14 MPa and 40 ° C. Further, the resin solution (C-1) was charged into the resin solution tank T1.
Next, liquid carbon dioxide was introduced into the dispersion tank T3 from a cylinder B1 of liquid carbon dioxide using a pump P3, and adjusted to a supercritical state (9 MPa, 40 ° C.).
Next, while stirring the inside of the dispersion tank T3 at 2,000 rpm, a mixed solution of the resin solution (C-1) was introduced into the dispersion tank T3 from the tank T1 using the pump P1. After the introduction, the pressure inside T3 was 14 MPa.

The weight ratio of the composition charged into the dispersion tank T3 is as follows.
Resin solution (C-1) 490 parts by weight Carbon dioxide 550 parts by weight

The weight of carbon dioxide introduced above is calculated from the temperature (40 ° C.) of carbon dioxide and the pressure (15 MPa) from the equation of state described in the following document from the pressure (15 MPa), and this is multiplied by the volume of dispersion tank T3. Calculated by the same rule (the same applies below).
Literature: Journal of Physical and Chemical Refarence data, vol. 25, P.I. 1509-1596

After the resin solution (C-1) was introduced, the mixture was stirred for 1 minute to obtain a dispersion (X1-1) in which resin particles (D-23) were dispersed in supercritical carbon dioxide.
Next, the dispersion (X1-1) was transferred from T3 to T4 by opening valve V1 and introducing carbon dioxide in a supercritical state into T3 and T4 using B1 to P3. During transfer of the dispersion (X1-1) from T3 to T4, the degree of opening of V2 was adjusted so that the pressure was kept constant. This operation was performed for 30 seconds and V1 was closed. By this operation, the solvent was extracted from the resin dispersion (X1) transferred into T4.
Further, by setting T4 at 40 ° C. and holding for 15 minutes, toner particles were generated.

Next, the pressure was maintained at 14 MPa by adjusting the opening degree of the pressure control valve V2 while introducing carbon dioxide from the pressure cylinder B2 into the particle recovery tank T4 using the pump P4.
By this operation, carbon dioxide containing the solvent was discharged to the solvent trap tank T5, and the toner particles were trapped in the filter F1. The operation of introducing carbon dioxide from the pressure cylinder B2 into the particle recovery tank T4 using the pump P4 was stopped when 5 times the weight of carbon dioxide introduced into the dispersion tank T3 was introduced into the particle recovery tank T4. . At the time of this stop, the operation of replacing the solvent-containing carbon dioxide with the solvent-free carbon dioxide and capturing the toner particles in the filter F1 is completed.
Further, the pressure control valve V2 is opened little by little, and the pressure in the particle recovery tank is reduced to atmospheric pressure, whereby the toner particles captured by the filter F1 are taken out and 49.5 parts by weight of toner particles and fluidizing agent 1 A toner (T-14) of the present invention having a volume average particle diameter of 5 μm was obtained by uniformly mixing 0.5 parts by weight of silica “Aerosil R972” (volume average particle diameter of primary particles: 16 nm, manufactured by Nippon Aerosil) .

For toners (T-1) to (T-14) and (T'-1) to (T'-3), low temperature fixability, gloss, heat resistant storage stability, moisture and heat storage stability, durability by the following methods And charging stability were evaluated. The results are shown in Table 3.

[1] Low-Temperature Fixing Properties Load uniformly on the paper so as to be 0.6 mg / cm ² (In this case, the powder is placed on the paper using a printer with the heat fixing device removed. Powder with the above weight density Other methods may be used if they can be uniformly placed). The temperature at which cold offset occurred when this paper was passed through a pressure roller under the conditions of a fixing speed (heat roller circumferential speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 1 MPa was measured. The lower the cold offset occurrence temperature, the better the low-temperature fixability.

[2] Glossiness Use a gloss meter (VG-1D) (made by Nippon Denshoku Co., Ltd.) to fix the image fixed at 140 ° C, adjust the projection angle and the light reception angle to 60 °, and switch S and S / 10. In accordance with S, using the 0 adjustment and the standard plate, the image was placed on the sample table after the standard setting, and the gloss was measured.
The higher the gloss value, the better the gloss.

[3] Heat-Resistant Storage Stability The sample was allowed to stand for 1 day in an atmosphere of 50 ° C., the degree of blocking was visually judged, and the heat-resistant storage stability was evaluated based on the following criteria.
[Evaluation criteria]
○: No blocking occurred Δ: Blocking occurred, but dispersed easily when force is applied ×: Blocking occurred, not dispersed even if force applied

[4] Moisture and Heat Storage Stability The sample was allowed to stand for 20 hours in an atmosphere of 40 ° C. and 80% relative humidity, the degree of blocking was visually judged, and moisture and heat storage stability was evaluated according to the following criteria.
[Evaluation criteria]
○: Blocking does not occur Δ: Blocking occurs, but disperses easily when force is applied ×: Blocking occurs, does not disperse even if force is applied

[5] Durability Continuous copying was carried out using a commercially available monochrome copying machine [AR 5030, manufactured by Sharp Corp.] as a two-component developer, and the durability was evaluated according to the following criteria.
[Evaluation criteria]
: 1: There is no change in image quality and no fogging after copying 10,000 sheets.: 1: Fogging occurs after copying 10,000 sheets. :: Fogging occurs after copying 6,000 sheets. A fog has occurred after copying

[6] Charge stability 50 g of resin particles and 10 g of iron powder ("F-150" manufactured by Nippon Iron Powder Co., Ltd.) are precisely weighed in a 50 cc stoppered glass bottle and stoppered at 23 ° C, 50 Set in a TURBRHA SEEKHA MIXER (manufactured by Willie a Bashofen) under an atmosphere of% RH and stir at a rotational speed of 90 rpm.
Load 0.2 g of the mixed powder after stirring into a blow-off powder charge measuring device (TB-203 manufactured by Kyocera Chemical Co., Ltd.) in which a 20 μm stainless steel wire mesh is set, and use a blow pressure of 10 KPa and a suction pressure of 5 KPa. Then, the charge amount of the residual iron powder is measured, and the charge amount (μC / g) of the resin particles is calculated by a standard method.
Stirring is continued for 1 hour, and the change in the amount of charge is measured by sampling after 3 minutes and after 60 minutes.

3 charge amount after minutes Q ₃ and after 3 minutes the charge amount Q ₆₀ was assessed charge amount change rate is calculated from Equation (6) below.
Rate of change = | Q _3- Q ₆₀ | / Q ₃ (6)
:: The rate of change is less than 0.05 ○: The rate of change is 0.05 or more and less than 0.07 Δ: The rate of change is 0.07 or more and less than 0.16 ×: The rate of change is 0.16 or more

The toners of the present invention of Examples 1 to 14 obtained excellent results in any of the performance evaluation items.
On the other hand, the toner of Comparative Example 1 not satisfying the relational expression (2) and the toner of Comparative Example 3 using a styrene-acrylic resin having a styrene monomer content of 50% or less have poor low-temperature fixability and glossiness. The toner of Comparative Example 2 not satisfying the relational expression (1) had poor heat resistance storage stability.

  The toner of the present invention is compatible with heat-resistant storage property, moisture-resistant heat storage property and low-temperature fixing property, and is excellent in toner durability, gloss, charge stability, and thus electrophotographic toner, electrostatic recording toner and electrostatic printing It is useful as a toner or the like.

T1: resin solution tank T2: fine particle dispersion tank T3: dispersion tank (maximum operating pressure: 20 MPa, maximum operating temperature: 100 ° C., with stirrer)
T4: Particle recovery tank (maximum operating pressure: 20MPa, maximum operating temperature: 100 ° C)
F1: Ceramic filter (mesh: 0.5 μm)
T5: solvent trap B1, B2: carbon dioxide cylinder P1, P2: solution pump P3, P4: carbon dioxide pump V1, V3, V4, V5, V6, V7, V8: valve V2: pressure regulating valve

Claims (6)

A method for producing a toner containing a colorant and a binder resin (TB), wherein the binder resin (TB) comprises 50 to 95% by weight of a crystalline resin (A) and a styrenic monomer (b1) as a component. % And the endothermic peak top temperature Ta (° C.) of the crystalline resin (A) are in the range of 50 to 100 ° C., and further the following relational expression (1) and (2) A method for producing a toner, characterized in that it comprises the step of mixing the crystalline resin (A) and the styrene-acrylic resin (B), and A method of producing a toner, wherein the temperature is maintained at 25 to 40 ° C.
Q ₁ / (Q ₀ × q / 100) ≧ 0.8 (1)
[Wherein, Q ₀ is a crystalline resin (in the first temperature rising process detected by differential scanning calorimetry when the temperature of the crystalline resin (A) is raised from 0 ° C. to 150 ° C. at 10 ° C./minute The endothermic energy [J / g] based on the endothermic peak of A) is represented. Q ₁ is an endothermic amount based on an endothermic peak derived from the crystalline resin (A) in the first temperature rising process which is detected when the temperature of the toner is raised from 10 ° C. to 150 ° C. Represents / g]. q represents the content (% by weight) of the crystalline resin (A) to the toner. ]
Q ₂ / Q ₁ ≦ 0.50 (2)
[Wherein, Q ₂ is measured at a temperature of 10 ° C./min from 150 ° C. to 0 ° C. after measuring Q _{1 in the first} temperature raising process of the toner, and then again 10 ° C./min from 0 ° C. The endothermic amount [J / g] based on the endothermic peak derived from the crystalline resin (A) in the second temperature raising process of raising the temperature by ° C. is shown. ] A styrene-acrylic resin (B) comprises a styrene monomer (b1), an acrylic monomer (b2), and a monomer containing a carboxyl group (b3) and / or a monomer containing a sulfonic acid group (b4) The method for producing a toner according to claim 1, wherein the crystalline resin (A) and the styrene-acrylic resin (B) have the following relational expression (3) as a unit.
20 ≦ X ≦ 55 (3)
X = 0.61 x AV-0.64 x (| SP _B- SP _A- 0.5 |)-0.35 x (| E _B- E _A + 20 |)-0.50 x Mw / 10,000 + 18 .0
[In the formula (3), AV styrene - acid value of the acrylic resin (B) (mgKOH / g) , SP B is a styrene - solubility parameter (SP value) of the acrylic resin (B), SP _A is solubility parameter of the crystalline resin (a), _{E B} is a styrene - ester group concentration of the acrylic resin (B) (wt%), _{E a} is an ester group concentration of the crystalline resin (a) (wt%), Mw is It represents the weight average molecular weight of the styrene-acrylic resin (B). ] The method for producing a toner according to any one of claims 1 and 2, wherein the toner satisfies the following relationship (4).
10 ≦ Tg ₁ −Tg ₂ ≦ 30 (4)
[In the formula (4), Tg ₁ is the glass transition temperature (° C.) in the first temperature rising process which is detected by differential scanning calorimetry when the temperature of the toner is raised from 10 ° C. to 150 ° C. Represents Further, Tg ₂ is measured at a temperature of 10 ° C./min from 150 ° C. to 0 ° C. after measuring Tg _{1 in the first} temperature raising process of the toner, and then raised again at 10 ° C./min from 0 ° C. to 150 ° C. It represents the glass transition temperature (° C.) in the second temperature raising process detected when the temperature is raised. ]   The method for producing a toner according to any one of claims 1 to 3, wherein the acid value of the styrene-acrylic resin (B) is 5.0 to 40.0 mg KOH / g.   The toner according to any one of claims 1 to 4, which has at least one peak in a region of 3,000 to 60,000 in a molecular weight distribution obtained by gel permeation chromatography of a styrene-acrylic resin (B). Production method. The method for producing a toner according to any one of claims 1 to 5, wherein the storage elastic modulus G '(120) of the styrene-acrylic resin (B) at 120 ° C is 1 × 10 ³ to 1 × 10 ⁶ Pa.

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