JP2017076124A - Toner and manufacturing method of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a toner that achieves both hot offset resistance and low-temperature fixability at a high level and is excellent in heat-resistant storage property and charge stability.SOLUTION: There is provided a toner comprising a polyurethane urea crystalline resin (P), an amorphous resin (Q), and a colorant (C), where the polyurethane urea crystalline resin (P) is a polyurethane urea crystalline resin obtained by reacting a urethane prepolymer (A) and diamine (e); the urethane prepolymer (A) is a urethane prepolymer including, as a component raw material, polymeric diol (a), carboxyl group-containing diol (b), and diisocyanate (c); the polymeric diol (a) has a number average molecular weight of 500 to 20,000.SELECTED DRAWING: None

Description

  The present invention relates to a toner used for developing an electrostatic charge image or a magnetic latent image in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and a manufacturing method thereof.

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.
In general, in an electrophotographic system, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed using toner to form a toner image. The toner image is transferred onto a recording medium such as paper and then fixed by a method such as heating.

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.

  In addition, when fixing a toner image by a hot roll fixing method, the hot roll and the molten toner are in direct contact at the time of fixing. At this time, the transfer paper to which the toner transferred onto the hot roll is sent next time, etc. It is premised that hot offset resistance is required since a so-called hot offset phenomenon occurs. Therefore, it is necessary to develop low-temperature fixability while maintaining hot offset resistance, and a toner having a wider working range, for example, a fixing temperature range of 50 ° C. or more, has been demanded.

  Non-crystalline resin for toner has a great influence on the above-mentioned toner characteristics, and vinyl resin such as polystyrene resin and styrene-acrylic resin, polyester resin, epoxy resin, polyurethane resin, polyamide resin, etc. are known. However, styrene-acrylic resins and polyester resins are often used because it is easy to balance storage and fixing properties.

In order to solve the problem of developing low-temperature fixability while maintaining the hot offset resistance of the toner, a method of incorporating a crystalline polyester into an amorphous resin has been proposed (Patent Document 1).
However, this method still has insufficient hot offset resistance and low-temperature fixability.

Further, a toner using a composite resin containing a polyester resin component and a styrene resin component comprising an alcohol component containing an aliphatic diol and a carboxylic acid component containing an aromatic dicarboxylic acid as a crystalline resin has also been proposed (for example, Patent Document 2).
However, with this method, a toner having excellent low-temperature fixability and excellent gloss of the resulting image can be obtained, but the heat-resistant storage stability and charge stability of the toner are insufficient.

JP 11-249339 A JP 2010-139659 A

  An object of the present invention is to provide a toner excellent in heat-resistant storage stability and charging stability, and a method for producing the same, while achieving high compatibility between hot offset resistance and low-temperature fixability.

The inventor of the present invention has arrived at the present invention as a result of studies to achieve the above object.
That is, the present invention relates to a toner comprising a polyurethane urea crystalline resin (P), an amorphous resin (Q) and a colorant (C), wherein the polyurethane urea crystalline resin (P) is a urethane prepolymer (A). And urethane diamine crystalline resin obtained by reacting diamine (e) with urethane prepolymer (A) containing polymer diol (a), carboxyl group-containing diol (b) and diisocyanate (c) as constituent raw materials And a toner having a number average molecular weight of the polymer diol (a) of 500 to 20,000, and a method for producing the toner.

  The toner of the present invention exhibits excellent performance in heat-resistant storage stability and charging stability while achieving high compatibility between hot offset resistance and low-temperature fixability.

The toner of the present invention is a toner containing a polyurethane urea crystalline resin (P), an amorphous resin (Q), and a colorant (C), and the polyurethane urea crystalline resin (P) is a urethane prepolymer (A). ) And diamine (e), and the urethane prepolymer (A) comprises a polymer diol (a), a carboxyl group-containing diol (b) and a diisocyanate (c) as constituent raw materials. The toner is a polymer, and the polymer diol (a) has a number average molecular weight of 500 to 20,000.
The “crystallinity” in the present invention means a crystal having a clear endothermic peak, not a stepwise change in endothermic amount, in the heating process of DSC measurement described later. The number average molecular weight may be described as Mn.

  The urethane prepolymer (A) is obtained by reacting a polymer diol (a) having a Mn of 500 to 20,000, a carboxyl group-containing diol (b), and a diisocyanate (c).

As the polymer diol (a) having a Mn of 500 to 20,000 as a constituent raw material of the urethane prepolymer (A), a polyester diol, a polyether diol, a polyether ester diol having a Mn of 500 to 20,000, Examples thereof include polycarbonate diol, polyolefin diol, polyalkadiene diol, and a mixture of two or more thereof.
Here, the polyester diol means a polyester in which both ends are hydroxyl groups.

  Examples of the polyester diol include a condensed polyester diol by condensation polymerization of a raw material diol and a dicarboxylic acid, a polylactone diol (poly ε-caprolactone diol, etc.) by ring-opening polymerization of a lactone using a diol as an initiator, and the like. A mixture of seeds or more can be mentioned.

Examples of the raw material diol include aliphatic diols having 2 to 12 carbon atoms (ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,3-butanediol, 1,5 -Pentanediol, neopentyl glycol, 1,6-hexanediol, 2,3-dimethylbutane-1,4-diol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, , 10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc.), alkylene ether glycols having 4 to 12 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, etc.), and those having 4 to 18 carbon atoms. Alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A etc.) and the like. Two or more of these may be used in combination.
Among these diols, linear glycol diols such as 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 are preferred, and ethylene More preferred are glycol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol.

Examples of the dicarboxylic acid include alkanedicarboxylic acids having 2 to 12 carbon atoms (including carbon in the carbonyl group) (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.), and carbon. Aliphatic dicarboxylic acids such as alkene dicarboxylic acids of 4 to 18 (maleic acid, fumaric acid, citraconic acid, etc.), aromatic dicarboxylic acids of 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid) Acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, etc.). Two or more of these may be used in combination. In addition, these acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) may be used.
Among these dicarboxylic acids, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, and octadecanedicarboxylic acid, which are linear aliphatic dicarboxylic acids, are preferable from the viewpoint of crystallinity of the polyurethane urea resin (P). Adipic acid, sebacic acid, and dodecanedicarboxylic acid are more preferable.

Examples of the polyether diol include alkylene ether glycols having 4 to 36 carbon atoms (polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diols having 4 to 36 carbon atoms (1,4-cyclohexanedimethanol, hydrogen). Added bisphenol A, etc.) alkylene oxide (hereinafter, “alkylene oxide” is abbreviated as AO) [ethylene oxide (hereinafter, “ethylene oxide” is abbreviated as EO), propylene oxide (hereinafter, “propylene oxide” is referred to as PO) Abbreviation), butylene oxide (hereinafter, “butylene oxide” is abbreviated as BO), etc.] adducts (addition mole number 1-30), AO (EO of bisphenol A, bisphenol F, bisphenol S, etc.) PO, BO, etc.) adducts (added mole number 2 to 30) or the like, and mixtures of two or more thereof.
Among these, polyethylene glycol and polytetramethylene ether glycol are preferable from the viewpoint of crystallinity of the polyurethane urea resin.

  The polyether ester diol as (a) is obtained by esterification of the polyether diol and the dicarboxylic acid exemplified as the raw material of the polyester diol, by ring-opening addition of a lactone to the polyether polyol. What is obtained is mentioned.

  Examples of the polycarbonate diol as (a) include polyhexamethylene carbonate diol, polytetramethylene carbonate diol, and a mixture of two or more thereof.

  Examples of the polyolefin diol as (a) include polyisobutene diol.

  Examples of the polyalkadiene diol as (a) include polyisoprene diol, polybutadiene diol, hydrogenated polyisoprene diol, hydrogenated polybutadiene diol, and the like, and mixtures of two or more thereof.

Among these polymer diols (a) having Mn of 500 to 20,000, polyester diol, polyether diol, polyether ester diol, polycarbonate diol, and two kinds thereof from the viewpoint of the melting point of polyurethane urea crystalline resin The above mixture is preferable, polyester diol, polycarbonate diol, and a mixture of two or more of these are more preferable, polyester diol is particularly preferable, condensation by condensation polymerization of linear aliphatic diol and linear aliphatic dicarboxylic acid Polyester diol is most preferred.
The Mn of the polymer diol (a) is preferably 750 to 15,000, more preferably 1,000 to 10,000, from the viewpoint of low-temperature fixability.

As the carboxyl group-containing diol (b) as a constituent raw material of the urethane prepolymer (A), α, α-dimethylolalkanoic acid (2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2, 2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid, 2,2-dimethylolnonanoic acid, etc.), tartaric acid, esterified product of 1 mol of citric acid and 1 mol of ethylene glycol, 1 mol of malic acid and ethylene glycol Examples thereof include esterified products with 1 mol, and salts thereof (sodium salt, potassium salt, ammonium salt, amine salt, etc.). Two or more of these may be used in combination.
Of these, α, α-dimethylolalkanoic acid is preferable, and 2,2-dimethylolpropion is more preferable, from the viewpoints of reactivity during synthesis of the urethane prepolymer and charging stability of the finally obtained toner. Acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid and 2,2-dimethyloloctanoic acid, and combinations of two or more thereof.

  Diisocyanate (c) as a constituent raw material of urethane prepolymer (A) includes aromatic diisocyanate, aliphatic diisocyanate, modified products of these diisocyanates (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione). Group, a uretoimine group, an isocyanurate group and an oxazolidone group-containing modified product) and a mixture of two or more thereof.

  The aromatic diisocyanate is preferably an aromatic diisocyanate having 6 to 20 carbon atoms (excluding the number of carbon atoms in the isocyanate group; the same shall apply hereinafter), specifically 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′-tetramethylxylylene diisocyanate (TMXDI), 2,4′- or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI {crude diaminophenylmethane [Condensation products of formaldehyde and aromatic amine (aniline) or a mixture thereof, a mixture thereof, and the like.

The aliphatic diisocyanate is preferably an aliphatic diisocyanate having 2 to 18 carbon atoms, and examples thereof include a chain aliphatic diisocyanate and a cyclic aliphatic diisocyanate.
Examples of chain aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethylcaproate. Bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, and mixtures thereof.

  Cycloaliphatic diisocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanatoethyl). Examples include -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 (c), 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 reaction (urethanization reaction) of the polymer diol (a) having a Mn of 500 to 20,000, the carboxyl group-containing diol (b) and the diisocyanate (c) is preferably 60 to 120 ° C., more preferably 70 to 100. Perform at ℃.
Since the urethane prepolymer (A) contains an isocyanate group, the equivalent ratio (NCO / OH ratio) of (a), (b) and (c) is preferably 1.01 to 2.00, more preferably 1. 0.05 to 1.75.

The urethanization reaction is preferably performed in an organic solvent in which the urethane prepolymer (A) is dissolved and inert to the isocyanate groups.
Examples of the organic solvent include methylene chloride, chloroform, ethylidene chloride, furan, 2-methylfuran, tetrahydrofuran (THF), acetone, ethyl formate, methyl formate, methyl acetate, ethyl acetate, methyl ethyl ketone (MEK), and two kinds thereof. The above mixed solvent is mentioned. Of these, THF, acetone, ethyl acetate, and MEK are preferred from the viewpoint of safety and the subsequent removal of the organic solvent.

  In the urethanization reaction, a catalyst used for the urethane reaction may be used as necessary in order to promote the reaction. Examples of the catalyst include amine catalysts (cycloamidines such as triethylamine, N-ethylmorpholine, triethylenediamine, 1,8-diaza-bicyclo (5,4,0) undecene-7 (DBU)), tin catalysts (dibutyltin). And dilaurylate, dioctyltin dilaurate and tin octylate), titanium catalysts (tetrabutyl titanate, etc.), bismuth catalysts (bismuth nitrate, triphenylbismuth, etc.) and the like.

  The polyurethane urea crystalline resin (P) is obtained by reacting (chain extending) the urethane prepolymer (A) and the diamine (e).

Examples of the diamine (e) include aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms. Two or more of these may be used in combination.
Examples of the aliphatic diamine having 2 to 18 carbon atoms include chain aliphatic diamines, alkyl (carbon number 1 to 4) or hydroxyalkyl (carbon numbers 2 to 4) substituents thereof, and cyclic aliphatic diamines.

  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).

  As alkyl (carbon number 1-4) or hydroxyalkyl (carbon number 2-4) substitution products of chain aliphatic diamine, dialkyl (carbon number 1-3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine 2,5-dimethyl-2,5-hexamethylenediamine and the like.

  Examples of cycloaliphatic diamines include alicyclic diamines having 4 to 15 carbon atoms [1,3-diaminocyclohexane, isophorone diamine, mensen diamine, 4,4′-methylene dicyclohexane diamine (hydrogenated methylene dianiline), etc.] Is mentioned.

  Aromatic diamines (having 6 to 20 carbon atoms) include unsubstituted aromatic diamines and alkyl groups (alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n- or isopropyl and butyl groups). Group diamines can be used.

  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 the like.

  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, diethyl Tolylenediamine, 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-diaminobenze 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′-diamino Diphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraisopropyl-4,4′-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′-diaminodiphenylsulfone and the like.

When chain | stretching with diamine (e), a sealing agent can be added and the reaction can be stopped in order to control molecular weight.
Examples of the sealing agent include monoamine and monool.
Examples of the monoamine include alkylamines having 1 to 20 carbon atoms (ethylamine, n-butylamine, t-butylamine, diethylamine, di-n-butylamine, etc.) and the like.
As monools, alkanols having 1 to 20 carbon atoms (methanol, ethanol, isopropanol, n-butanol, n-hexanol, n-octanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), 3 to 3 carbon atoms Examples include 20 alkenols (eg, allyl alcohol, propenyl alcohol, and oleyl alcohol), aromatic alcohols having 7 to 36 carbon atoms (eg, benzyl alcohol), AO adducts thereof, and AO adducts of monohydric phenols.
Of these, monoamines are preferable, and alkylamines having 2 to 12 carbon atoms are more preferable.

The toner production method of the present invention is a toner production method including the following steps.
The method for obtaining the polyurethane urea crystalline resin (P) by extending the urethane prepolymer (A) with the diamine (e) is not particularly limited, but the following [1] to [6] are exemplified.
[1] When the urethanization reaction is carried out in the absence of a solvent, the urethane prepolymer (A) and the diamine (e) (sealant if necessary) mixed by heating or the like are mixed so that the isocyanate group is substantially To obtain a polyurethane urea crystalline resin (P) by allowing the chain to extend until it disappears.

[2] When the urethanization reaction is carried out in an organic solvent, diamine (e) (sealant if necessary) is mixed in the solution of the urethane prepolymer (A) and reacted until the isocyanate groups are substantially eliminated. A method of obtaining a solution of polyurethane urea crystalline resin (P) by chain elongation.

[3] When the urethanization reaction is carried out in the absence of a solvent, a urethane prepolymer (A) that has been melted by heating or the like is obtained, and then the melt is dispersed in the aqueous medium (X). ) (If necessary, a sealant) is mixed with the dispersion and reacted until the isocyanate groups are substantially eliminated to extend the chain, thereby obtaining an aqueous dispersion of the polyurethane urea crystalline resin (P).

[4] When the urethanization reaction is carried out in an organic solvent, a solution of the urethane prepolymer (A) is obtained, and then the solution is dispersed in the aqueous medium (X) and then the diamine (e) (seal if necessary). A method in which an aqueous dispersion of a polyurethane urea crystalline resin (P) is obtained by mixing a stopper with a dispersion and reacting until the isocyanate groups are substantially eliminated to extend the chain.

[5] When the urethanization reaction is carried out in the absence of a solvent, the neutralized product (N) is obtained by reacting the urethane prepolymer (A) that has been melted by heating or the like with the base (B) described below, After the neutralized product (N) is dispersed in the aqueous medium (X), the diamine (e) (sealant if necessary) is mixed with the dispersion and reacted until the isocyanate group substantially disappears, thereby extending the chain. A method for obtaining an aqueous dispersion of polyurethane urea crystalline resin (P).

[6] When the urethanization reaction is carried out in an organic solvent, the base (B) described later is reacted with the urethane prepolymer (A) solution to obtain a neutralized product (N) solution, and then neutralized. After the solution of the product (N) is dispersed in the aqueous medium (X), the diamine (e) (sealant if necessary) is mixed with the dispersion, and reacted until the isocyanate group is substantially eliminated to chain-extend. A method for obtaining an aqueous dispersion of polyurethane urea crystalline resin (P). If necessary, the organic solvent may be distilled off. Examples of the method for distilling off the organic solvent include a method for removing the organic solvent under reduced pressure. However, when the organic solvent is distilled off under reduced pressure, it is necessary to adjust the degree of reduced pressure and the temperature so that the aqueous medium (X) is not removed at the same time.

In [5] and [6], the neutralized product (N) or the solution of the neutralized product (N) is added to the aqueous medium (X) in which the diamine (e) (sealant if necessary) is mixed. It may be dispersed.
Among these, from the viewpoint of Mn of the polyurethane urea crystalline resin (P), [3] to [6] are preferable, [5] and [6] are more preferable, and [6] is most preferable.

The base (B) used in [5] or [6] is formed by neutralizing the carboxyl group derived from the carboxyl group-containing diol (b) in the urethane prepolymer (A) to form a neutralized salt. Used for the purpose of hydrophilizing the polymer (A).
Examples of the base (B) used for this purpose include ammonia, monoamines having 1 to 30 carbon atoms, quaternary ammonium, alkali metals (sodium, potassium, etc.), and alkaline earth metals (calcium salts, magnesium salts, etc.). Can be mentioned.

Examples of the monoamine having 1 to 30 carbon atoms include primary and / or secondary amines having 1 to 30 carbon atoms (ethylamine, n-butylamine, isobutylamine, etc.), tertiary amines having 3 to 30 carbon atoms (trimethylamine, triethylamine, Lauryl dimethylamine, etc.). Examples of the quaternary ammonium include trialkylammonium having 4 to 30 carbon atoms (such as lauryltrimethylammonium).
Among these, preferred are alkali metals, quaternary ammoniums, and monoamines, more preferred are sodium and monoamines having 1 to 20 carbon atoms, and particularly preferred are tertiary monoamines having 3 to 20 carbon atoms. It is.

  At least a part of the carboxyl group may be neutralized with a base. The base neutralization rate of the carboxyl group is preferably 20 to 100%, more preferably 40 to 100%.

Examples of the aqueous medium (X) include water and a mixture of water and a water-soluble organic solvent. Water-soluble organic solvents include ketone solvents; acetone, MEK, etc., ester solvents; ethyl acetate, γ-butyrolactone, ether solvents, THF, amide solvents, N, N-dimethylformamide, N, N -Dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, and the like, and alcohol solvents; methyl alcohol, ethyl alcohol, isopropyl alcohol, and the like, and mixed solvents of two or more of these.
When a water-soluble organic solvent is used, it may be distilled off if necessary during or after the production of the aqueous resin dispersion.

  In addition to the polymer diol (a) having a number average molecular weight of 500 to 20,000, the carboxyl group-containing diol (b), and the diisocyanate (c), the urethane prepolymer (A) further contains a carboxyl group-containing diol (b). From the viewpoint of low-temperature fixability of the finally obtained toner, it is preferable to use a diol (d) having a number average molecular weight of less than 500, which does not contain any carboxyl group, as a constituent raw material.

  Examples of the diol (d) having a number average molecular weight of less than 500 include alkylene glycols having 2 to 10 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol). 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, etc.), C4-10 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, etc.), carbon number 11 -20 alkylene glycol (1,12-dodecanediol, etc.), C11-20 alkylene ether glycol (polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), C6-18 alicyclic diol 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.), among polyoxyalkylene ethers of the above alicyclic diols, those having a number average molecular weight of less than 500, among polyoxyalkylene ethers of dihydric phenols and bisphenols Examples include those having a number average molecular weight of less than 500.

As (d), a diol having at least one group selected from the group consisting of a sulfonic acid (salt) group, a sulfamic acid (salt) group, and a phosphoric acid (salt) group can also be used. “Acid (salt)” means an acid or an acid salt.
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, alkali metal salts (sodium salts and potassium salts, etc.).

  Among these, alkylene glycols having 2 to 10 carbon atoms are preferable from the viewpoint of achieving both low-temperature fixability and hot offset resistance of the finally obtained toner, such as ethylene glycol, 1,4-butanediol, 1,6- Hexanediol, 1,9-nonanediol, and 1,10-decanediol are more preferred.

  The Mn of the polyurethane urea crystalline resin (P) is preferably from 3,000 to 200,000, more preferably from 4,000 to 200, from the viewpoint of achieving both low temperature fixability and hot offset resistance of the finally obtained toner. 170,000, particularly preferably 5,000 to 150,000.

Mn is measured under the following conditions using gel permeation chromatography (GPC) by dissolving polyurethane urea crystalline resin (P) in tetrahydrofuran (THF) and using it as a sample solution.
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Solution injection amount: 100 μl
Detection device: Refractive index detector Reference material: TOSANDO standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 1900000 355000 1090000
2890000)

  The melting point of the polyurethane urea crystalline resin (P) is preferably from 50 to 90 ° C., more preferably from 55 to 85 ° C., particularly preferably from 60 to 80 ° C., from the viewpoint of heat resistant storage stability of the finally obtained toner. .

The melting point can be measured by the following method using a differential scanning calorimeter (DSC) (for example, “DSC210” manufactured by Seiko Instruments Inc.).
(P) was cooled to 0 ° C. by DSC at a temperature decrease rate of 10 ° C./min, then heated at a temperature increase rate of 20 ° C./min to measure the endothermic change, and the temperature corresponding to the maximum peak of the endotherm was determined. The melting point.

  The amorphous resin (Q) used in the present invention is not particularly limited as long as it is amorphous, but from the viewpoint of low-temperature fixability and charge stability of the finally obtained toner. It is preferably at least one non-crystalline resin selected from the group consisting of non-crystalline polyester resin, polyurethane resin, epoxy resin, and vinyl resin, and preferably non-crystalline polyester resin and vinyl resin. More preferred.

The amorphous polyester resin is obtained by reacting a polyol component and a carboxylic acid component as raw materials.
Examples of the polyol component of the amorphous polyester resin include a diol and a trivalent or higher polyol.
Examples of the diol include alkylene glycols having 2 to 10 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1, 9-nonanediol, 1,10-decanediol, etc.); alkylene ether glycols having 4 to 10 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, etc.); alkylene glycols having 11 to 36 carbon atoms (1,12- Dodecanediol, etc.); C11-36 alkylene ether glycol (polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); C6-C36 alicyclic diol (1,4-cyclohexanedimethano) And (poly) oxyalkylene (alkylene group having 2 to 4 carbon atoms (oxyethylene, oxypropylene, etc.). The same is true for the following polyoxyalkylene groups) ether [ Number 1 to 30 of oxyalkylene units (hereinafter abbreviated as AO units); and polyoxy of dihydric phenol [monocyclic dihydric phenol (for example, hydroquinone) and bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.)] Alkylene ether (number of AO units 2 to 30);
Among these, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1 from the viewpoint of achieving both low temperature fixability and hot offset resistance of the finally obtained toner , 6-hexanediol, neopentyl glycol, and polyoxyalkylene ethers of bisphenols (number of AO units 2 to 30) are preferred.

Examples of the trivalent or higher polyol include 3 to 8 or higher aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyol and intramolecular or intermolecular dehydrates such as glycerin, trimethylolethane, and trimethylolpropane. , Pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; saccharides and derivatives thereof such as sucrose and methylglucoside; (poly) oxyalkylene ethers of the above aliphatic polyhydric alcohols (number of AO units 1-30) ); Polyoxyalkylene ethers of trisphenols (trisphenol PA, etc.) (number of AO units 2-30); polyoxyalkylene ethers of novolak resins (phenol novolak, cresol novolac, etc., average degree of polymerization 3-60) (AO) single It includes the number 2 to 30) or the like is.
Among these, 3 to 8 or higher aliphatic polyhydric alcohols and novolak resin polyoxyalkylene ethers (2 to 30 AO units) are preferable.

Examples of the carboxylic acid component of the amorphous polyester resin include dicarboxylic acid, trivalent or higher polycarboxylic acid, and monocarboxylic acid.
Examples of the dicarboxylic acid include aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid); alkanedicarboxylic acids having 4 to 36 carbon atoms (such as succinic acid, adipic acid, And sebacic acid); alicyclic dicarboxylic acid having 6 to 40 carbon atoms [for example, dimer acid (dimerized linoleic acid)]; alkene dicarboxylic acid having 4 to 36 carbon atoms (for example, alkenyl succinic acid such as dodecenyl succinic acid, maleic acid) , Fumaric acid, citraconic acid, and mesaconic acid); and their ester-forming derivatives;

  Examples of the ester-forming derivatives include acid anhydrides, alkyl (C1-C24: methyl, ethyl, butyl, stearyl, etc., preferably C1-C4) esters, and partial alkyl (same as above) esters. Can be mentioned. The same applies to the following ester-forming derivatives.

  Of these, aromatic dicarboxylic acids having 8 to 36 carbon atoms; alkanedicarboxylic acids having 4 to 36 carbon atoms; alkene dicarboxylic acids having 4 to 36 carbon atoms and ester-forming derivatives thereof are more preferable. Is phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, maleic acid, fumaric acid and / or their ester-forming derivatives.

Examples of tricarboxylic or higher (preferably 3 to 6) polycarboxylic acids include aromatic carboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatics having 6 to 36 carbon atoms (fats). Examples thereof include carboxylic acids (including cyclic) (hexanetricarboxylic acid, decanetricarboxylic acid and the like), and ester-forming derivatives thereof.
Of these, trimellitic acid, pyromellitic acid, and ester-forming derivatives thereof are preferable.

  Examples of the monocarboxylic acid include aliphatic (including alicyclic) monocarboxylic acids having 1 to 30 carbon atoms and aromatic monocarboxylic acids having 7 to 36 carbon atoms.

  As an amorphous polyurethane resin, those having the above-mentioned amorphous polyester resin and the above-mentioned diisocyanate as structural units, those having the above-mentioned amorphous polyester resin, the diol component and the diisocyanate as structural units, etc. Is mentioned.

  Examples of the amorphous epoxy resin include a ring-opening polymer of polyepoxide, a polyaddition product of polyepoxide and an active hydrogen-containing compound (water, polyol, dicarboxylic acid, trivalent or higher polycarboxylic acid, polyamine, etc.), and the like. .

Examples of the amorphous vinyl resin include a polymer obtained by homopolymerizing or copolymerizing a radical polymerizable monomer using a radical polymerization initiator. Examples of the radical polymerizable monomer include the following monomers (w1) to (w9).
The polymerization can be performed by a known method such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.
Examples of radical polymerization initiators 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 radical polymerization initiator used is preferably 0.01 to 10% by weight, more preferably 0.05 to 8% by weight, particularly preferably 0.1 to 6% by weight, based on the total amount of monomers. is there.

(W1) Hydrocarbon having a polymerizable double bond:
Examples thereof include the following (w11) aliphatic hydrocarbon having a polymerizable double bond and (w12) aromatic hydrocarbon having a polymerizable double bond.
(W11) Aliphatic hydrocarbon having a polymerizable double bond:
For example, the following (w111) and (w111) are mentioned.
(W111) Chain hydrocarbon having a polymerizable double bond: Alkene having 2 to 30 carbon atoms (for example, ethisoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, etc.).
(W112) Cyclic hydrocarbon having a polymerizable double bond: mono- or dicycloalkene having 6 to 30 carbon atoms (such as cyclohexene, vinylcyclohexene and ethylidenebicycloheptene) and mono- or dicycloalkoxy having 5 to 30 carbon atoms Diene [for example, (di) cyclopentadiene and the like] and the like.

(W12) Aromatic hydrocarbon having a polymerizable double bond: Styrene; Hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl having 1 to 30 carbon atoms) substituted styrene (eg, α-methylstyrene, vinyl) Toluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, etc.); and vinylnaphthalene, etc. .

(W2) Monomers having a carboxyl group and a polymerizable double bond and their salts:
C3-C15 unsaturated monocarboxylic acid {For example, (meth) acrylic acid ["(meth) acryl" means acryl or methacryl. ], Crotonic acid, isocrotonic acid, cinnamic acid and the like}; C3-C30 unsaturated dicarboxylic acid (anhydride) [for example, (anhydrous) maleic acid, fumaric acid, itaconic acid, (anhydrous) citraconic acid, mesaconic acid, etc. And monoalkyl (C1-10) esters of unsaturated dicarboxylic acids having 3 to 10 carbon atoms (eg maleic acid monomethyl ester, maleic acid monodecyl ester, fumaric acid monoethyl ester, itaconic acid monobutyl ester and citracone) Acid monodecyl ester, etc.).

Examples of the salt constituting the monomer salt having a carboxyl group and a polymerizable double bond include alkali metal salts (such as sodium salt and potassium salt), alkaline earth metal salts (such as calcium salt and magnesium salt), and ammonium. Examples thereof include salts, amine salts, and quaternary ammonium salts.
The amine salt is not particularly limited as long as it is an amine compound. For example, primary amine salts (such as ethylamine salts, butylamine salts and octylamine salts), secondary amines (such as diethylamine salts and dibutylamine salts), tertiary amines ( Triethylamine salt and tributylamine salt). Examples of the quaternary ammonium salt include tetraethylammonium salt, triethyllaurylammonium salt, tetrabutylammonium salt, and tributyllaurylammonium salt.

  Examples of the salt of the monomer having a carboxyl group and a polymerizable double bond include sodium acrylate, sodium methacrylate, monosodium maleate, disodium maleate, potassium acrylate, potassium methacrylate, monopotassium maleate, acrylic Examples include lithium acid, cesium acrylate, ammonium acrylate, calcium acrylate, and aluminum acrylate.

(W3) Monomers having a sulfo group and a polymerizable double bond and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms (for example, vinyl sulfonic acid, (meth) allyl sulfonic acid and methyl vinyl sulfonic acid); styrene sulfonic acid and alkyl (2 to 24 carbon) derivatives thereof (for example, α-methyl styrene sulfone) Acid etc .; C5-C18 sulfo (hydroxy) alkyl- (meth) acrylate (for example, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloyloxy) Ethanesulfonic acid and 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid); sulfo (hydroxy) alkyl (meth) acrylamide having 5 to 18 carbon atoms [eg 2- (meth) acryloylamino-2,2- Dimethylethanesulfonic acid, 2- (meth) acrylic Do-2-methylpropanesulfonic acid and 3- (meth) acrylamide-2-hydroxypropanesulfonic acid, etc.]; alkyl (C3-C18) allylsulfosuccinic acid (for example, propylallylsulfosuccinic acid, butylallylsulfosuccinic acid, 2- Ethylhexyl-allylsulfosuccinic acid, etc.); poly [n (degree of polymerization, the same applies hereinafter) = 2-30] oxyalkylene (oxyethylene, oxypropylene, oxybutylene, etc.). Oxyalkylene may be used alone or in combination. The addition type may be random addition or block addition.) Sulfate ester of mono (meth) acrylate [for example, poly (n = 5-15) oxyethylene monomethacrylate sulfate and poly (n = 5-15) oxypropylene monomethacrylate sulfate Esters etc.]; And salts thereof.

  In addition, as a salt, what was illustrated as a salt which comprises the salt of the monomer which has (w2) a carboxyl group and a polymerizable double bond is mentioned.

(W4) Monomer having phosphono group and polymerizable double bond and salt thereof:
(Meth) acryloyloxyalkyl phosphate monoester (alkyl group having 1 to 24 carbon atoms) (for example, 2-hydroxyethyl (meth) acryloyl phosphate and phenyl-2-acryloyloxyethyl phosphate), (meth) acryloyloxyalkyl Phosphonic acid (alkyl group having 1 to 24 carbon atoms) (for example, 2-acryloyloxyethylphosphonic acid).
In addition, as a salt, what was illustrated as a salt which comprises the monomer which has (w2) a carboxyl group and a polymerizable double bond is mentioned.

(W5) Monomer having a hydroxyl group and a polymerizable double bond:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(W6) Nitrogen-containing monomer having a polymerizable double bond:
For example, (w61) a monomer having an amino group and a polymerizable double bond, (w62) a monomer having an amide group and a polymerizable double bond, (w63) carbon having a nitrile group and a polymerizable double bond. Examples thereof include a monomer having 3 to 10 carbon atoms, a (w64) monomer having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond.
(W61) Monomer having amino group and polymerizable double bond:
Aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole Aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof.

(W62) Monomer having an amide group and a polymerizable double bond:
(Meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N′-methylene-bis (meth) acrylamide, cinnamic amide, N, N -Dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.
(W63) C3-C10 monomer having a nitrile group and a polymerizable double bond:
(Meth) acrylonitrile, cyanostyrene, cyanoacrylate and the like.
(W64) C8-12 monomer having a nitro group and a polymerizable double bond:
Nitrostyrene etc.

(W7) C6-C18 monomer having an epoxy group and a polymerizable double bond:
Glycidyl (meth) acrylate and p-vinylphenylphenyl oxide.

(W8) C2-C16 monomer having a halogen element and a polymerizable double bond:
Vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, chloroprene and the like.

(W9) An ester having a polymerizable double bond, an ether having a polymerizable double bond, a ketone having a polymerizable double bond, and a sulfur-containing compound having a polymerizable double bond:
For example, (w91) an ester having 2 to 24 carbon atoms having a polymerizable double bond, (w92) an ether having 3 to 16 carbon atoms having a polymerizable double bond, and (w93) a carbon number having a polymerizable double bond. Examples thereof include 4 to 12 ketones and (w94) a sulfur-containing compound having 2 to 16 carbon atoms having a polymerizable double bond.
(W91) C2-C24 ester having a polymerizable double bond:
Vinyl acetate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl -(Alpha) -ethoxy acrylate, (meth) acrylic acid ester having 1 to 22 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 and eicosyl (meth) acrylate Rate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two alkyl groups are carbon atoms 2-8 linear, branched or alicyclic groups), poly (meth) allyloxyalkanes (diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetra Monomers having a polyalkylene glycol chain and a polymerizable double bond [polyethylene glycol [Mn = 300] mono (meth) acrylate, polypropylene glycol (Mn = 500) mono), such as allyloxybutane and tetrametaallyloxyethane) Acrylate, methyl alcohol EO 10 mol adduct (meth) acrylate and lauryl alcohol EO 30 mol adduct (meth) a Acrylates, 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 and polyethylene glycol di (meth) acrylate, etc.].
(W92) C3-C16 ether having a polymerizable double bond:
Vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxyethyl ether, 3,4-dihydro -1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, acetoxystyrene, phenoxystyrene, and the like.
(W93) C4-C12 ketone having a polymerizable double bond:
Examples include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.
(W94) a sulfur-containing compound having 2 to 16 carbon atoms having a polymerizable double bond:
Examples thereof include divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, and divinyl sulfoxide.

The glass transition temperature (Tg) of the amorphous resin (Q) is preferably 40 to 80 ° C., more preferably 45 to 78 ° C., and still more preferably 50 from the viewpoints of low-temperature fixability, heat-resistant storage stability and charging stability. ~ 75 ° C. Two or more types of amorphous resins (Q) having different Tg can be used in combination.
In addition, Tg is measured by the method (DSC method) prescribed | regulated to ASTMD3418-82 using DSC.

The softening point (Tm) measured with the flow tester of the amorphous resin (Q) is preferably 60 to 170 ° C, more preferably 65 to 165 ° C, and still more preferably 70 to 160 ° C.
Two or more types of amorphous resins (Q) having different Tm can be used in combination.

The softening point (Tm) is measured by the following method.
Using a Koka-type 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 heating 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).

As the colorant (C) used in the present invention, 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, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazole Brown B, Oil Pink OP, etc. Or 2 or more types can be mixed and used.
Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel, or a compound such as magnetite, hematite, ferrite) can also be included as a colorant.

The content of the colorant (C) is preferably 1 to 40 parts by weight, more preferably 3 to 3 parts by weight when the total of the polyurethane urea crystalline resin (P) and the amorphous resin (Q) is 100 parts by weight. 10 parts by weight.
In addition, when using magnetic powder, Preferably it is 20-150 weight part, More preferably, it is 40-120 weight part.

The toner of the present invention may be obtained by any known method such as kneading and pulverizing method, emulsion aggregation method, dissolution suspension polymerization method and the like.
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. After further classification, it can be produced by mixing a fluidizing agent.
In addition, when the toner is obtained by the emulsion aggregation method, the components constituting the toner excluding the fluidizing agent are dissolved or dispersed in an organic solvent, and then dispersed in an aqueous medium to obtain a dispersion, and then the dispersion is aggregated. It can be manufactured by heat-sealing and then separating and classifying.

  The toner production method described below is preferable from the viewpoints of easy particle size reduction, easy obtaining of a narrow particle size distribution, and easy shape control.

In the method for producing a toner of the present invention, in a state of a dispersion (W) in which a polyurethane urea crystalline resin (P), an amorphous resin (Q), and a colorant (C) are dispersed in an aqueous medium (X). And a step of removing the aqueous medium (X) after the polyurethane urea crystalline resin (P), the amorphous resin (Q) and the colorant (C) are aggregated and thermally fused.
In the toner production method of the present invention, an aqueous dispersion (Wp) of polyurethane urea crystalline resin (P), an aqueous dispersion (Wq) of amorphous resin (Q), and an aqueous dispersion of colorant (Wc) are used. After mixing to obtain a dispersion (W), the crystalline resin (P), the amorphous resin (Q) and the colorant (C) in the dispersion (W) are aggregated and thermally fused. It is preferable to remove the aqueous medium (X).

The aqueous dispersion (Wp) of the polyurethane urea crystalline resin (P) can be used as it is when it is obtained as an aqueous dispersion in the above-described method for obtaining the polyurethane urea crystalline resin (P).
When obtained as a resin or a resin solution, the following methods [7] and [8] are exemplified.
[7] If necessary, an aqueous medium containing a surfactant (K) is gradually added to the organic solvent solution of the polyurethane urea crystalline resin (P) with stirring to perform phase inversion emulsification. Next, the organic solvent is distilled off by reducing the pressure while heating as necessary to obtain an aqueous dispersion (Wp).
[8] If necessary, an aqueous medium is gradually added to the organic solvent solution of the polyurethane urea crystalline resin (P) containing the surfactant (K) with stirring to perform phase inversion emulsification. Next, the organic solvent is distilled off by reducing the pressure while heating as necessary to obtain an aqueous dispersion (Wp).

  Examples of the surfactant (K) include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Two or more surfactants may be used in combination.

  The aqueous dispersion (Wq) of the amorphous resin (Q) can be obtained by the same method as [7] and [8] described above.

  The aqueous colorant dispersion (Wc) can be obtained by dispersing the aforementioned colorant (C) in an aqueous medium containing a surfactant (K) as necessary.

  Dispersion (W) can also be obtained by mixing (Wp), (Wq) and (Wc). In mixing, the aqueous medium (X) may be adjusted for the purpose of adjusting the concentration of the dispersion (W).

In the production of (Wp), (Wq), (Wc) and (W), a disperser can be used as necessary.
The disperser is not particularly limited as long as it is generally commercially available as an emulsifier or a disperser. For example, a batch emulsifier {“homogenizer” (manufactured by IKA), “polytron” (manufactured by Kinematica) and “ TK Auto Homo Mixer "[manufactured by Primix Co., Ltd.]}, continuous emulsifier {" Ebara Milder "[manufactured by Ebara Corporation]," TK Filmix "," TK Pipeline Homo Mixer "[Primix ( Co., Ltd.], “Colloid Mill” [manufactured by Shinko Pantech Co., Ltd.], “Slasher”, “Trigonal Wet Fine Crusher” [Suntech Co., Ltd.], “Capitol” (manufactured by Eurotech) and “Fine” Flow Mill "[manufactured by Taiheiyo Kiko Co., Ltd.]}, high-pressure emulsifier {" Microfluidizer "[manufactured by Mizuho Industry Co., Ltd.]," Nanomizer "[SG Njiniaring Co., Ltd.] and "APV Gaurin" (manufactured by Gaurin Co., Ltd.)}, membrane emulsifier {"membrane emulsifier" [manufactured by Chilling Industries Co., Ltd.]}, vibratory emulsifier {"Vibro mixer" Etc.}, an ultrasonic emulsifier {“ultrasonic homogenizer” (manufactured by Branson), etc.}, and the like.

  Further, in the production of (Wp), (Wq), (Wc) and (W), from the viewpoint of the stability of the dispersion, in addition to the surfactant (K), an inorganic dispersant, a water-soluble polymer, etc. Can also be used. Moreover, a plasticizer etc. can also be used together as a dispersion aid.

  As a method of aggregating the polyurethane urea crystalline resin (P), the amorphous resin (Q) and the colorant (C) in the dispersion (W), a method of adding an aggregating agent to the dispersion (W) is available. Can be mentioned.

Examples of the flocculant include inorganic flocculants such as inorganic metal salts, inorganic ammonium salts, and metal complexes, cationic flocculants, and organic flocculants such as polyethyleneimine. Examples of the inorganic metal salt include sodium chloride, magnesium sulfate, and magnesium chloride, and are preferable. The valence of the salt is not particularly limited, and may be monovalent or divalent or higher.
The addition amount of the flocculant is preferably 0.1 to 20% by weight, more preferably 0.2 to 15% by weight, based on the total weight of (P), (Q) and (C).

The heating temperature in the step of heat-sealing the agglomerated material is preferably 30 to 100 ° C, more preferably 40 to 100 ° C.
The heating time is preferably 1 to 12 hours, more preferably 2 to 10 hours.

After heat fusion, the toner particles can be separated by passing through a step of removing the aqueous medium (X).
The method for removing the aqueous medium (X) is not particularly limited, and examples thereof include a method for removing by a reduced pressure and a method for performing individual liquid separation using a filtration and / or centrifugal separator and drying.
The volatile content of the aqueous medium after drying is preferably 5% by weight or less, more preferably 1% by weight or less, and particularly preferably 0.5% by weight or less based on the weight of the toner.

From the viewpoint of achieving both hot offset resistance and low-temperature fixability, the weight ratio (P) / (Q) of the polyurethane urea crystalline resin (P) to the amorphous resin (Q) in the present invention is preferably 2/98. Is 50/50, more preferably 4/96 to 45/55, and particularly preferably 5/95 to 40/60.
If the weight ratio (P) / (Q) is less than 2/98, the low-temperature fixability may be poor, and if it exceeds 50/50, the hot offset resistance may be poor. The range of 2/98 to 50/50 is preferable in that both hot offset resistance and low-temperature fixability can be achieved.

  The toner of the present invention preferably contains a release agent (R). Further, the toner can contain a charge control agent. These can be contained in the toner by containing them in advance when the dispersion liquid (W) is obtained.

  Examples of the release agent (R) 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, polyethylene oxide wax). And oxidized polypropylene wax) 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).

  The melting point of (R) 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.

Kinematic viscosity at 100 ° C. of (R) is a low-temperature fixability of the preferable from the viewpoint 3~20 ^[mm 2 / s], and more preferably 4~19 ^[mm 2 / s], particularly preferably from 5 to 18 [mm ² / s].

  As charge control agents, nigrosine compounds, triphenylmethane compounds containing tertiary amines as side chains, quaternary ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo compounds, copper phthalocyanine compounds , 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 charge control agent may be dispersed inside the toner, may cover the surface, or may be dispersed inside and coated on the surface.

In addition, a fluidizing agent can be added to the toner of the present invention from the viewpoint of fluidity.
Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder.

The volume average particle size of the toner of the present invention is preferably 1 to 20 μm, more preferably 2 to 18 μm, and still more preferably 3 to 15 μm.
The volume average particle diameter can be measured using “Coulter Multisizer 3” (manufactured by Beckman Coulter, Inc.).

  The toner of the present invention is mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.) as necessary to cause an electrical latent. Used as an image developer. The weight ratio of toner to carrier particles is 1/99 to 100/0. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.

  The toner of the present invention is fixed on a support (paper, polyester film, etc.) by a copying machine, a printer or the like to be used as a recording material. As a method for fixing to the support, a known hot roll fixing method, flash fixing method, or the like can be applied.

  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
[Production of polyester diol (a-1)]
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling tube, nitrogen introduction tube and decompression device, 571 parts of 1,6-hexanediol, 566 parts of adipic acid, and 2 parts of tetrabutoxy titanate as a polymerization catalyst. The mixture was allowed to react at 170 ° C. 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 cooled and took out and obtained polyester diol (a-1). Mn of (a-1) is 1,000.

Production Example 2
[Production of polyester diol (a-2)]
In Production Example 1, 571 parts of 1,6-hexanediol and 566 parts of adipic acid were changed to 537 parts of 1,12-dodecanediol and 500 parts of dodecanedioic acid, and the same operation as in Production Example 1 was carried out. Diol (a-2) was obtained. Mn of (a-2) is 2,000.

Production Example 3
[Production of Urethane Prepolymer (A-1)]
Polyester diol having a Mn of 2,000 consisting of 1,6-hexanediol and sebacic acid in a pressurized reaction vessel equipped with a stirrer, heating / cooling device, thermometer and nitrogen introduction tube "HS2H-200S") 208 parts, 2,2-dimethylolpropionic acid 7 parts, HDI 35 parts, and acetone 250 parts. Then, it heated at 80 degreeC and urethanation reaction was performed for 10 hours, and the solution of the urethane prepolymer (A-1) was obtained.

Production Example 4
[Production of aqueous dispersion (Wp-1) of polyurethane urea crystalline resin (P-1)]
After cooling 500 parts of the urethane prepolymer (A-1) solution to 40 ° C., 5.3 parts of triethylamine was added and the mixture was stirred at 40 ° C. for 30 minutes. After pouring and dispersing using a TK auto homomixer (manufactured by Primix Co., Ltd.), 1.9 parts of n-butylamine and 4.5 parts of hexamethylenediamine are added, and the mixture is allowed to undergo chain extension reaction for 5 hours with stirring. The aqueous solution of polyurethane urea crystalline resin (P-1) having a solid content concentration of 25% is obtained by distilling off the solvent under reduced pressure of 30 kPa at 50 ° C. and adding ion exchange water for the purpose of adjusting the solid content concentration. A dispersion (Wp-1) was obtained.
Mn of (P-1) obtained by washing and drying was 21,000, and the melting point was 69 ° C.

Production Example 5
[Production of Urethane Prepolymer (A-2)]
178 parts of polyester diol (a-1), 12 parts of 2,2-dimethylolpropionic acid, 60 parts of HDI, and 250 parts of acetone are added to a pressure reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer and a nitrogen introduction tube. Prepared. Thereafter, the mixture was heated to 80 ° C. and subjected to a urethanization reaction for 10 hours to obtain a urethane prepolymer (A-2) solution.

Production Example 6
[Production of aqueous dispersion (Wp-2) of polyurethane urea crystalline resin (P-2)]
In Production Example 4, the solution of (A-1) was added to the solution of (A-2), 5.3 parts of triethylamine was added to 9.0 parts, 1.9 parts of n-butylamine and 4.5 parts of hexamethylenediamine were added. Except for 6.5 parts of n-butylamine and 5.2 parts of hexamethylenediamine, the same operation as in Production Example 4 was carried out, and an aqueous polyurethane urea resin (P-2) having a solid content concentration of 25% A dispersion (Wp-2) was obtained.
Mn of (P-2) obtained by washing and drying was 5,000, and the melting point was 60 ° C.

Production Example 7
[Production of Urethane Prepolymer (A-3)]
A pressurized reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer and a nitrogen introduction tube was charged with 208 parts of polyester diol (a-2), 8 parts of 2,2-dimethylolbutanoic acid, 35 parts of HDI, and 250 parts of MEK. It is. Then, it heated at 80 degreeC and urethanation reaction was performed for 10 hours, and the solution of the urethane prepolymer (A-3) was obtained.

Production Example 8
[Production of aqueous dispersion (Wp-3) of polyurethane urea crystalline resin (P-3)]
In Production Example 4, the solution of (A-1) was added to the solution of (A-3), 5.3 parts of triethylamine was added to 5.2 parts, 1.9 parts of n-butylamine and 4.5 parts of hexamethylenediamine were added. An aqueous dispersion of a polyurethane urea crystalline resin (P-3) having the same solid content concentration of 25%, except that 2.5 parts of n-butylamine and 2.1 parts of ethylenediamine were used. (Wp-3) was obtained.
Mn of (P-3) obtained by washing and drying was 14,000, and the melting point was 81 ° C.

Production Example 9
[Production of Urethane Prepolymer (A-4)]
197 parts of polycaprolactone diol having a Mn of 4,000 (trade name “Placcel 240”, manufactured by Daicel Corporation) in a pressurized reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer and a nitrogen introduction tube, 2, 2 -7 parts of dimethylolpropionic acid, 8 parts of 1,9-nonanediol, 38 parts of IPDI and 250 parts of acetone were charged. Thereafter, the mixture was heated to 80 ° C. and subjected to urethanization for 10 hours to obtain a solution of a urethane prepolymer (A-4).

Production Example 10
[Production of aqueous dispersion (Wp-4) of polyurethane urea crystalline resin (P-4)]
In Production Example 4, the solution of (A-1) was added to the solution of (A-4), 5.3 parts of triethylamine was added to 5.0 parts, 1.9 parts of n-butylamine and 4.5 parts of hexamethylenediamine were added. Except for 0.6 parts of t-butylamine and 3.5 parts of isophoronediamine, the same operation as in Production Example 4 was carried out, and an aqueous dispersion of a polyurethane urea crystalline resin (P-4) having a solid content concentration of 25% The body (Wp-4) was obtained.
Mn of (P-4) obtained by washing and drying was 68,000, and the melting point was 55 ° C.

Production Example 11
[Production of Urethane Prepolymer (A-5)]
Polyester diol having a Mn of 10,000 consisting of 1,6-hexanediol and sebacic acid (made by Toyokuni Oil Co., Ltd., trade name) in a pressurized reaction vessel equipped with a stirrer, heating / cooling device, thermometer and nitrogen introduction tube “HS2H-1000S”) 204 parts, 2,2-dimethylolpropionic acid 8 parts, 1,4-butanediol 10 parts, HDI 28 parts, and MEK 250 parts. Thereafter, the mixture was heated to 80 ° C. and subjected to urethanization reaction for 10 hours to obtain a solution of urethane prepolymer (A-5).

Production Example 12
[Production of aqueous dispersion (Wp-5) of polyurethane urea crystalline resin (P-5)]
In Production Example 4, the solution of (A-1) was added to the solution of (A-5), 5.3 parts of triethylamine was 6.2 parts, 1.9 parts of n-butylamine and 4.5 parts of hexamethylenediamine were added. Except for 0.2 parts of n-butylamine and 2.2 parts of hexamethylenediamine, the same operation as in Production Example 4 was performed, and the aqueous solution of polyurethane urea crystalline resin (P-5) having a solid content concentration of 25% A dispersion (Wp-5) was obtained.
Mn of (P-5) obtained by washing and drying was 161,000, and the melting point was 66 ° C.

Production Example 13
[Production of Urethane Prepolymer (A-6)]
208 parts of polycarbonate diol having a Mn of 2,000 (trade name “PLAXEL CD220”, manufactured by Daicel Corporation) in a pressurized reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer and a nitrogen introduction tube, 2,2- 7 parts of dimethylolpropionic acid, 35 parts of HDI, and 250 parts of acetone were charged. Thereafter, the mixture was heated to 80 ° C. and subjected to urethanization reaction for 10 hours to obtain a urethane prepolymer (A-6) solution.

Production Example 14
[Production of aqueous dispersion (Wp-6) of polyurethane urea crystalline resin (P-6)]
In Production Example 4, except that the solution of (A-1) was changed to the solution of (A-6), the same operation as in Production Example 4 was performed, and the polyurethane urea crystalline resin (P An aqueous dispersion (Wp-6) of -6) was obtained.
Mn of (P-6) obtained by washing and drying was 20,000, and its melting point was 54 ° C.

Production Example 15
[Production of aqueous dispersion (Wp-7) of polyurethane urea crystalline resin (P-7)]
After cooling 500 parts of the urethane prepolymer (A-1) solution to 40 ° C., 1.9 parts of n-butylamine and 4.5 parts of hexamethylenediamine were added, and a chain elongation reaction was carried out for 3 hours while stirring. Next, 5.3 parts of triethylamine was added and the neutralized product obtained by stirring at 40 ° C. for 30 minutes was poured into 750 parts of ion-exchanged water, and dispersed using a TK auto homomixer (manufactured by Primics Co., Ltd.). After that, the solvent was distilled off at 50 ° C. under a reduced pressure of 30 kPa, and ion-exchanged water was added for the purpose of adjusting the solid content concentration. The polyurethane urea crystalline resin (P-7) having a solid content concentration of 25% An aqueous dispersion (Wp-7) of was obtained.
Mn of (P-7) obtained by washing and drying was 18,000, and the melting point was 67 ° C.

Comparative production example 1
[Production of Aqueous Dispersion (Wp′-1) of Polyurethane Crystalline Resin (P′-1) Not Elongated with Diamine]
To 500 parts of the urethane prepolymer (A-1) solution, 1.9 parts of n-butyl alcohol and 2.4 parts of ethylene glycol were added, and a chain elongation reaction was performed for 10 hours while stirring at 80 ° C. After cooling to 40 ° C., 5.3 parts of triethylamine is added and stirred for 30 minutes, and the neutralized product obtained is poured into 750 parts of ion-exchanged water and dispersed using a TK auto homomixer (manufactured by Primics Co., Ltd.). After that, the solvent was distilled off at 50 ° C. under a reduced pressure of 30 kPa, and ion-exchanged water was added for the purpose of adjusting the solid content concentration. A polyurethane crystalline resin (P′-1) having a solid content concentration of 25% was added. ) Aqueous dispersion (Wp′-1) was obtained.
Mn of (P′-1) obtained by washing and drying was 20,000, and the melting point was 65 ° C.

Comparative production example 2
[Production of urethane prepolymer (A′-2) not containing carboxyl group-containing diol (b)]
Polyester diol having a Mn of 2,000 consisting of 1,6-hexanediol and sebacic acid in a pressurized reaction vessel equipped with a stirrer, heating / cooling device, thermometer and nitrogen introduction tube "HS2H-200S") 222 parts, HDI 28 parts, and acetone 250 parts were charged. Thereafter, the mixture was heated to 80 ° C. and subjected to urethanization for 10 hours to obtain a urethane prepolymer (A′-2) solution.

Comparative production example 3
[Production of aqueous dispersion (Wp′-2) of polyurethane urea crystalline resin (P′-2) not containing carboxyl group-containing diol (b)]
After cooling 500 parts of the urethane prepolymer (A′-2) solution to 40 ° C., adding 12.5 parts of sodium dodecylbenzenesulfonate as a surfactant and stirring for 30 minutes, it was poured into 750 parts of ion-exchanged water, The mixture was dispersed using a TK auto homomixer (manufactured by Primics Co., Ltd.), then 1.9 parts of n-butylamine and 4.5 parts of hexamethylenediamine were added, and the mixture was allowed to undergo chain extension reaction for 5 hours with stirring. Aqueous dispersion of polyurethane urea crystalline resin (P′-2) having a solid content concentration of 25% by adding ion-exchanged water for the purpose of adjusting the solid content concentration by distilling off the solvent at 30 ° C. under reduced pressure of 30 kPa. A body (Wp′-2) was obtained.
Mn of (P′-2) obtained by washing and drying was 24,000, and the melting point was 66 ° C.

Comparative production example 4
[Production of Urethane Prepolymer (A′-3) not Containing Polymer Diol (a) with Mn of 500 to 20,000]
85 parts of polyethylene glycol (trade name “PEG-400” manufactured by Sanyo Chemical Industries, Ltd.) having a Mn of 400 in a pressure reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a nitrogen introduction tube, 2, 2 -7 parts of dimethylolpropionic acid, 51 parts of 1,9-nonanediol, 107 parts of HDI and 250 parts of acetone were charged. Then, it heated at 80 degreeC and urethanation reaction was performed for 10 hours, and the solution of the urethane prepolymer (A'-3) was obtained.

Comparative Production Example 5
[Production of Aqueous Dispersion (Wp′-3) of Polyurethane Urea Crystalline Resin (P′-3) not Containing Polymer Diol (a) with Mn of 500 to 20,000]
In Production Example 4, the solution of (A-1) was changed to the solution of (A′-3), 5.3 parts of triethylamine was added to 5.4 parts, 1.9 parts of n-butylamine and 4.5 parts of hexamethylenediamine. A polyurethane urea crystalline resin (P′-3) having a solids concentration of 25% was prepared in the same manner as in Production Example 4 except that 2.0 parts of n-butylamine and 4.6 parts of hexamethylenediamine were used. An aqueous dispersion (Wp′-3) was obtained.
Mn of (P′-3) obtained by washing and drying was 23,000, and the melting point was 53 ° C.

Production Example 16
[Production of non-crystalline resin (Q-1, polyester resin)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube, a nitrogen introduction tube and a decompression device, 522 parts of 1,2-propylene glycol, 468 parts of terephthalic acid, 90 parts of adipic acid, 20 parts of benzoic acid, 26 parts of trimellitic anhydride and 3 parts of tetrabutoxy titanate as a condensation catalyst were added and reacted at 170 ° C. under pressure for 8 hours while distilling off generated water. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 12 hours while distilling off the water produced, and the reaction is further carried out under a reduced pressure of 0.5 to 2.5 kPa, and the reaction is cooled when Tm reaches 130 ° C. To obtain an amorphous resin (Q-1H) having a high softening point. Tg of (Q-1H) was 66 ° C. and Tm was 130 ° C.

In a separate reaction vessel, 458 parts 1,2-propylene glycol, 40 parts propylene oxide 2-mole adduct of bisphenol A, 493 parts terephthalic acid, 6 parts adipic acid, 70 parts benzoic acid, 46 parts trimellitic anhydride, And 3 parts of tetrabutoxy titanate was added as a condensation catalyst, and the reaction was carried out for 8 hours while distilling off the water produced under pressure at 170 ° C. Next, while gradually raising the temperature to 220 ° C., the reaction is carried out for 12 hours while distilling off the generated water, and further under a reduced pressure of 0.5 to 2.5 kPa. When Tm reaches 105 ° C., normal pressure is reached. And cooled to 180 ° C. Next, after 14 parts of trimellitic anhydride was added and reacted for 1 hour, it was cooled and taken out to obtain an amorphous resin (Q-1L) having a low softening point. Tg of (Q-1L) was 62 ° C. and Tm was 105 ° C.
The obtained (Q-1H) and (Q-1L) were homogenized with a Henschel mixer ("FM10B" manufactured by Nippon Coke Industries) so that the weight ratio (Q-1H) / (Q-1L) was 50/50. A noncrystalline resin (Q-1) was obtained.

Production Example 17
[Production of Aqueous Dispersion (Wq-1) of Amorphous Resin (Q-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device and a thermometer, 400 parts of an amorphous resin (Q-1) and 200 parts of MEK are added and dissolved, and 20 parts of sodium dodecylbenzenesulfonate is added as a surfactant. After stirring for 30 minutes, the mixture is poured into 600 parts of ion-exchanged water, dispersed using a TK auto homomixer (manufactured by Primics Co., Ltd.), and the solvent is distilled off at 50 ° C. under a reduced pressure of 30 kPa. For the purpose of adjusting the concentration, ion-exchanged water was added to obtain an aqueous dispersion (Wq-1) of an amorphous resin (Q-1) having a solid content concentration of 40%.

Production Example 18
[Production of Aqueous Dispersion (Wq-2) of Amorphous Resin (Q-2, Vinyl Resin)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer, 240 parts of styrene, 60 parts of n-butyl methacrylate, 92 parts of methyl methacrylate, and 8 parts of acrylic acid are weighed and stirred for homogenization. An oily liquid was obtained.
In another reaction vessel, 10 parts of tricalcium phosphate was added to 600 parts of ion-exchanged water to adjust the aqueous medium, and the temperature was adjusted to 70 ° C. 16 parts of t-butyl peroxypivalate which is a polymerization initiator is added to the oily liquid, this is put into an aqueous medium, and stirred at 10,000 rpm for 5 minutes with a TK auto homomixer (manufactured by Primics Co., Ltd.) The oily liquid was dispersed in an aqueous medium. Thereafter, the stirrer was changed to a propeller stirring blade, and polymerization was performed for 8 hours while maintaining 70 ° C. while stirring at 200 rpm. Ion exchange water was added for the purpose of adjusting the solid content concentration to obtain an aqueous dispersion (Wq-2) of an amorphous resin (Q-2) having a solid content concentration of 40%. Tg of (Q-2) obtained by washing and drying was 64 ° C. and Tm was 120 ° C.

Production Example 19
[Production of Colorant Aqueous Dispersion (Wc-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, 20 parts of carbon black (trade name “MA100” manufactured by Mitsubishi Chemical Corporation), 1 part of sodium dodecylbenzenesulfonate, and ion-exchanged water 80 parts was added, the temperature was raised to 30 ° C. with stirring, the mixture was stirred at the same temperature for 30 minutes, and then wet pulverized with Ultravisco mill (manufactured by Imex), and ion-exchanged water was added for the purpose of adjusting the solid content concentration. An aqueous colorant dispersion (Wc-1) having a solid content concentration of 20% was obtained.

Production Example 20
[Production of Release Agent Aqueous Dispersion (Wr-1)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, 20 parts of paraffin wax (manufactured by Nippon Seiki Co., Ltd., trade name “HNP-9”), 1 part of sodium dodecylbenzenesulfonate, and Add 80 parts of ion-exchanged water, raise the temperature to 78 ° C. with stirring, stir at the same temperature for 30 minutes, cool to 30 ° C. over 1 hour to crystallize the paraffin wax into fine particles, and further ultraviscomil For the purpose of adjusting the solid content concentration by wet pulverization (made by Imex), ion-exchanged water was added to obtain an aqueous release agent dispersion (Wr-1) having a solid content concentration of 20%.

Examples 1-8, Comparative Examples 1-5
[Production of toner]
In a reaction vessel equipped with a stirrer, a dripping device, a heating / cooling device, a temperature sensor, a cooling pipe, and a nitrogen introducing device, an aqueous dispersion (Wp) of polyurethane urea crystalline resin (P), an amorphous resin (Q) The aqueous dispersion (Wq), the colorant aqueous dispersion (Wc), and the release agent aqueous dispersion (Wr) were charged so as to have the solid content shown in Table 1, and mixed to obtain the dispersion (W). Thereafter, 1,000 parts of ion-exchanged water was added and the liquid temperature was adjusted to 30 ° C., and then a 25% aqueous sodium hydroxide solution was added to adjust the pH to 10.0.

Next, an aqueous solution in which 54 parts of magnesium chloride hexahydrate is dissolved in 54 parts of ion-exchanged water is dropped, and the polyurethane urea crystalline resin (P) in the dispersion (W) (or a comparative polyurethane if necessary) Urea crystalline resin (P ′)), amorphous resin (Q), colorant (C) and release agent (R) are aggregated to obtain a particle size distribution measuring device (“Coulter Multisizer 3” manufactured by Beckman Coulter, Inc.) The sample was appropriately sampled using and was confirmed to have a particle size of 5 μm, and then the temperature of the system was raised to 60 ° C. to perform heat fusion. Thereafter, the mixture was cooled to 30 ° C. to obtain a dispersion of toner particles.
Next, the aqueous medium was removed by washing, filtering, and drying at 40 ° C. for 18 hours to obtain toner particles having a volatile content of 0.5% or less. Toners (T-1) to (T-1) to (T) obtained by uniformly mixing 100 parts of the obtained toner particles and 0.5 parts of colloidal silica (product name “Aerosil R972” manufactured by Nippon Aerosil Co., Ltd.) -8) and comparative toners (T′-1) to (T′-5).

  Toners (T-1) to (T-8) obtained by the toner production method of the present invention obtained in Examples 1 to 8 and comparative toners (T′-1) to (T) obtained in Comparative Examples 1 to 5 Regarding '-5), the low-temperature fixability, the hot offset resistance, the heat-resistant storage stability, and the charging stability were evaluated by the evaluation methods described below. The results are shown in Table 1.

[Evaluation method]
A measurement method and an evaluation method for low-temperature fixability, hot offset resistance, heat-resistant storage stability, and charging stability will be described including criteria.

<Low temperature fixability>
The toner is uniformly placed on the paper so as to be 0.85 mg / cm ² . At this time, as a method of placing the powder on the paper surface, a printer from which the heat fixing machine is removed is used. Other methods may be used as long as the powder can be uniformly loaded with the above-described weight density.
A cold offset generation temperature (MFT) was measured 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 10 kg / cm ² .
The lower the temperature at which cold offset occurs, the better the low-temperature fixability. Under these measurement conditions, 120 ° C. or lower is generally preferable.

<Hot offset resistance (hot offset temperature)>
Fixation was evaluated in the same manner as the 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.). Under these measurement conditions, 180 ° C. or higher is generally preferable.

<Heat resistant storage stability>
The toner 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.
[Criteria]
○: Blocking has not occurred.
Δ: Blocking occurs in part.
X: Blocking has occurred throughout.

<Charging stability>
(1) 0.5 g of toner and 20 g of ferrite carrier (“F-150” manufactured by Powdertech Co., Ltd.) are put in a 50 ml glass bottle, and this is conditioned at 23 ° C. and 50% relative humidity for 8 hours or more.
(2) Friction stirring was performed at 50 rpm × 20 minutes and 60 minutes with a tumbler shaker mixer, and the charge amount at each time was measured.
A blow-off charge measuring device (manufactured by Toshiba Chemical Corporation) was used for the measurement.
“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]
○: Charge amount of 60 minutes of friction time / charge amount of 10 minutes of friction time is 0.7 or more Δ: 0.6 or more and less than 0.7 ×: Less than 0.6

The toners (T-1) to (T-8) obtained by the toner production method of the present invention obtained in Examples 1 to 8 showed excellent results in any performance evaluation items.
On the other hand, the comparative toner (T′-1) obtained in Comparative Example 1 containing no (P) and containing only (Q) has remarkably poor low-temperature fixability, and instead of (P), a polyurethane crystal that does not extend diamine. The comparative toner (T′-2) obtained in Comparative Example 2 using the conductive resin (P′-1) had poor hot offset resistance and heat resistant storage stability.
Further, the comparative toner (T′-3) obtained in Comparative Example 3 using the polyurethane urea crystalline resin (P′-2) not containing the carboxyl group-containing diol (b) instead of (P) is charged stable. Comparison obtained in Comparative Example 4 using polyurethane urea crystalline resin (P′-3) not containing polymer diol (a) having Mn of 500 to 20,000 instead of (P) The toner (T′-4) had poor hot offset resistance and charging stability.
The comparative toner (T′-5) obtained in Comparative Example 5 containing only (P) but not containing (Q) was poor in hot offset resistance, heat resistant storage stability and charging stability.

  The toner obtained by the toner production method of the present invention is highly compatible with hot offset resistance and low-temperature fixability, and is excellent in heat storage stability and charge stability. It is useful as an electroprinting toner.

Claims (12)

  A toner comprising a polyurethane urea crystalline resin (P), an amorphous resin (Q) and a colorant (C), wherein the polyurethane urea crystalline resin (P) comprises a urethane prepolymer (A) and a diamine (e). The urethane prepolymer (A) is a urethane prepolymer containing a polymer diol (a), a carboxyl group-containing diol (b), and a diisocyanate (c) as constituent raw materials. A toner having (a) a number average molecular weight of 500 to 20,000.   The toner according to claim 1, wherein the polymer diol (a) is a polyester diol.   The toner according to claim 1, wherein the polyurethane urea crystalline resin (P) has a number average molecular weight of 3,000 to 200,000.   The toner according to claim 1, wherein the polyurethane urea crystalline resin (P) has a melting point of 50 to 90 ° C. 5.   The toner according to claim 1, wherein the carboxyl group-containing diol (b) is α, α-dimethylolalkanoic acid.   The toner according to claim 1, wherein the urethane prepolymer (A) further contains a diol (d) having a number average molecular weight of less than 500 excluding the carboxyl group-containing diol (b) as a constituent raw material.   The toner according to claim 1, wherein the amorphous resin (Q) is at least one amorphous resin selected from the group consisting of a polyester resin, a polyurethane resin, an epoxy resin, and a vinyl resin.   The toner according to claim 1, wherein the weight ratio (P) / (Q) of the polyurethaneurea crystalline resin (P) and the amorphous resin (Q) is 2/98 to 50/50.   The toner according to claim 1, further comprising a release agent (R).   10. The method for producing a toner according to claim 1, wherein the urethane prepolymer (A) is chain-extended with the diamine (e) in a dispersion state in which the urethane prepolymer (A) is dispersed in the aqueous medium (X). A method for producing a toner comprising a step of obtaining a polyurethane urea crystalline resin (P).   10. The method for producing a toner according to claim 1, wherein a neutralized product (N) of the urethane prepolymer (A) and the base (B) is dispersed in the aqueous medium (X). In this state, the method for producing a toner includes a step of obtaining a polyurethane urea crystalline resin (P) by extending a chain with diamine (e).   In the state of dispersion (W) in which the polyurethane urea crystalline resin (P), the amorphous resin (Q) and the colorant (C) are dispersed in the aqueous medium (X), the polyurethane urea crystalline resin (P), The method for producing a toner according to claim 10 or 11, comprising a step of removing the aqueous medium (X) after the amorphous resin (Q) and the colorant (C) are aggregated and thermally fused.