JP2018165816A - Toner binder and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner binder that achieves low-temperature fixability, glossiness, and hot offset resistance, and is excellent in heat-resistant storage property, charge stability, image strength, and document offset resistance of toner, and toner.SOLUTION: A toner binder contains a crystalline resin (A) containing an alcohol component (x) and a carboxylic acid component (y) as constitutional materials, where the carboxylic acid component (y) contains straight-chain aliphatic dicarboxylic acid (y1) having odd number in 5 to 15 of carbon atoms in an amount of 50 mol% or more based on the number of moles of the carboxylic acid component (y), and a cyclic ester compound derived from the crystalline resin (A) in an amount of 0.01 wt.% to 1 wt.% based on the weight of the toner binder.SELECTED DRAWING: None

Description

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

In recent years, there has been a strong demand for improvement in low-temperature fixability of toners from the viewpoint of energy saving, that is, reduction of energy consumption in the fixing process as well as promotion of downsizing, high speed and high image quality of electrophotographic apparatuses.
As a means for lowering the toner fixing temperature, a technique for lowering the glass transition point of the binder resin is generally used.
However, if the glass transition point is too low, the hot offset resistance is reduced, and the aggregation of the powder (blocking) is likely to occur, so the storage stability of the toner is reduced. Therefore, the lower limit of the glass transition point is practically used. 50 ° C. This glass transition point is a design point of the binder resin, and a toner that can be fixed at a lower temperature cannot be obtained by a method of lowering the glass transition point.

  Among them, a toner composition containing a polyester-based toner binder that is excellent in both low-temperature fixability and hot offset resistance is known (see Patent Documents 1 and 2). However, in recent years, there has been an increasing demand for storage stability and compatibility between low-temperature fixability and hot offset resistance (fixing temperature range), which is still insufficient.

As another method, it is known that the use of an amorphous resin and a crystalline resin in combination with the binder resin improves the low-temperature fixability and glossiness of the toner due to the melting characteristics of the crystalline resin.
However, if the content of the crystalline resin is increased, the resin strength may decrease, and the crystalline resin becomes amorphous due to the compatibilization of the crystalline resin and the binder resin during melt kneading, resulting in a glass transition of the toner. The problem similar to the above arises because the point is lowered.

On the other hand, a method of regenerating the crystallinity of the crystalline resin by performing a heat treatment after the melt-kneading step (Patent Document 3), a method of changing the monomer component to be used (Patent Documents 4 to 6), and the like have been proposed.
Such a method can secure the low-temperature fixability and glossiness of the toner, but has a problem that the hot offset resistance, the fluidity of the toner, and the pulverization property during pulverization are reduced. Furthermore, they have a problem that the amount of cyclic ester compound produced as an impurity when synthesizing a crystalline resin is large, and heat resistance storage stability and charging stability at high temperature and high humidity are lowered.
A method of coating with a shell layer obtained using a melt suspension method or an emulsion aggregation method has also been proposed (Patent Documents 7 to 10). However, the crystalline resin is compatible with the binder resin of the core and is short. Due to insufficient time for reprecipitation of crystals, image strength after fixing and bending resistance are still insufficient.

JP 2005-77930 A JP 2012-98719 A JP 2005-308995 A JP 2012-8371 A JP 2007-292816 A International Publication No. 2015/170705 JP 2011-197193 A JP 2011-197192 A JP 2011-186053 A JP 2006-251564 A

  An object of the present invention is to provide a toner binder and a toner that are excellent in heat-resistant storage stability, charging stability, image strength, and document offset property of a toner while achieving both low-temperature fixability, glossiness, and hot offset resistance. To do.

  As a result of intensive studies to solve these problems, the present inventors have reached the present invention. That is, the present invention is a toner binder containing a crystalline resin (A) having an alcohol component (x) and a carboxylic acid component (y) as constituent raw materials, wherein the carboxylic acid component (y) has a carbon number. The linear aliphatic dicarboxylic acid (y1) which is an odd number of 5 to 15 is contained in an amount of 50 mol% or more based on the number of moles of the carboxylic acid component (y), and the cyclic ester compound derived from the crystalline resin (A) is added in an amount of 0.00. A toner binder containing from 01% by weight to 1% by weight.

  According to the present invention, it is possible to provide a toner binder and a toner excellent in heat-resistant storage stability, charging stability, image strength, and document offset property of a toner while achieving both low-temperature fixability, glossiness, and hot offset resistance. became.

The present invention is described in detail below.
The toner binder of the present invention is a toner binder containing a crystalline resin (A) having an alcohol component (x) and a carboxylic acid component (y) as constituent materials, and the carboxylic acid component (y) contains carbon atoms. A cyclic ester compound derived from the crystalline resin (A), containing 50 mol% or more of a linear aliphatic dicarboxylic acid (y1) having an odd number of 5 to 15 carbon atoms based on the number of moles of the carboxylic acid component (y) Is contained in an amount of 0.01% by weight to 1% by weight.
In addition, carbon number of a carbonyl group shall be included in carbon number 5-15 of linear aliphatic dicarboxylic acid (y1).

  The toner binder of the present invention contains the crystalline resin (A) as an essential component. “Crystallinity” in the present invention refers to a resin having a clear endothermic peak rather than a stepwise change in endothermic amount in the first temperature rising process of DSC measurement described later.

The crystalline resin (A) is composed of an alcohol component (x) and a carboxylic acid component (y) as constituent raw materials, and the carboxylic acid component (y) is a linear aliphatic dicarboxylic acid having an odd number of 5 to 15 carbon atoms. If it is an acid (y1), the chemical structure in particular will not be limited.
Examples of the crystalline resin (A) include crystalline polyester (a11), crystalline polyurethane (a12), crystalline polyurea (a13), crystalline polyamide (a14), and crystalline polyvinyl (a15). Among these, those having one or more groups selected from the group consisting of ester groups, urethane groups, urea groups, amide groups, epoxy groups, and vinyl groups are preferable. The alcohol component (x) and the carboxylic acid component (y The crystalline polyester (a11) is more preferable from the viewpoint of ease of introduction. These crystalline resins may be used in combination.

  A more preferable crystalline polyester (a11) is a polyester resin obtained by reacting an alcohol component (x) with a carboxylic acid component (y).

  Examples of the alcohol component (x) include a diol component (x1), a trivalent or higher valent alcohol component (x2), and the like.

  Examples of the diol of the diol component (x1) include aliphatic diols, alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); 4 to 36 alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); alkylene oxides of the above alicyclic diols (hereinafter “alkylene oxide” is abbreviated as AO) [ethylene oxide (hereinafter referred to as “AO”) , “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.) Product (addition mole number 1-30); AO (EO, PO, BO, etc.) addition product (addition mole number 2-30) of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); polylactone diol (polyε -Caprolactone diol etc.); polybutadiene diol etc. are mentioned. Two or more of these may be used in combination.

  Among these diols, aliphatic diols are preferable from the viewpoint of crystallinity. Preferably carbon number is 2-36, More preferably, it is the range of 2-20. Further, from the same viewpoint, a linear aliphatic diol is preferable to a branched aliphatic diol.

  Examples of the linear aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1 , 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, , 18-octadecanediol, 1,20-eicosanediol, etc., and alkylene glycols having 2 to 20 carbon atoms. Of these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10 are preferable from the viewpoint of low-temperature fixability and heat-resistant storage stability. -Decanediol and 1,12-dodecanediol.

  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 (x1) used.

Examples of the trivalent or higher alcohol component (x2) include trivalent or higher polyols, specifically, polyols having a valence of 3 to 8 or higher.
The polyol having a valence of 3 to 8 or higher that is used in combination with the diol component (x1) as necessary includes a polyhydric aliphatic alcohol (alkane having a valence of 3 to 8 or more having 3 to 36 carbon atoms). Polyols and intramolecular or intermolecular dehydrates thereof such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin; sugars and derivatives thereof such as sucrose and methylglucoside); trisphenols AO adduct (addition mole number 2-30) of (trisphenol PA etc.); AO adduct (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [hydroxyethyl (meth) Copolymer of acrylate and other vinyl monomers ]; And the like.

  Of these, preferred are polyhydric aliphatic alcohols having a valence of 3 to 8 or higher and AO adducts of novolac resins, and more preferred are AO adducts of novolac resins.

The crystalline polyester (a11) 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 component (x1). A diol (x1 ′) having at least one group may be a structural unit.
By using the diol (x1 ′) having these functional groups as a structural unit, the chargeability and heat resistant storage stability of the toner are improved.
The “acid (salt)” in the present invention means an acid or an acid salt.
A polyester resin obtained by reacting a diol component (x1), a diol (x1 ′) having a functional group and a carboxylic acid component (y) as raw materials is preferred as the crystalline polyester (a11). The diol (x1 ′) having a functional group may be used alone or in combination of two or more.

  Examples of the diol (x1 ′) having a carboxylic acid (salt) group include tartaric acid (salt), 2,2-bis (hydroxymethyl) propanoic acid (salt), and 2,2-bis (hydroxymethyl) butanoic acid (salt). And 3- [bis (2-hydroxyethyl) amino] propanoic acid (salt) and the like.

  Examples of the diol (x1 ′) having a sulfonic acid (salt) group include 2,2-bis (hydroxymethyl) ethanesulfonic acid (salt) and 2- [bis (2-hydroxyethyl) amino] ethanesulfonic acid (salt). And 5-sulfo-isophthalic acid-1,3-bis (2-hydroxyethyl) ester (salt) and the like.

  Examples of the diol (x1 ′) having a sulfamic acid (salt) group include N, N-bis (2-hydroxyethyl) sulfamic acid (salt), N, N-bis (3-hydroxypropyl) sulfamic acid (salt), Examples thereof include N, N-bis (4-hydroxybutyl) sulfamic acid (salt) and N, N-bis (2-hydroxypropyl) sulfamic acid (salt).

Examples of the diol (x1 ′) 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 the functional group-containing diols (x1 ′), those having a carboxylic acid (salt) group-containing diol (x1 ′) and a sulfonic acid (salt) group are preferable from the viewpoint of toner chargeability and heat-resistant storage stability. Diol (x1 ′).

  Examples of the carboxylic acid component (y) include linear aliphatic dicarboxylic acids (y1) having an odd number of 5 to 15 carbon atoms (y1) and other polycarboxylic acids (y2) other than (y1).

  Examples of the linear aliphatic dicarboxylic acid (y1) having an odd number of carbon atoms of 5 to 15 include 1,3-propanedicarboxylic acid, 1,5-pentanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 1, Examples include 9-nonanedicarboxylic acid, 1,11-undecanedicarboxylic acid, and 1,13-tridecanedicarboxylic acid. Of these, 1,5-pentanedicarboxylic acid, 1,7-heptanedicarboxylic acid, 1,9-nonanedicarboxylic acid, and more preferably 1,7-heptanedicarboxylic acid are preferred from the viewpoint of heat-resistant storage stability and charging characteristics. is there.

Examples of the other polycarboxylic acid (y2) include dicarboxylic acids different from (y1) and trivalent or higher carboxylic acid components.
Examples of dicarboxylic acids include alkanedicarboxylic acids having 2 to 50 carbon atoms (including carbon in the carbonyl group) (1,12-dodecanedicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedioic acid, octadecanedicarboxylic acid, and decylsuccinic acid. Alkene dicarboxylic acids having 4 to 50 carbon atoms (alkenyl succinic acids such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, etc.); -40 cycloaliphatic dicarboxylic acid [dimer acid (dimerized linoleic acid), etc.]; C8-36 aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6- Naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid and the like). Two or more of these may be used in combination.

Examples of the trivalent or higher carboxylic acid component include polycarboxylic acids having a valence of 3 to 6 or higher. Examples of polycarboxylic acids having 3 to 6 or more valences include, for example, aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and aliphatic tricarboxylic acids having 6 to 36 carbon atoms. (Hexanetricarboxylic acid etc.), vinyl polymer of unsaturated carboxylic acid [number average molecular weight (Mn): 450-10,000] (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, and styrene / fumarate) Acid copolymer, etc.).
The number average molecular weight (Mn) is determined by gel permeation chromatography (GPC).

Among these carboxylic acids, it is preferable to use an aliphatic dicarboxylic acid of an alkane dicarboxylic acid and an alkene dicarboxylic acid from the viewpoint of crystallinity, and an aliphatic dicarboxylic acid having 2 to 50 carbon atoms and an aliphatic dicarboxylic acid having 4 to 50 carbon atoms. A group dicarboxylic acid is more preferable, and a linear dicarboxylic acid is particularly preferable. For example, adipic acid, sebacic acid, dodecanedioic acid and the like are particularly preferable.
Likewise preferred are those obtained by copolymerizing an aliphatic dicarboxylic acid and an aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, t-butylisophthalic acid, and lower alkyl esters thereof). The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

  The content of the linear aliphatic dicarboxylic acid (y1) having an odd number of carbon atoms of 5 to 15 with respect to the number of moles of the carboxylic acid component (y) is based on the number of moles of the carboxylic acid component (y). It is 50 mol% or more. Further, from the viewpoint of heat resistant storage stability and charging characteristics, it is preferably 70 mol% or more, particularly preferably 90 mol% or more. When the content of (y1) is less than 50 mol%, the content of the cyclic ester compound is increased, so that the heat resistant storage stability and charging characteristics may be problematic.

As the crystalline polyurethane (a12), those having the crystalline polyester (a11) and the diisocyanate (v2) as structural units, and the crystalline polyester (a11), the diol component (x) and the diisocyanate (v2) are used. And the like as structural units.
The crystalline polyurethane (a12) having the crystalline polyester (a11) and the diisocyanate (v2) as structural units can be obtained by reacting the crystalline polyester (a11) and the diisocyanate (v2). The crystalline polyurethane (a12) having the crystalline polyester (a11), the diol component (x1) and the diisocyanate (v2) as structural units is obtained by reacting the crystalline polyester (a11), the diol component (x1) and the diisocyanate (v2). Can be obtained.

  In addition to the diol component (x1), the diol (x1 ′) having the functional group described above is used as a structural unit, whereby the chargeability and heat resistant storage stability of the toner are improved.

  As the diisocyanate (v2), an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, a modified product of these diisocyanates (urethane group, Carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified product) and mixtures of two or more thereof.

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

Examples of the aliphatic diisocyanate having 2 to 18 carbon atoms include a chain aliphatic diisocyanate having 2 to 18 carbon atoms and a cyclic aliphatic diisocyanate having 3 to 18 carbon atoms.
Examples of the chain aliphatic diisocyanate having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6- And diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and mixtures thereof. It is done.

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

  The modified product of diisocyanate is a modified product containing at least one selected from the group consisting of urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group. Etc., modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), urethane modified TDI and mixtures thereof [for example, mixtures of modified MDI and urethane modified TDI (isocyanate-containing prepolymer)], etc. Is mentioned.

  Among these diisocyanates (v2), aromatic diisocyanates having 6 to 15 carbon atoms and aliphatic diisocyanates having 4 to 15 carbon atoms are more preferable, and TDI, MDI, HDI, hydrogenated MDI and IPDI are more preferable. It is.

Crystalline polyurea (a13)
Examples of the crystalline polyurea (a13) include those having the crystalline polyester (a11), the diamine (z), and the diisocyanate (v2) as structural units. Such crystalline polyurea (a13) can be obtained by reacting crystalline polyester (a11), diamine (z) and diisocyanate (v2).

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

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

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

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

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

  As the diisocyanate (v2), an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group; the same shall apply hereinafter), an aliphatic diisocyanate having 2 to 18 carbon atoms, a modified product of these diisocyanates (urethane group, Carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group-containing modified product) and mixtures of two or more thereof.

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

Examples of the aliphatic diisocyanate having 2 to 18 carbon atoms include a chain aliphatic diisocyanate having 2 to 18 carbon atoms and a cyclic aliphatic diisocyanate having 3 to 18 carbon atoms.
Examples of the chain aliphatic diisocyanate having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6- And diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and mixtures thereof. It is done.

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

  The modified product of diisocyanate is a modified product containing at least one selected from the group consisting of urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group and oxazolidone group. Etc., modified MDI (urethane modified MDI, carbodiimide modified MDI, trihydrocarbyl phosphate modified MDI, etc.), urethane modified TDI and mixtures thereof [for example, mixtures of modified MDI and urethane modified TDI (isocyanate-containing prepolymer)], etc. Is mentioned.

  Among these diisocyanates (v2), aromatic diisocyanates having 6 to 15 carbon atoms and aliphatic diisocyanates having 4 to 15 carbon atoms are more preferable, and TDI, MDI, HDI, hydrogenated MDI and IPDI are more preferable. It is.

Crystalline polyamide (a14)
Examples of the crystalline polyamide (a14) include those having the crystalline polyester (a11), the diamine (z), and the dicarboxylic acid component (y) as structural units. Such a crystalline polyamide (a14) can be obtained by reacting the crystalline polyester (a11), the diamine (z) and a dicarboxylic acid component.

Crystalline polyvinyl resin (a15)
Examples of the crystalline polyvinyl resin (a15) include a polymer obtained by homopolymerizing or copolymerizing an ester having a polymerizable double bond.
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-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meta ) Acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxy acrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate , Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) ) Acrylate and eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (two The alkyl group is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes (dialyloxyethane, triaryloxyethane, tetraallyloxyethane) Monomers having a polyalkylene glycol chain and a polymerizable double bond, such as tetraallyloxypropane, tetraallyloxybutane and tetrametaallyloxyethane, etc. [polyethylene glycol (Mn = 300) mono (meth) acrylate, polypropylene Glycol (Mn = 500) monoacrylate, methyl alcohol EO 10 mol adduct (meth) acrylate and laur Lyl alcohol EO 30 mol adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate 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 and the like] and the like.

  In addition to the ester having a polymerizable double bond, the crystalline polyvinyl resin (a15) can contain compounds such as the following monomers (w1) to (w9) as constituent monomers.

Monomer (w1) Hydrocarbon having a polymerizable double bond:
Examples thereof include the following aliphatic hydrocarbon (w11) having a polymerizable double bond and aromatic hydrocarbon (w12) having a polymerizable double bond.
Aliphatic hydrocarbon having a polymerizable double bond (w11):
For example, the following (w111) and (w112) are mentioned.
Chain hydrocarbon (w111) having a polymerizable double bond: Alkene having 2 to 30 carbon atoms (for example, isoprene, 1,4-pentadiene, 1,5-hexadiene, 1,7-octadiene, etc.).
Cyclic hydrocarbon having a polymerizable double bond (w112): mono- or dicycloalkene having 6 to 30 carbon atoms (for example, 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.

Aromatic hydrocarbon having a polymerizable double bond (w12):
Styrene; hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl having 1 to 30 carbon atoms) substitution of styrene (for example, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, Butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, and trivinyl benzene); and vinyl naphthalene.

Monomers having a carboxyl group and a polymerizable double bond and their salts (w2):
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.

Monomers having a sulfo group and a polymerizable double bond and their salts (w3):
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 and the like]; sulfo (hydroxy) alkyl (meth) acrylamide having 5 to 18 carbon atoms [for example, 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 (w2) of the monomer which has a carboxyl group and a polymerizable double bond is mentioned.

Monomer having phosphono group and polymerizable double bond and salt thereof (w4):
(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 Examples thereof include phosphonic acid (alkyl group having 1 to 24 carbon atoms) (for example, 2-acryloyloxyethylphosphonic acid) and the like.
In addition, as a salt, what was illustrated as a salt (w2) which comprises the monomer which has a carboxyl group and a polymerizable double bond is mentioned.

Monomer (w5) 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- Examples include buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, and sucrose allyl ether.

Nitrogen-containing monomer having a polymerizable double bond (w6):
For example, a monomer having an amino group and a polymerizable double bond (w61), a monomer having an amide group and a polymerizable double bond (w62), a carbon number of 3 to 3 having a nitrile group and a polymerizable double bond 10 monomer (w63), C8-C12 monomer (w64) having a nitro group and a polymerizable double bond, and the like.
Monomer having amino group and polymerizable double bond (w61):
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.

Monomer having amide group and polymerizable double bond (w62):
(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.
Monomer having 3 to 10 carbon atoms having a nitrile group and a polymerizable double bond (w63):
(Meth) acrylonitrile, cyanostyrene, cyanoacrylate, etc. are mentioned.
Monomer having 8 to 12 carbon atoms having a nitro group and a polymerizable double bond (w64):
Nitrostyrene etc. are mentioned.

Monomer having 6 to 18 carbon atoms having an epoxy group and a polymerizable double bond (w7):
Examples thereof include glycidyl (meth) acrylate and p-vinylphenylphenyl oxide.

Monomer having 2 to 16 carbon atoms having a halogen element and a polymerizable double bond (w8):
Examples thereof include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, and chloroprene.

Ether having a polymerizable double bond, a ketone having a polymerizable double bond, and a sulfur-containing compound having a polymerizable double bond (w9):
For example, C3-C16 ether having a polymerizable double bond (w91), C4-C12 ketone having a polymerizable double bond (w92), C2-C16 having a polymerizable double bond And a sulfur-containing compound (w93).
C3-C16 ether having a polymerizable double bond (w91):
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.
C4-C12 ketone having a polymerizable double bond (w92):
Examples include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.
Sulfur-containing compound having 2 to 16 carbon atoms having a polymerizable double bond (w93):
Examples thereof include divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, and divinyl sulfoxide.

  The toner binder of the present invention contains 0.01 wt% to 1 wt% of the cyclic ester compound derived from the crystalline resin (A) based on the weight of the toner binder. The cyclic ester compound is preferably from 0.01% by weight to 0.5% by weight, more preferably from 0.01% by weight to 0.3% by weight, and particularly preferably from 0.01% by weight, from the viewpoint of heat resistant storage stability and charging characteristics. % To 0.2% by weight, most preferably 0.1% by weight or less. If it exceeds 1% by weight, heat-resistant storage stability and charging characteristics may be deteriorated.

The cyclic ester compound is produced as a by-product when the crystalline resin (A) is synthesized. If a large amount of the cyclic ester compound as an oligomer component is present in the toner binder, the heat resistant storage stability and charging characteristics are adversely affected.
On the other hand, when a linear aliphatic dicarboxylic acid (y1) having an odd number of carbon atoms of 5 to 15 is used as a constituent material, the amount of by-product of the cyclic ester compound can be suppressed. This is because when a raw material having an odd number of carbon atoms is used, the generated cyclic compound becomes thermodynamically unstable.

Examples of the cyclic ester compound include compounds in which the alcohol component (x) and the carboxylic acid component (y) are condensed in equimolar amounts in the range of 1 to 10 mol to form a cyclic ester.
Specifically, a cyclic ester compound of an alkanedicarboxylic acid having 4 to 32 carbon atoms and an alkylene glycol having 2 to 30 carbon atoms (a cyclic condensate of adipic acid and 1,2-propylene glycol (1: 1 molar ratio)) , Cyclic condensate of sebacic acid and 1,2-propylene glycol (1: 1 molar ratio), cyclic condensate of adipic acid and ethylene glycol (2: 2 molar ratio), succinic acid and 1,2-propylene glycol (3: 3 molar ratio) cyclic condensate, adipic acid and 1,2-propylene glycol (5: 5 molar ratio) cyclic condensate, and sebacic acid and 1,2-propylene glycol (10:10 mol) A cyclic ester compound of an aromatic dicarboxylic acid having 8 to 20 carbon atoms and an alkylene glycol having 2 to 30 carbon atoms (phthalic acid and 1,2-propylene). Cyclic condensate with ethylene glycol (1: 1 molar ratio), cyclic condensate with phthalic acid and 1,2-propylene glycol (1: 1 molar ratio), isophthalic acid and 1,2-propylene glycol (2: 2) Cyclic condensate with a molar ratio), cyclic condensate with terephthalic acid and 1,2-propylene glycol (3: 3 molar ratio), cyclic with terephthalic acid and 1,2-propylene glycol (5: 5 molar ratio) Condensate, cyclic condensate of sebacic acid and 1,6-hexanediol (1: 1 molar ratio), cyclic condensate of sebacic acid and 1,6-hexanediol (2: 2 molar ratio), sebacic acid and Cyclic condensate with 1,6-hexanediol (3: 3 molar ratio), cyclic condensate with sebacic acid and 1,6-hexanediol (4: 4 molar ratio), sebacic acid and 1,6-hexanediol (5: 5 molar ratio) Jochijimigobutsu, and cyclic condensates, etc.) and the like of terephthalic acid and 1,2-propylene glycol (10:10 molar ratio) and the like.

  The content of the cyclic ester compound in the toner binder can be measured by liquid chromatography (hereinafter abbreviated as LC), and was measured under the following conditions.

The apparatus used was the following manufactured by Shimadzu Corporation.
LC: LC-30 Nextera
Ion source: ESI
MS: LCMS-8030
<LC measurement conditions>
Mobile phase: A; 10 mM aqueous ammonium acetate solution / methanol = 80/20
B; Methanol LC time program: A / B = 25/75 → 5/95 (v / v%)
B liquid ratio 75% (0 minutes), B liquid ratio 95% (10 minutes), B liquid ratio 95% (31 minutes), B liquid ratio 100% (32 minutes), B liquid ratio 100% (35 minutes), B liquid ratio 75% (36 minutes), STOP (40 minutes),
Flow rate: 0.3 mL / min Autosampler: Injection volume 1 μL, sample cooler 25 ° C.
Column: Inert SustainSwift (GL Science Co., Ltd., particle diameter 1.9 μm, inner diameter 2.1 mm, length 50 mm)
Column oven: 40 ° C
<MS measurement conditions>
Ionization mode: ESI (+)
Analysis mode: SCAN m / z 100-1500
Interface temperature: 350 ° C
DL temperature: 250 ° C
Nebulizer gas flow rate: 3L / min Heat block temperature: 400 ° C
Drying gas flow rate: 15L / min

<Sample solution preparation method>
1) 0.96 g of toner or toner binder is put in a screw bottle and dissolved with 8.64 g of tetrahydrofuran (hereinafter THF).
2) After dissolution, add 28 g of LC / MS methanol to the screw bottle to precipitate the insoluble matter.
3) Using a centrifuge, sediment the insoluble matter at 2000 rpm × 5 minutes.
4) Filter the supernatant obtained in 3) using a syringe and a membrane filter, take it into a special vial, and use it as the sample solution.
5) Perform LC / MS measurement on a part of the sample solution.

<Calculation method of cyclic ester compound amount>
6) Calculate the THF meta-soluble content from the ER of the sample solution of 5) and the resin sample amount.
ER measurement conditions: After cooling at 150 ° C. for 45 minutes, cooling is performed in a desiccator.
7) Calculate the ratio of the cyclic compound from the LC / MS area ratio.
8) Multiply the THF meta-soluble component by the area ratio of the cyclic compound to obtain the amount of the cyclic ester compound in the toner or toner binder.

For example, when the alcohol component (x) is 1,6-hexanediol and the carboxylic acid component (y) is sebacic acid, the content of the cyclic ester compound is calculated as follows. The molecular weight of the cyclic condensate of sebacic acid and 1,6-hexanediol (1: 1 molar ratio) is 302, and the molecular weight of the cyclic condensate of sebacic acid and 1,6-hexanediol (2: 2 molar ratio) is 587, the molecular weight of the cyclic condensate of sebacic acid and 1,6-hexanediol (3: 3 molar ratio) is 871, and the peak area of the molecular weight derived from the cyclic as described above detected by LC-MS The total value is obtained by dividing by the total area of the toner or toner binder.
When two or more alcohol components (x) and carboxylic acid components (y) are used in combination, the respective peak area values are summed with respect to the molecular weights of the conceivable cyclic compounds, and the toner or toner binder is similarly obtained. It is obtained by dividing by the total area.

In the toner binder of the present invention, the endothermic amount of the endothermic peak derived from the crystalline resin (A) in the first temperature raising process when the temperature is raised, cooled, and raised as measured by DSC is S ₁ , 2. when the heat absorption amount of times th of the crystalline resin (a) derived from the endothermic peak Atsushi Nobori process and S _2, the heat absorption amount S ₁ and S ₂ of an endothermic peak during heating satisfy the following relationship (1) It is preferable.
(S ₂ / S ₁ ) × 100 ≧ 35 (1)

In the present invention, the temperature raising / cooling conditions for the measurement by DSC are as follows: 30 ° C. to 180 ° C. under the condition of 10 ° C./min (first temperature raising process). Next, after standing at 180 ° C. for 10 minutes, it is cooled to 0 ° C. under the condition of 10 ° C./min (first cooling process). Next, after standing at 0 ° C. for 10 minutes, the temperature is raised to 180 ° C. under the condition of 10 ° C./min (second temperature raising process).
In the toner binder of the present invention, the endothermic amount of the endothermic peak derived from the crystalline resin (A) in the first temperature raising process measured by DSC when the temperature is raised, cooled and heated under the above conditions is S. ₁ , assuming that the endothermic amount of the endothermic peak derived from the crystalline resin (A) in the second temperature raising process is S ₂ , the endothermic amounts S ₁ and S ₂ of the endothermic peak at the time of temperature raising are expressed by the above relational expression (1 ).

When there are two or more endothermic peaks derived from the crystalline resin (A), both S ₁ and S ₂ are calculated by the total area.
Further, when the endothermic peak derived from the crystalline resin (A) overlaps with an endothermic peak not derived from the crystalline resin (A), it is decomposed into each peak to obtain the endothermic peak area derived from the crystalline resin (A). Of the raw materials further blended in the toner binder, crystalline raw materials such as waxes may exhibit an endothermic peak.
The endothermic amount of the endothermic peak is calculated by drawing a line perpendicular to the base line at the peak valley and using the area divided by the dividing line.
If the peak can be identified, DSC may be measured with toner instead of toner binder.

  The value on the left side of the relational expression (1) is preferably 40 to 99 from the viewpoints of low-temperature fixability, fluidity, heat resistant storage stability, grindability, image strength after fixing, folding resistance, and document offset property of the toner. Preferably it is 50-98.

  The endothermic peak (J / g) of the endothermic peak derived from the crystalline resin (A) in the second temperature raising process is preferably 1 to 30 J / g, more preferably 2 to 27 J / g, still more preferably 3 to 15 J. / G. From the viewpoint of low-temperature fixability and gloss, the endothermic peak of the endothermic peak derived from the crystalline resin (A) is preferably 1 J / g or more, and preferably 30 J / g or less from the viewpoint of hot melt resistance. The endothermic amount of the endothermic peak derived from the crystalline resin (A) in the temperature raising process is measured by DSC.

The endothermic peak top temperature (Tp) derived from the crystalline resin (A) is preferably 45 ° C. or higher from the viewpoint of heat-resistant storage stability of the toner, image strength after fixing, and document offset property, and has low temperature fixability and glossiness. From the viewpoint, it is preferably 100 ° C. or lower.
The range of Tp (° C.) is preferably 45 to 100 ° C., more preferably 50 to 95 ° C., and particularly preferably 55 to 90 ° C.
The endothermic peak top temperature (Tp) refers to the temperature at the deepest portion of the recess of the endothermic peak.
When there are two or more endothermic peaks derived from the crystalline resin (A), the temperature indicating the endothermic peak top of at least one endothermic peak may be in this range.

  The acid value (hereinafter sometimes abbreviated as AV) of the crystalline resin (A) is preferably 10 mgKOH / g or less, more preferably 7 mgKOH / g or less, particularly preferably from the viewpoint of heat-resistant storage stability and charging characteristics of the toner. Is 5 mg KOH / g or less, most preferably 3 mg KOH / g or less.

  The toner binder of the present invention contains a polyester resin containing the alcohol component (x) and the carboxylic acid component (y) excluding the crystalline resin (A) or a resin (B) that is a modified resin thereof. Is preferable from the viewpoint of hot offset resistance, chargeability, and thermal stability of a fixed image.

The method for mixing the resin (B) and the crystalline resin (A) is not particularly specified. For example, the method of mixing the resin (B) and the crystalline resin (A) with a melt kneader, or dissolving and mixing with a solvent or the like. Then, there are a method of removing the solvent, a method of mixing the crystalline resin (A) during the production of the resin (B), and the like. The mixing temperature is preferably 100 to 200 ° C., more preferably 110 to 190 ° C. from the viewpoint of resin viscosity.
The toner binder of the present invention can be obtained, for example, by mixing the crystalline resin (A) and the resin (B) as described above.

  The weight ratio (B) / (A) of the resin (B) to the crystalline resin (A) is from the viewpoint of toner fluidity, heat-resistant storage stability, grindability, image strength after fixing, low-temperature fixability, and glossiness. Preferably it is 50 / 50-95 / 5, More preferably, it is 60 / 40-92 / 8, More preferably, it is 70 / 30-90 / 10. A mixture containing the resin (B) and the crystalline resin (A) in the above ratio is preferable as the toner binder of the present invention. That is, the weight ratio (B) / (A) between the resin (B) and the crystalline resin (A) in the toner binder of the present invention is preferably in the above range.

The crystalline resin (A) may be a resin in which at least two types of segments are chemically bonded. For example, the crystalline segment (a1) compatible with the resin (B) and the resin (B) Some have a segment (a2) that is incompatible with each other. In the present specification, the crystalline segment (a1) that is compatible with the resin (B) is also simply referred to as segment (a1) or crystalline segment (a1). The segment (a2) that is incompatible with the resin (B) is also simply referred to as segment (a2).
In the present invention, the incompatibility with the resin (B) means that the resin (B) and the compound constituting each segment are mixed, and when the mixture is visually observed at room temperature, the whole or a part of the mixture becomes cloudy. Say something.

  Further, the crystalline segment (a1) is the crystalline polyester (a11), crystalline polyurethane (a12), crystalline polyurea (a13), crystalline polyamide (a14), crystalline polyvinyl (a15), etc. described above. That is.

  The segment (a2) contained in the crystalline resin (A) together with the crystalline segment (a1) compatible with the resin (B) has a structure composed of a compound that is incompatible with the resin (B). There is no particular limitation. Examples of the compound incompatible with the resin (B) include, for example, a long-chain alkyl monoalcohol (preferably having 18 to 42 carbon atoms), a long-chain alkyl monocarboxylic acid (preferably having 18 to 42 carbon atoms), an alcohol-modified product of butadiene, Examples include alcohol-modified dimethylsiloxane and the like, and preferred are a long-chain alkyl monoalcohol having 18 to 42 carbon atoms and a long-chain alkyl monocarboxylic acid having 18 to 42 carbon atoms. The segment (a2) is preferably a structure composed of such a compound. As the long-chain alkyl monoalcohol having 18 to 42 carbon atoms, for example, behenyl alcohol, stearyl alcohol and the like are preferable. As the long-chain alkyl monocarboxylic acid, for example, behenic acid, stearyl acid and the like are preferable.

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

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

The chemical bond is preferably one or more functional groups selected from the group consisting of an ester group, a urethane group, a urea group, an amide group, and an epoxy group from the viewpoint of low-temperature fixability, and more preferably an ester group and It is a urethane group.
In the present invention, the segment (a1) and the segment (a2) in the crystalline resin (A) are one or more functional groups selected from the group consisting of ester groups, urethane groups, urea groups, amide groups, and epoxy groups. It may be bonded with a group.

The weight average molecular weight of the crystalline resin (A) (hereinafter, the weight average molecular weight may be abbreviated as Mw) is preferably 5,000 to 100,000, more preferably from the viewpoint of low-temperature fixability and gloss. Is from 8,000 to 80,000, particularly preferably from 10,000 to 60,000, most preferably from 12,000 to 50,000.
Mw and number average molecular weight (also referred to as Mn in this specification) are obtained by dissolving the crystalline resin (A) in tetrahydrofuran (THF), and using it as a sample solution, using gel permeation chromatography (GPC). And measured under the following conditions.
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 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 resin (B) used in the toner and toner binder of the present invention is a polyester resin obtained by reacting an alcohol component (X) and a carboxylic acid component (Y) as raw materials or a modified resin thereof and a crystalline resin (A). The composition of the resin is not particularly limited as long as it excludes.
The alcohol component (X) is preferably a polyol component such as a diol.
As the modified resin of the polyester resin, one obtained by modifying the polyester resin with at least one selected from the group consisting of a urethane group, a urea group, an amide group, an epoxy group, and a vinyl group is preferable.
Examples of the polyester resin or the resin (B) that is a modified resin thereof include an amorphous polyester resin (B1), an amorphous styrene (co) polymer polyester-modified resin (B2), and an amorphous epoxy resin. Examples thereof include a polyester-modified resin (B3) and a polyester-modified resin (B4) of an amorphous urethane resin. Of these, the polyester resin or the resin (B) which is a modified resin thereof is preferably an amorphous polyester resin (B1).
For example, a polyester-modified resin (B2) of an amorphous styrene (co) polymer, a polyester-modified resin (B3) of an amorphous epoxy resin, and a polyester-modified resin (B4) of an amorphous urethane resin, respectively, It is preferable as a resin obtained by modifying a polyester resin with a vinyl group, an epoxy group, or a urethane group.
In the present invention, “amorphous” refers to a resin that shows a stepwise endothermic change and does not have a clear endothermic peak in the first temperature rising process of the DSC measurement.

The amorphous polyester resin (B1) is a polyester resin obtained by reacting the alcohol component (X) and the carboxylic acid component (Y) as raw materials.
As the polyol component constituting the amorphous polyester resin (B1), the same diol component (x1) as used in the crystalline polyester (a11) can be used. Moreover, a trivalent or more polyol (x2) can be used with a diol component (x1) as needed. As the trivalent or higher polyol, the same polyol as the trivalent or higher polyol used in the crystalline polyester (a11) can be used.

  Among them, as the alcohol component (X), from the viewpoint of low-temperature fixability and hot offset resistance, alkylene glycols having 2 to 12 carbon atoms, polyoxyalkylene ethers of bisphenols (2 to 30 AO units) [bisphenols] AO adduct of A (addition mole number 2 to 30)], polyhydric aliphatic alcohol having 3 to 8 or more valences, and polyoxyalkylene ether of novolac resin (2 to 30 AO units) [ AO adduct of novolak resin (2-30 addition moles)].

More preferred are alkylene glycols having 2 to 10 carbon atoms, polyoxyalkylene ethers of bisphenols (2 to 5 of AO units), polyoxyalkylene ethers of novolak resins (2 to 30 of AO units), Preferred are alkylene glycols having 2 to 6 carbon atoms and polyoxyalkylene ethers of bisphenol A (number of AO units 2 to 5), and most preferred are polyoxyalkylene ethers of ethylene glycol, propylene glycol and bisphenol A (AO). The number of units is 2-3).
In order to obtain an amorphous resin, the content of the linear diol is preferably 70 mol% or less, more preferably 60 mol% or less of the diol component (x1) used. Moreover, it is preferable that diol component (x1) is 90-100 mol% in alcohol component (X) which comprises an amorphous polyester resin (B1).

  As the carboxylic acid component (Y) constituting the amorphous polyester resin (B1), the same carboxylic acid component (y2) as used in the crystalline polyester (a11) can be used.

Among these carboxylic acid components, benzoic acid, alkanedicarboxylic acid having 2 to 50 carbon atoms, alkenedicarboxylic acid having 4 to 50 carbon atoms, and 8 to 20 carbon atoms are preferred from the viewpoint of achieving both low-temperature fixability and hot offset resistance. And aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid) are preferred.
More preferably, it is benzoic acid, adipic acid, alkenyl succinic acid having 16 to 50 carbon atoms, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid, and a combination of two or more thereof. Particularly preferred are adipic acid, terephthalic acid, trimellitic acid, and combinations of two or more thereof.
In addition, anhydrides and lower alkyl esters of these carboxylic acids are also preferable.

The glass transition point (Tg) of the resin (B) is 40 to 75 ° C. from the viewpoints of low-temperature fixability, glossiness and toner fluidity, heat-resistant storage stability, image strength after fixing, bending resistance, and document offset property. Is more preferable, it is 45-72 degreeC, More preferably, it is 50-70 degreeC.
In addition, Tg is measured by the method (DSC method) prescribed | regulated to ASTMD3418-82 using DSC.

Mw of the amorphous polyester resin (B1) is 2 from the viewpoints of low-temperature fixability, glossiness and toner fluidity, heat-resistant storage stability, grindability, image strength after fixing, folding resistance, and document offset. 1,000 to 200,000 is preferable, 2,500 to 180,000 is more preferable, and 3,000 to 150,000 is particularly preferable.
Mw and Mn of the resin (B) are obtained by GPC in the same manner as the crystalline resin (A) described above.

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

  The method for reducing the acid value of the resin (B) is not particularly limited. For example, the trifunctionality increases the molecular weight, reduces the amount of trimellitic anhydride charged for half esterification, and caps the end with a monoalcohol or the like. For example, the crosslinking reaction may be performed with the above acid or alcohol, the ratio of the acid such as urethane and the alcohol ratio may be adjusted, and the terminal functional group may be converted into an alcohol with a slight excess of alcohol.

The hydroxyl value of the resin (B) is preferably from the viewpoints of low-temperature fixability, glossiness, toner fluidity, heat-resistant storage stability, charge stability, grindability, image strength after fixing, folding resistance, and document offset. Is not more than 50 mgKOH / g, more preferably not more than 30 mgKOH / g, still more preferably not more than 20 mgKOH / g, particularly preferably not more than 10 mgKOH / g, most preferably not more than 5 mgKOH / g.
In the present invention, the hydroxyl value can be measured by a method defined in JIS K0070.

  The method for reducing the hydroxyl value of the resin (B) is not particularly limited. For example, the molecular weight is increased, the terminal is capped with a monocarboxylic acid or the like, and a crosslinking reaction is performed with a trifunctional or higher functional acid or alcohol. Examples include adjusting the ratio of the charged acid and alcohol to slightly add an acid to make the terminal functional group an acid.

  The molecular content of the resin (B) having a molecular weight of 1,000 or less is determined from the viewpoints of toner fluidity, heat-resistant storage stability, charge stability, grindability, image strength after fixing, bending resistance, and document offset. When expressed by the peak area when the molecular weight of the resin (B) is measured by gel permeation chromatography, it is preferably 10% or less, more preferably 8% or less, and even more preferably 6% of the total peak area. % Or less, particularly preferably 4% or less, and most preferably 2% or less. When the content of the molecule having a molecular weight of 1,000 or less contained in the resin (B) is in the above range, the fluidity of the toner, heat resistant storage stability, charging stability, pulverization property, image strength after fixing, bending resistance, Good document offset

In the present invention, the molecular content of the resin (B) having a molecular weight of 1,000 or less is determined by data processing of the molecular weight measurement result of the resin (B) by GPC as described below.
(1) A retention time at which the molecular weight becomes 1,000 is determined from a calibration curve with the molecular weight and the retention time as axes.
(2) Obtain the total peak area (Σ1).
(3) The peak area after the retention time obtained in (1) (peak area with a molecular weight of 1,000 or less) (Σ2) is obtained.
(4) The content of molecules having a molecular weight of 1,000 or less is determined from the following formula.
Content of molecules having a molecular weight of 1,000 or less (%) = (Σ2) × 100 / (Σ1)

  There is no particular limitation on the method of reducing the content of the molecule having a molecular weight of 1,000 or less in the resin (B). For example, the molecular weight of the resin (B) is increased, and the terminal is capped with a monocarboxylic acid or the like. For example, a crosslinking reaction may be performed with an acid.

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

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

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

As the resin (B) in the present invention, an amorphous styrene (co) polymer polyester-modified resin (B2) can also be used.
This amorphous styrene (co) polymer polyester-modified resin (B2) is obtained by reacting a polymer of a styrene monomer alone or a copolymer of a styrene monomer and a (meth) acrylic monomer with a polyester. is there.
Examples of the styrenic monomer include styrene and alkyl styrene having an alkyl group having 1 to 3 carbon atoms (for example, α-methyl styrene, p-methyl styrene). Styrene is preferred.

Examples of (meth) acrylic monomers that can be used in combination include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. Alkyl esters having 1 to 18 carbon atoms in the alkyl group; hydroxyl group-containing (meth) acrylates having 1 to 18 carbon atoms in the alkyl group such as hydroxylethyl (meth) acrylate; dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( C1-C18 amino group-containing (meth) acrylate of alkyl group such as meth) acrylate; nitrile group-containing acrylonitrile, methacrylonitrile, methacrylonitrile methyl group replaced with C2-C18 alkyl group Meth) acrylic compound and (meth) acrylic acid.
Of these, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid and a mixture of two or more of these are preferred.

The polyester-modified resin (B2) of amorphous styrene (co) polymer may be used in combination with other vinyl ester monomers and aliphatic hydrocarbon vinyl monomers as necessary.
Examples of vinyl ester monomers include aliphatic vinyl esters (C4-15, such as vinyl acetate, vinyl propionate, isopropenyl acetate, etc.), unsaturated carboxylic acid polyvalent (2-3 valent) alcohol esters (C8-200). For example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, 1,6-hexanediol diacrylate and polyethylene glycol di (meth) ) Acrylate, etc.), aromatic vinyl esters (C9-15, such as methyl-4-vinylbenzoate), and the like.
Aliphatic hydrocarbon vinyl monomers include olefins (2 to 10 carbon atoms such as ethylene, propylene, butene, octene, etc.), dienes (4 to 10 carbon atoms such as butadiene, isoprene, 1,6-hexadiene, etc.) and the like. Can be mentioned.

  The Mw of the amorphous styrene (co) polymer polyester-modified resin (B2) used in the present invention is Mw 100,000 to 300,000, preferably 130,000 to 300,000 from the viewpoint of the fixing temperature range. It is 280,000, More preferably, it is 150,000-250,000.

  The ratio Mw / Mn between the Mw and the number average molecular weight (Mn) of the amorphous styrene (co) polymer polyester-modified resin (B2) is, for example, usually 10 to 70 from the viewpoint of the fixing temperature range. Yes, preferably 15 to 65, more preferably 20 to 60.

  It is preferable to use two or more types of amorphous styrene (co) polymer polyester-modified resins (B2) having different molecular weights from the viewpoint of the fixing temperature range.

As the resin (B) in the present invention, an amorphous epoxy resin polyester-modified resin (B3) can also be used.
As the polyester-modified resin (B3) of an amorphous epoxy resin, a ring-opening polymer of polyepoxide, a polyepoxide and an active hydrogen-containing compound {water, polyol [diol and trivalent or higher polyol], dicarboxylic acid, trivalent or higher Polycarboxylic acid, polyamine, etc.} and those obtained by reacting with a polyester.

Moreover, the polyester-modified resin (B4) of an amorphous urethane resin can also be used as the resin (B) in the present invention.
Examples of the polyester-modified resin (B4) of amorphous urethane resin include those obtained by reacting the diisocyanate (v2), monoisocyanate (v1), trifunctional or higher polyisocyanate (v3) with polyester. .

  As monoisocyanate (v1), phenyl isocyanate, tolylene isocyanate, xylylene isocyanate, α, α, α ′, α′-tetramethylxylylene isocyanate, naphthylene isocyanate, ethyl isocyanate, propyl isocyanate, hexyl isocyanate, octyl isocyanate Decyl isocyanate, dodecyl isocyanate, tetradecyl isocyanate, hexadecyl isocyanate, octadecyl isocyanate, cyclobutyl isocyanate, cyclohexyl isocyanate, cyclooctyl isocyanate, cyclodecyl isocyanate, cyclododecyl isocyanate, cyclotetradecyl isocyanate Nates, isophorone isocyanate, dicyclohexylmethane-4-isocyanate, cyclohexane Ren isocyanate, methyl cyclohexylene diisocyanate, norbornane diisocyanate and bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, and the like.

  The trifunctional or higher polyisocyanate (v3) is not particularly limited as long as it is a compound having three or more isocyanate groups, and examples thereof include compounds having a chemical structure of triisocyanate, tetraisocyanate, isocyanurate, biuret, and the like. It is done.

  The toner binder of the present invention may be composed of a crystalline resin (A) and a resin (B), and may contain other components as necessary as long as the effects of the present invention are not impaired. A toner binder made of a crystalline resin (A) and a resin (B) is preferable.

The toner containing the toner binder and the colorant of the present invention is also one aspect of the present invention.
The toner of the present invention is preferably a composition containing a toner binder comprising a resin (B) and a crystalline resin (A) and a colorant.

As the colorant, all of dyes and pigments used as toner colorants can be used.
Specifically, carbon black, iron black, Sudan Black SM, First Yellow G, Benzidine Yellow, 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 is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight, when the total of the resin (B) and the crystalline resin (A) is 100 parts by weight.
In addition, when using magnetic powder, Preferably it is 20-150 weight part with respect to a total of 100 weight part of resin (B) and crystalline resin (A), More preferably, it is 40-120 weight part. Above and below, parts mean parts by weight.

In addition to the crystalline resin (A), the resin (B), and the colorant, the toner of the present invention contains one or more additives selected from a mold release agent, a charge control agent, a fluidizing agent, and the like as necessary. .
As the release agent, those having a softening point [Tm] of 50 to 170 ° C. by a flow tester are preferable, polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms and these. A mixture etc. are mentioned.

  Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides by oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid and maleic anhydride, etc.] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl of 1 to 18 carbon atoms) ester and Maleic acid alkyl (C1-18 alkyl) copolymers of an ester, etc.] or the like, and Sasol wax.

  Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax. Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol. Examples of the fatty acid having 30 to 50 carbon atoms include triacontane carboxylic acid.

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

  Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder.

The method for producing the toner of the present invention is not particularly limited.
The toner of the present invention may be obtained by any known method such as kneading and pulverization method, emulsion phase inversion method and polymerization method.
For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry blended, and then melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. Further, by further classifying, the volume average particle diameter (D50) is preferably 5 to 20 μm and then mixed with a fluidizing agent.
The volume average particle diameter (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].
When the toner is obtained by the emulsion phase inversion method, the components constituting the toner excluding the fluidizing agent are dissolved or dispersed in an organic solvent, and then emulsified by adding water, etc., and then separated and classified for production. it can. The volume average particle diameter of the toner is preferably 3 to 15 μm.
When a toner is obtained by a polymerization method, a dispersion in which the crystalline resin (A) is finely dispersed in an organic solvent in advance is mixed in an organic solvent solution in which the amorphous resin (B) is dissolved. You may manufacture by removing. The method for dispersing the crystalline resin (A) in the organic solvent is not particularly limited. For example, the crystalline resin (A) may be crystallized in the organic solvent and then finely dispersed by a disperser (for example, a bead mill or a colloid mill).
Further, it may be produced by a method using organic fine particles described in JP-A No. 2002-284881 or a method of dispersing in carbon dioxide in a supercritical state described in JP-A No. 2007-277511.

  The toner of the present invention is mixed with carrier particles such as ferrite whose surface is coated with iron powder, glass beads, nickel powder, ferrite, magnetite, and resin (acrylic resin, silicone resin, etc.) as necessary to form an electrical latent image. Used as a developer. The weight ratio of toner to carrier particles is usually 1/99 to 100/0 for toner / carrier particles. 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, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, “%” represents “% by weight”.

Production Example 1
[Synthesis of Crystalline Resin (A-1)]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 683 parts by weight (100 mol%) of 1,7-heptanedicarboxylic acid (y1-1) (EMEROX 1144, manufactured by Emery Co.), 1,6-hexane 445 parts by weight (100 mol%) of diol and 0.5 parts by weight of tetrabutoxytitanate as a condensation catalyst were added and reacted at 170 ° C. under a nitrogen stream for 8 hours while distilling off generated water. Next, while gradually raising the temperature to 210 ° C., the mixture is reacted for 4 hours while distilling off the generated water, and further reacted under reduced pressure of 0.5 to 2.5 kPa. When it became below, it took out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-1).

Production Example 2
[Synthesis of Crystalline Resin (A-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 674 parts by weight (100 mol%) of 1,7-heptanedicarboxylic acid (y1-1) and 430 parts by weight of 1,6-hexanediol (98 mol) %), 22 parts by weight (2 mol%) of behenyl alcohol and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were allowed to react at 170 ° C. for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction is performed for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction is further performed under a reduced pressure of 0.5 to 2.5 kPa. When it became below, it took out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-2).

Production Example 3
[Synthesis of Crystalline Resin (A-3)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 416 parts by weight (50 mol%) of 1,7-heptanedicarboxylic acid (y1-1), 443 parts by weight of sebacic acid (50 mol%), ethylene 543 parts by weight of glycol (98 mol%), 22 parts by weight of behenyl alcohol (2 mol%) and 0.5 parts by weight of tetrabutoxytitanate as a condensation catalyst were added, and the generated water and ethylene glycol were distilled under a nitrogen stream at 170 ° C. The reaction was allowed to proceed for 8 hours. Next, while gradually raising the temperature to 220 ° C., the reaction is performed for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction is further performed under a reduced pressure of 0.5 to 2.5 kPa. When it became below, it took out. The removed ethylene glycol was 268 parts by weight. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-3).

Production Example 4
[Synthesis of Crystalline Resin (A-4)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 617 parts by weight (80 mol%) of 1,9-nonanedicarboxylic acid (y1-2), 152 parts by weight (19 mol%) of dodecanedioic acid, 18 parts by weight (2 mol%) of behenic acid, 339 parts by weight of 1,4-butanediol (100 mol%) and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst are added and produced at 170 ° C. in a nitrogen stream. The reaction was allowed to proceed for 8 hours while distilling off water. Next, while gradually raising the temperature to 220 ° C., the reaction is performed for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction is further performed under a reduced pressure of 0.5 to 2.5 kPa. When it became below, it took out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-4).

Production Example 5
[Synthesis of Crystalline Resin (A-5)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 557 parts by weight (100 mol%) of 1,7-heptanedicarboxylic acid (y1-1), 548 parts by weight of 1,10-decanediol (100 mol) %) And 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were allowed to react at 170 ° C. under a nitrogen stream for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction is performed for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction is further performed under a reduced pressure of 0.5 to 2.5 kPa. When it became below, it took out. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-5).

Production Example 6
[Synthesis of Crystalline Resin (A-6)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 509 parts by weight (100 mol%) of 1,7-heptanedicarboxylic acid (y1-1) and 587 parts by weight of 100 mol of 1,12-dodecanediol (100 mol) %) And 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were allowed to react at 170 ° C. under a nitrogen stream for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction is performed for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction is further performed under a reduced pressure of 0.5 to 2.5 kPa. When it became below, it took out. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-6).

Production Example 7
[Synthesis of Crystalline Resin (A-7)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 572 parts by weight (98 mol%) of 1,7-heptanedicarboxylic acid (y1-1), 21 parts by weight of behenic acid (2 mol%), 1 , 10-decanediol 516 parts by weight (100 mol%) and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were added and reacted at 170 ° C. for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction is performed for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction is further performed under a reduced pressure of 0.5 to 2.5 kPa. When it became below, it took out. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-7).

Production Example 8
[Synthesis of Crystalline Resin (A-8)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 531 parts by weight (100 mol%) of 1,7-heptanedicarboxylic acid (y1-1) and 551 parts by weight (98 mol of 1,12-dodecanediol) %), 18 parts by weight (2 mol%) of behenyl alcohol and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst were allowed to react at 170 ° C. for 8 hours while distilling off the generated water. Next, while gradually raising the temperature to 220 ° C., the reaction is performed for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction is further performed under a reduced pressure of 0.5 to 2.5 kPa. When it became below, it took out. The taken-out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A-8).

Production Example 9
[Synthesis of Resin (B-1)]
In the reaction vessel, 734 parts by weight of 1.2-propylene glycol, 1 part by weight of bisphenol A ethylene oxide 2-mole adduct, 1 part by weight of bisphenol A propylene oxide 2-mole adduct, 670 parts by weight of terephthalic acid, 38 parts by weight of adipic acid Part, 34 parts by weight of benzoic acid, 53 parts by weight of trimellitic anhydride, and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst, reacted at 220 ° C. under pressure, and reacted for 20 hours while distilling off the generated water. It was. Subsequently, the pressure was returned to normal pressure while gradually releasing the pressure, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When Tm reached 130 ° C., the resin (b-1) was taken out using a steel belt cooler. The removed propylene glycol was 353 parts by weight.

  In a separate reaction vessel, 581 parts by weight of 1.2-propylene glycol, 1 part by weight of bisphenol A ethylene oxide 2-mole adduct, 49 parts by weight of bisphenol A propylene oxide 2-mole adduct, 625 parts by weight of terephthalic acid, adipic acid 8 parts by weight, 49 parts by weight of benzoic acid, 58 parts by weight of trimellitic anhydride, and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst, reacted at 220 ° C. under pressure, and 10 hours while distilling off the generated water Reacted. Subsequently, the pressure was returned to normal pressure while gradually releasing the pressure, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When Tm reached 105 ° C., the pressure was returned to normal pressure and cooled to 180 ° C. 14 parts of trimellitic anhydride was added and reacted for 1 hour. It cooled to 150 degreeC and took out resin (b-2) using the steel belt cooler. The removed propylene glycol was 234 parts by weight.

  Henschel mixer [FM10B manufactured by Nippon Coke Industries, Ltd.] so that the weight ratio (b-1) / (b-2) of the obtained resin (b-1) and resin (b-2) is 50/50. To obtain a resin (B-1).

Production Example 10
[Synthesis of Resin (B-2)]
In a reaction vessel, 322 parts by weight of bisphenol A ethylene oxide 2-mole adduct, 419 parts by weight of bisphenol A propylene oxide 2-mole adduct, 274 parts by weight of terephthalic acid, and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst were added. The reaction was carried out at 220 ° C. under pressure, and the reaction was carried out for 10 hours while distilling off the water produced. Subsequently, the pressure was returned to normal pressure while gradually releasing the pressure, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When Tm reached 100 ° C, the pressure was returned to normal pressure and cooled to 180 ° C. 42 parts by weight of trimellitic anhydride was added and reacted for 1 hour. It cooled to 150 degreeC and resin (b-3) was obtained using the steel belt cooler.

  In a separate reactor, 167 parts by weight of bisphenol A ethylene oxide 2-mole adduct, 128 parts by weight of bisphenol A propylene oxide 2-mole adduct, 468 parts by weight of bisphenol A propylene oxide 3-mole adduct, 184 parts by weight of terephthalic acid Then, 53 parts by weight of trimellitic anhydride and 3 parts by weight of tetrabutoxy titanate as a condensation catalyst were added, reacted at 220 ° C. under pressure, and reacted for 10 hours while distilling off the generated water. Subsequently, the pressure was returned to normal pressure while gradually releasing the pressure, and the reaction was further carried out under a reduced pressure of 0.5 to 2.5 kPa. When Tm reached 110 ° C., the pressure was returned to normal pressure and cooled to 180 ° C. 52 parts by weight of trimellitic anhydride was added, the temperature was raised to 210 ° C., and the reaction was further proceeded under reduced pressure of 0.5 to 2.5 kPa. When Tm reached 145 ° C., a steel belt cooler was used to obtain a resin (b-4).

  In Henschel mixer [FM10B manufactured by Nippon Coke Industries, Ltd.] so that the weight ratio (b-3) / (b-4) of the obtained resin (b-3) and resin (b-4) is 50/50. To obtain resin (B-2).

<Production Example 11> [Synthesis of Resin (B-3)]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 315 parts by weight of propylene glycol, 404 parts by weight of a PO2 molar adduct of bisphenol A, 459 parts by weight of terephthalic acid, 61 parts by weight of benzoic acid Then, 2.5 parts by weight of titanium diisopropoxybistriethanolamate is added as a polymerization catalyst and reacted for 5 hours while distilling off the water produced at 210 ° C. under a nitrogen stream, and then 0.007-0. The reaction was performed for 1 hour under a reduced pressure of 026 MPa. Subsequently, it cooled to 180 degreeC, the trimellitic anhydride 27.3 weight part was added, and it was made to react under a normal pressure for 1 hour, and resin (B-3) was obtained. The removed propylene glycol was 161 parts by weight.

<Production Example 12> [Preparation of precursor (M-1) solution]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 681 parts by weight of an EO2 molar adduct of bisphenol A, 81 parts by weight of a PO2 molar adduct of bisphenol A, 275 parts by weight of terephthalic acid Then, 7 parts by weight of adipic acid, 22 parts by weight of trimellitic anhydride and 2 parts by weight of dibutyltin oxide were added, and after dehydration reaction at normal pressure and 230 ° C. for 5 hours, the pressure was reduced to 0.01 to 0.03 MPa. And a dehydration reaction was performed for 5 hours to obtain a polyester resin.
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer, 350 parts by weight of a polyester resin, 50 parts by weight of isophorone diisocyanate, 600 parts by weight of ethyl acetate, and 0.5 parts by weight of ion-exchanged water are put in a sealed state. Reaction was performed at 90 ° C. for 5 hours to obtain a precursor (M-1) solution having an isocyanate group at the molecular end. The urethane group concentration of the (M-1) solution was 5.2% by weight, and the urea group concentration was 0.3% by weight. The solid content was 45% by weight.

<Production Example 13> [Production of fine particle dispersion]
In a reaction vessel equipped with a stirrer, heating / cooling device, thermometer, cooling pipe and nitrogen introduction pipe, 690 parts by weight of water, sodium salt of polyoxyethylene monomethacrylate sulfate “Eleminol RS-30” [Sanyo Chemical Industries Co., Ltd. )] 9 parts by weight, 90 parts by weight of styrene, 90 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate and 1 part by weight of ammonium persulfate, and stirred for 15 minutes at 350 rpm, a white emulsion was obtained. was gotten. Next, the temperature was raised to 75 ° C., and the reaction was performed at the same temperature for 5 hours. Further, 30 parts by weight of a 1% by weight aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours to vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A fine particle dispersion was obtained. The volume average particle size of the particles dispersed in the fine particle dispersion was measured using a laser diffraction / scattering particle size distribution measuring apparatus “LA-920” (manufactured by Horiba, Ltd.). there were. When a part of the fine particle dispersion was taken out and Tg and Mw were measured, Tg was 65 ° C. and Mw was 150,000.

<Production Example 14> [Production of Colorant Dispersion]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, a cooling tube and a nitrogen introduction tube, 557 parts by weight of propylene glycol, 569 parts by weight of dimethyl terephthalate, 184 parts by weight of adipic acid and tetrabutoxytitanate 3 as a condensation catalyst A part by weight was added, and the reaction was carried out for 8 hours while distilling off the methanol produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 0.007 to 0.026 MPa. The recovered propylene glycol was 175 parts by weight. Next, the mixture was cooled to 180 ° C., 121 parts by weight of trimellitic anhydride was added, reacted for 2 hours under normal pressure sealing, reacted at 220 ° C. and normal pressure until the softening point reached 180 ° C., and polyester resin (Mn = 8 , 500).
Into a beaker, 20 parts by weight of copper phthalocyanine, 4 parts by weight of a colorant dispersant “Solsper's 28000” (manufactured by Avicia), 20 parts by weight of the obtained polyester resin and 56 parts by weight of ethyl acetate were added and stirred uniformly After the dispersion, copper phthalocyanine was finely dispersed by a bead mill to obtain a colorant dispersion. The volume average particle diameter measured with “LA-920” of the colorant dispersion was 0.2 μm.

<Production Example 15> [Production of modified wax]
In a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device, a thermometer, and a dropping cylinder, 454 parts by weight of xylene, low molecular weight polyethylene “Sun Wax LEL-400” [Tm: 128 ° C., manufactured by Sanyo Chemical Industries, Ltd.] 150 Part by weight was added, and after nitrogen substitution, the temperature was raised to 170 ° C. with stirring, and at the same temperature, 595 parts by weight of styrene, 255 parts by weight of methyl methacrylate, 34 parts by weight of di-t-butylperoxyhexahydroterephthalate and 119 parts by weight of xylene. Part of the mixed solution was added dropwise over 3 hours, and the mixture was further maintained at the same temperature for 30 minutes. Subsequently, xylene was distilled off under a reduced pressure of 0.039 MPa to obtain a modified wax. The SP value of the graft chain of the modified wax was 10.35 (cal / cm3) 1/2, Mn was 1,900, Mw was 5,200, and Tg was 56.9 ° C.

<Production Example 16> [Production of release agent dispersion]
In a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling tube and a thermometer, paraffin wax “HNP-9” [Maximum heat of fusion peak temperature: 73 ° C., manufactured by Nippon Seiki Co., Ltd.] 10 parts by weight, production example 1 part by weight of the modified wax obtained in 11 and 33 parts by weight of ethyl acetate were added, the temperature was raised to 78 ° C. with stirring, the mixture was stirred at the same temperature for 30 minutes, and then cooled to 30 ° C. over 1 hour to obtain paraffin wax. Crystallization was performed in the form of fine particles, and further wet pulverized with Ultraviscomil (manufactured by IMEX) to obtain a release agent dispersion. The volume average particle diameter was 0.25 μm.

<Production Example 17> [Production of Resin Solution (L-1)]
In a reaction vessel equipped with a stirrer, 15 parts by weight of crystalline resin (A-1), 85 parts by weight of resin (B-3), 30 parts by weight of colorant dispersion, 40 parts by weight of release agent dispersion and acetic acid 153 parts by weight of ethyl was added and stirred to obtain a resin solution (L-1).

<Production Example 18> [Synthesis of Curing Agent (β-1)]
Into a reaction vessel equipped with a stirrer, heating / cooling device, cooling tube and thermometer, 50 parts by weight of isophorone diamine and 300 parts by weight of methyl ethyl ketone are added, and after 5 hours of reaction at 50 ° C., the solvent is removed and the curing agent is removed. (Β-1) was obtained. The total amine value of (β-1) was 415.

Comparative production example 1
[Synthesis of Crystalline Resin (A′-1)]
In Production Example 1, 683 parts by weight (100 mol%) of 1,7-heptanedicarboxylic acid (y1-1) and 445 parts by weight (100 mol%) of 1,6-hexanediol were mixed with 696 parts by weight (100 mol of sebacic acid). %) (Manufactured by Toyokuni Oil Co., Ltd.), except for changing to 427 parts by weight (100 mol%) of 1,6-hexanediol, the reaction was conducted in the same manner as in Production Example 1 to obtain a crystalline resin (A′-1). .

Comparative production example 2
[Synthesis of Crystalline Resin (A′-2)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 331 parts by weight (40 mol%) of 1,7-heptanedicarboxylic acid (y1-1), 529 parts by weight of sebacic acid (60 mol%), ethylene 540 parts by weight of glycol (98 mol%), 22 parts by weight of behenyl alcohol (2 mol%) and 0.5 parts by weight of tetrabutoxytitanate as a condensation catalyst were added, and the generated water and ethylene glycol were distilled at 170 ° C. in a nitrogen stream. The reaction was allowed to proceed for 8 hours. Next, while gradually raising the temperature to 220 ° C., the reaction is performed for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction is further performed under a reduced pressure of 0.5 to 2.5 kPa. When it became below, it took out. The removed ethylene glycol was 267 parts by weight. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A′-2).

Comparative production example 3
[Synthesis of Crystalline Resin (A′-3)]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 822 parts by weight of adipic acid (100 mol%), 698 parts by weight of ethylene glycol (100 mol%) and 0.5 parts by weight of tetrabutoxy titanate as a condensation catalyst The reaction was carried out for 8 hours at 170 ° C. under a nitrogen stream while distilling off the water and ethylene glycol produced. Next, while gradually raising the temperature to 220 ° C., the reaction is performed for 4 hours while distilling off the generated water under a nitrogen stream, and the reaction is further performed under a reduced pressure of 0.5 to 2.5 kPa. When it became below, it took out. The removed ethylene glycol was 319 parts by weight. The taken out resin was cooled to room temperature and then pulverized into particles to obtain a crystalline resin (A′-3).

<Comparative Production Example 4> [Production of Resin Solution (L′-1)]
In a reaction vessel equipped with a stirrer, 15 parts by weight of crystalline resin (A′-1), 85 parts by weight of resin (B-3), 30 parts by weight of colorant dispersion, 40 parts by weight of release agent dispersion, and 153 parts by weight of ethyl acetate was added and stirred to obtain a resin solution (L′-1).

The temperature (Tp) showing the endothermic peak top of the crystalline resin (A) was measured by a differential scanning calorimeter (DSC) by the following method.
Apparatus: Q Series Version 2.8.0.394 (TA Instruments)
The pattern of temperature rise, cooling and temperature rise is as follows:
(1) Temperature rise from 20 ° C to 180 ° C at a rate of temperature rise of 10 ° C / min. (2) Hold at 180 ° C for 10 minutes, then cool to 0 ° C at a rate of temperature drop of 10 ° C / min. (3) Hold at 0 ° C for 10 minutes Thereafter, the temperature was raised again to 180 ° C. at a rate of temperature rise of 10 ° C./min, and about 5 mg of the resin was precisely weighed, placed in an aluminum pan, and measured once. An aluminum empty pan was used as a reference. At that time, the temperature at the deepest portion of the recess of the endothermic peak of the crystalline resin (A) in the temperature raising process (second temperature raising process) of (3) was defined as a temperature Tp indicating the endothermic peak top. When there were two or more endothermic peaks of the crystalline resin (A), the temperature showing the highest endothermic peak among them was defined as Tp.

The weight average molecular weight (Mw) of the resin was measured under the following conditions using gel permeation chromatography (GPC) using the resin dissolved in tetrahydrofuran (THF) as a sample solution.
Apparatus: HLC-8120 manufactured by Tosoh Corporation
Column: 2 TSK GEL GMH6 [manufactured by Tosoh Corporation]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF solution Injection amount: 100 μL
Detection apparatus: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

The Tg (Tg1) of the resin (B) was measured by a method (DSC method) defined in ASTM D3418-82 using DSC (Model Q Series Version 2.8.0.394 manufactured by TA Instruments).
The acid value and hydroxyl value of the crystalline resin (A) and the resin (B) were measured by the method specified in JIS K0070.

The molecular content of the resin (B) having a molecular weight of 1,000 or less was determined by data processing of the measurement results of each resin by GPC as described below.
(1) The retention time at which the molecular weight was 1,000 was determined from a calibration curve with the molecular weight and the retention time as axes.
(2) The total peak area (Σ1) was determined.
(3) The peak area after the retention time determined in (1) (peak area with a molecular weight of 1,000 or less) (Σ2) was determined.
(4) The content of molecules having a molecular weight of 1,000 or less was determined from the following formula.
Content of molecules having a molecular weight of 1,000 or less (%) = (Σ2) × 100 / (Σ1)
The content (%) of molecules having a molecular weight of 1,000 or less determined as described above was described as “content of molecules having a molecular weight of 1,000 or less”.

Examples 1-9 and Comparative Examples 1-3
Using the crystalline resin (A) and the resin (B) obtained in the production example and the comparative production example, the crystalline resin (A) and, if necessary, the resin (B) according to the blending ratio (parts by weight) shown in Table 1. Obtained toner binders (N-1) to (N-9) and (N′-1) to (N′-3) were obtained, and toner materials further containing the toner binder and additives were obtained by the following method. As a result, toners (T-1) to (T-9) and (T′-1) to (T′-3) were obtained.
Carbon black [MA-100 manufactured by Mitsubishi Chemical Corporation] as the colorant (C-1), polyolefin wax [Biscol 550P manufactured by Sanyo Chemical Industries, Ltd.] as the release agent (D-1), charge Eisenspiron black [T-77 manufactured by Hodogaya Chemical Co., Ltd.] was used as the control agent (E-1), and colloidal silica [Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.] was used as the fluidizing agent (F-1).
First, after adding a colorant, a release agent, and a charge control agent, and premixing using a Henschel mixer [FM10B manufactured by Nippon Coke Industries, Ltd.], a biaxial kneader [PCM-30 manufactured by Ikegai Co., Ltd.] Kneaded. Then, after finely pulverizing using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.], and the particle size D50 is 7 μm toner particles were obtained. Next, 100 parts by weight of toner particles were mixed with colloidal silica by a sample mill to obtain a toner.

<Example 10>
In a beaker, 170 parts by weight of ion-exchanged water, 0.3 parts by weight of the fine particle dispersion, 1 part by weight of sodium carboxymethylcellulose, 48.5% by weight aqueous solution of “doleminyl MON-7”, “ELEMINOL MON-7” [Sanyo Kasei Co., Ltd. ) Made] 36 parts by weight and 15 parts by weight of ethyl acetate were added and stirred to dissolve uniformly. Next, the temperature was raised to 50 ° C., and the TK auto homomixer was stirred at 10,000 rpm at the same temperature, while 11 parts by weight of the precursor (M-1) solution, 5.5 parts by weight of the curing agent (β-1), and the resin. 63 parts by weight of the solution (L-1) was added and stirred for 2 minutes. Next, this mixed solution is transferred to a reaction vessel equipped with a stirrer, a heating / cooling device, a cooling pipe and a thermometer, and ethyl acetate is distilled off at 50 ° C. until the concentration becomes 0.5% by weight or less. A resin dispersion was obtained. Next, the product was washed, filtered, and dried at 40 ° C. for 18 hours to obtain a toner (T-10) of the present invention with a volatile content of 0.5% by weight or less.

<Comparative example 4>
A toner (T′-4) was obtained by reacting in the same manner as in Example 10 except that the resin solution (L-1) was changed to the resin solution (L′-1).

When the toner binder is heated, cooled, and heated, the endothermic peak area derived from the crystalline resin (A) in the first heating process measured by DSC is S1, and the second heating process is crystallized. The endothermic peak area derived from the conductive resin (A) was S2, and S1 and S2 (endothermic peak area at the time of temperature increase) were measured as follows.
About 5 mg of a mixture of the crystalline resin (A) and the resin (B) blended in the proportions shown in Table 1 was precisely weighed and placed in an aluminum pan, and DSC was measured under the following temperature rise conditions.
Apparatus: Q Series Version 2.8.0.394 (TA Instruments)
The temperature was raised from 20 ° C. to 180 ° C. under the condition of 10 ° C./min (the first temperature raising process), then left at 180 ° C. for 10 minutes and then cooled to 0 ° C. under the condition of 10 ° C./min. First cooling process), and then allowed to stand at 0 ° C. for 10 minutes, and then heated to 180 ° C. under a condition of 10 ° C./min (second heating process).
DSC was measured from the beginning of the first temperature raising process (20 ° C.) to the end of the second temperature raising process (180 ° C.).
The value of (S2 / S1) × 100 is shown in Table 1. Further, the endothermic heat amount (J / g) derived from the crystalline resin (A) in the second temperature raising process measured by DSC is shown in Table 1 as “endothermic amount (J) / g derived from (A)”. .

[Evaluation method]
The following describes the low-temperature fixability, glossiness, hot offset resistance, heat-resistant storage stability, charge stability, image strength, document offset test measurement method, evaluation method, and judgment criteria of the obtained toner.

<Low temperature fixability>
The toner was uniformly placed on the paper surface so as to be 0.6 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 was removed was used. Other methods may be used as long as the powder can be uniformly loaded with the above-described weight density.
Measures the low temperature fixing temperature, which is the temperature at which cold offset occurs when this paper is 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. did.
The lower the low temperature fixing temperature, the better the low temperature fixing property. The low temperature fixing temperature (° C.) of the toner is shown in Table 1 and Table 2 as the low temperature fixing property (° C.).

<Glossiness>
The fixing evaluation was performed in the same manner as the low temperature fixing property. White cardboard was laid under the image, and the glossiness of the printed image was measured at an incident angle of 60 degrees using a gloss meter (“IG-330” manufactured by Horiba, Ltd.).
[Criteria]
◎: 20 or more ○: 15 or more and less than 20 △: 10 or more and less than 15 ×: Less than 10

<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.).

<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.
X: Blocking has occurred.

<Charging stability>
(1) 0.5 g of toner and 20 g of ferrite carrier (P-Tech, F-150) were placed in a 50 mL glass bottle and conditioned at 23 ° C. and 50% relative humidity for 8 hours or more.
(2) Friction stirring was performed at 50 rpm for 10 minutes and 60 minutes with a tumbler shaker mixer, and the charge amount at each time was measured.
For the measurement, a blow-off charge measuring device [manufactured by Toshiba Chemical Co., Ltd.] was used.
“Charging amount of 60 minutes friction time / charging amount of 10 minutes friction time” was calculated and used as an index of charging stability.
[Criteria]
◎: 0.8 or more ○: 0.7 or more and less than 0.8 △: 0.6 or more and less than 0.7 ×: Less than 0.6

<Image intensity>
Load of 10 g from right above the pencil in which the test paper used for measuring the low temperature fixing temperature (the paper on which the image is fixed obtained by the evaluation of the low temperature fixing property) is fixed at an angle of 45 degrees according to JIS K5600 A scratch test was conducted, and the image strength was evaluated from the pencil hardness without scratches.
Higher pencil hardness means better image strength.

<Document offset property>
Two sheets of A4 paper on which the image obtained in the evaluation of the low-temperature fixability was fixed were overlapped with each other on the fixing surface, applied with a load of 420 g (0.68 g / cm 2), and allowed to stand at 65 ° C. for 10 minutes.
The document offset property was evaluated according to the following criteria for the state when the stacked papers were pulled apart.
[Criteria]
○: No resistance △: Sounds crispy but image does not peel off from paper ×: Image peels off from paper

  The evaluation results are shown in Table 3.

  As is clear from the evaluation results in Table 3, all of the toners of Examples 1 to 10 of the present invention were excellent in performance evaluation. On the other hand, Comparative Examples 1 to 4, which do not contain 50 mol% or more of (y1) based on the number of moles of the carboxylic acid component (y), were poor in some performance items such as heat resistant storage stability and charging characteristics.

The toner of the present invention has both low-temperature fixability, glossiness and hot offset resistance, and is excellent in heat storage stability, charging stability, image strength and document offset property of the toner. It is useful as a toner for developing an electrostatic image used for printing or the like.

Claims (10)

  A toner binder containing a crystalline resin (A) having an alcohol component (x) and a carboxylic acid component (y) as constituent raw materials, wherein the carboxylic acid component (y) has 5 to 15 carbon atoms. Cyclic ester compound derived from crystalline resin (A) based on the weight of toner binder, containing 50 mol% or more of linear aliphatic dicarboxylic acid (y1) which is an odd number based on the number of moles of carboxylic acid component (y) A toner binder containing 0.01 wt% to 1 wt%.   The toner binder according to claim 1, wherein the linear aliphatic dicarboxylic acid (y1) having an odd number of 5 to 15 carbon atoms is 1,7-heptanedicarboxylic acid. The toner binder according to claim 1 or 2, wherein the endothermic amount of the endothermic peak at the time of temperature rise satisfies the following relational expression (1).
(S ₂ / S ₁ ) × 100 ≧ 35 (1)
However, when the temperature of the toner binder is increased from 30 ° C. to 180 ° C. under the condition of 10 ° C./min, cooled, and the temperature is increased from 0 ° C. to 180 ° C. under the condition of 10 ° C./min. The endothermic amount of the endothermic peak derived from the crystalline resin (A) is S ₁ , and the endothermic amount of the endothermic peak derived from the crystalline resin (A) in the second temperature raising process is S ₂ .   The toner according to any one of claims 1 to 3, wherein the endothermic amount of the endothermic peak derived from the crystalline resin (A) in the second temperature rising process is 1 to 30 J / g on a chart by a differential scanning calorimeter (DSC). binder.   The chart with a differential scanning calorimeter (DSC) has at least one endothermic peak top temperature derived from the crystalline resin (A) in the second temperature raising process in the range of 45 ° C to 100 ° C. The toner binder described.   The toner binder according to claim 1, wherein the acid value of the crystalline resin (A) is 10 mg KOH / g or less.   Furthermore, polyester resin which uses alcohol component (x) and carboxylic acid component (y) as constituent materials, excluding the crystalline resin (A), or resin (B) which is a modified resin thereof, A toner binder according to any one of the above.   The toner binder according to claim 7, wherein the weight ratio (B / A) of the resin (B) to the crystalline resin (A) is 50/50 to 95/5.   The chromatogram obtained by measuring the molecular weight of the resin (B) by gel permeation chromatography has a peak area with a molecular weight of 1,000 or less of the resin (B) of 10% or less of the total peak area. Toner binder. A toner comprising the toner binder according to claim 1 and a colorant.