JP6529340B2 - toner - Google Patents

Description

  The present invention relates to toners used in imaging methods such as electrophotography, electrostatic recording and toner jet methods.

  An image forming method for developing an electrostatic latent image is applied to a copying machine, a multifunction machine, and a printer.

  In recent years, energy saving of the image forming apparatus has been strongly demanded.

  As one of effective means for energy saving of the image forming apparatus, lowering the set temperature of a fixing member such as a heat roller or a film can be mentioned. However, for that purpose, the low temperature fixability of the toner has to be further improved. As one method for improving the low temperature fixability of the toner, it has been proposed to set the softening point of the toner lower by using a crystalline resin (see Patent Documents 1 and 2). By these measures, it has become possible to set the softening temperature of the toner lower by utilizing the sharp melt property of the crystalline resin and to improve the low temperature fixability.

JP 2012-255957 A Japanese Patent Application Laid-Open No. 63-27855

  Today, as colorization of multifunction machines and printers has progressed, not only low-temperature fixability but also high gloss of fixed images has been required. In particular, in terms of in-plane gloss uniformity in the low temperature fixing area, sufficient performance can not be obtained even with the use of the toner, and further improvement is required for the toner.

  An object of the present invention is to provide a toner which is excellent in low temperature fixability and which can obtain an in-plane uniform gloss in any temperature range.

The present invention is a toner having toner particles containing a binder resin containing a styrene acrylic resin and a modified polyester, and a dispersant for dispersing the modified polyester,
The modified polyester is a crystalline polyester having a polyester moiety C and a vinyl polymer moiety A,
The polyester portion C has a unit represented by the following formula (1),
The mass ratio (C / A ratio) of the polyester portion C to the vinyl polymer portion A is 40/60 to 95/5,
The dispersant is a resin having the following site a and the following site d ,
Part position a: polyester portion having a unit represented by the following formula (2),
Part position d: the absolute value of the difference between the SP value of the styrene-acrylic resin (whose ASP value), the site to be 0.10 or less,
The present invention relates to a toner characterized in that a mass ratio (a / d ratio) between the portion a and the portion d is 2/98 to 30/70.

［式（１）中、ｍは、６以上１４以下の整数を示す。ｎは、６以上１６以下の整数を示す。
式（２）中、ｏは、６以上１４以下の整数を示す。ｐは、６以上１６以下の整数を示す。］

[In the formula (1), m represents an integer of 6 or more and 14 or less. n represents an integer of 6 or more and 16 or less.
In Formula (2), o shows 6 or more and 14 or less integer. p represents an integer of 6 or more and 16 or less. ]

  According to the present invention, it is possible to provide a toner which is excellent in low-temperature fixability and which can obtain in-plane uniform gloss in any temperature range.

  Hereinafter, embodiments of the present invention will be specifically described.

The present invention is a toner having toner particles containing a binder resin containing a styrene acrylic resin and a modified polyester, and a dispersant for dispersing the modified polyester,
The modified polyester is a crystalline resin having a polyester portion C and a vinyl polymer portion A,
The said polyester part C has a unit shown by following formula (1),
The mass ratio (C / A ratio) of the polyester portion C to the vinyl polymer portion A is 40/60 to 95/5,
The dispersant has a polyester moiety having a unit represented by the following formula (2), or a moiety a where an aliphatic hydrocarbon having 12 or more carbon atoms, and the solubility parameter (SP) value of the styrene acrylic resin It is a resin having a portion d where the absolute value of the difference (ΔSP value) is 0.10 or less,
It is characterized in that a mass-based ratio (a / d ratio) of the site a to the site d is 2/98 to 30/70.

［式（１）中、ｍは、６以上１４以下の整数を示す。ｎは、６以上１６以下の整数を示す。
式（２）中、ｏは、６以上１４以下の整数を示す。ｐは、６以上１６以下の整数を示す。］

[In the formula (1), m represents an integer of 6 or more and 14 or less. n represents an integer of 6 or more and 16 or less.
In Formula (2), o shows 6 or more and 14 or less integer. p represents an integer of 6 or more and 16 or less. ]

  The present inventors are excellent in low-temperature fixability by using a specific dispersant for dispersing modified polyester in a binder resin containing a styrene acrylic resin and a modified polyester, and also in any temperature region. It has been found that a toner capable of obtaining uniform gloss can be obtained.

  Specifically, the modified polyester used in the present invention is a crystalline polyester having a polyester site C exhibiting crystallinity and a vinyl polymer site A. The softening point of the toner is lowered to achieve low temperature fixing by being compatible with the styrene acrylic resin used as a binder and the vinyl polymer site A in the fixing process. On the other hand, the styrene acrylic resin and the modified polyester have a phase separation structure at normal temperature to maintain the softening point and obtain high heat resistance.

  Furthermore, according to the present invention, by using the dispersant as defined above, the dispersant is uniformly compatible in the styrene acrylic resin due to the site d having a high affinity to the styrene acrylic resin. The dispersing agent uniformly compatible with the styrene acrylic resin interacts with the polyester portion C of the modified polyester through the portion a having high affinity to the modified polyester to promote crystallization of the polyester portion C. Thereby, the modified polyester can be highly dispersed in the styrene acrylic resin. By suppressing the bias of the crystalline material in the toner, it is presumed that the toner is uniformly melted at the time of fixing, the fixing unevenness is suppressed, and it is possible to obtain an in-plane uniform high gloss.

  The modified polyester is a crystalline polyester having a polyester site C and a vinyl polymer site A. Here, “crystalline” of crystalline polyester means having a clear endothermic peak (melting point) in measurement of differential scanning calorimetry (DSC) described later. On the other hand, a resin in which no clear endothermic peak is observed means that it is amorphous.

The polyester portion C of the modified polyester has a unit represented by the above formula (1), and, for example, a dicarboxylic acid represented by the following formula (A) or an alkyl ester compound or acid anhydride thereof and the following formula (B) And a diol represented by The polyester portion is formed by condensation polymerization of these.
HOOC- (CH ₂₎ m-COOH Formula (A)
[Wherein, m represents an integer of 6 or more and 14 or less (preferably 6 or more and 10 or less). ]
HO- (CH ₂₎ n-OH Formula (B)
[Wherein, n represents an integer of 6 or more and 16 or less (preferably 6 or more and 12 or less). ]

  As the dicarboxylic acid, a compound in which a carboxyl group is alkyl-esterified (preferably having 1 to 4 carbon atoms), a compound in which an acid anhydride is formed, or the like may be used as long as they generate the same partial skeleton in the polyester portion C.

  As the dicarboxylic acid, suberic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid and the like are preferable.

  As the diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and the like are preferable.

  The composition of the vinyl polymer portion A of the modified polyester can use known vinyl monomers such as styrene, methyl methacrylate or n-butyl acrylate. Particularly preferred is styrene, which effectively acts as a site compatible with the styrene acrylic resin, and plasticity at the time of melting is more exerted.

  The mass ratio (C / A ratio) of the polyester portion C to the vinyl polymer portion A of the modified polyester is required to be in the range of 40/60 to 95/5. When it is smaller than 40/60, the properties of the polyester portion are lost, so that the sharp melt property is insufficient and the low temperature fixability is inferior. In some cases, the polyester can not maintain its crystallinity and heat resistance may be reduced. If it is larger than 95/5, the low temperature fixability is poor because the origin of compatibility due to the vinyl polymer site is reduced. Preferably, it is in the range of 45/55 to 90/10.

  The melting point (Tm) of the modified polyester is preferably 50 ° C. or more and 90 ° C. or less. When the melting point (Tm) is 50 ° C. or more and 90 ° C. or less, blocking does not easily occur, the storage stability is excellent, and the low temperature fixability is also excellent. More preferably, the temperature is from 60 ° C. to 85 ° C.

  The melting point of the block polymer can be controlled by the monomer for forming the polyester moiety or the ratio of the polyester moiety C to the vinyl polymer moiety A.

  The modified polyester is preferably a block polymer. In addition, as a definition of a block polymer, a polymer composed of a plurality of linearly connected blocks (a glossary of basic terms of polymer science by the International Pure Applied Chemistry Association Polymer Nomenclature Committee of the Polymer Society of Japan) and Yes, and the invention follows its definition. When the modified polyester is a block polymer, a gloss at fixing is easily obtained because it is a linear polymer.

  The weight average molecular weight (Mw) of the vinyl polymer portion A of the modified polyester is preferably 3,000 or more and 14,000 or less. If it is 3000 or more and 14000 or less, it is possible to combine the properties of the vinyl polymer portion and the properties of the polyester portion, so it is easy to act as a compatible starting point with the styrene acrylic resin and is excellent in low temperature fixability. Furthermore, the performance of the vinyl polymer portion is exhibited and the durability is also excellent. 3500 or more and 12500 or less are preferable, and 4000 or more and 10000 or less are more preferable.

  The weight average molecular weight (Mw) of the modified polyester is preferably 15,000 or more and 45,000 or less, and more preferably 20,000 or more and 45,000 or less. When the weight average molecular weight is 15000 or more (more preferably 20000 or more), the mechanical strength of the modified polyester is excellent and the durability is high. If it is 45000 or less, the movement of the molecule is unlikely to be slow and the plasticizing effect at the time of melting is easily obtained. More preferably, it is 23,000 or more and 40000 or less, and further preferably 25,000 or more and 37,000 or less.

  The content of the modified polyester in the binder resin is preferably in the range of 2.0% by mass to 50.0% by mass, and is in the range of 6.0% by mass to 50.0% by mass. More preferable. When the content is 2.0% by mass or more (more preferably 6.0% by mass or more), the plasticizing effect at the time of melting and the binding effect by the block polymer are easily obtained, and the low-temperature fixability is improved. If the content is 50.0% by mass or less, charge leakage from the crystalline polyester portion is unlikely to occur, the chargeability is not easily reduced, and fogging is less likely to occur. In addition, since the stress resistance is hardly reduced, the durability is not easily reduced, and image defects such as development streaks are hardly generated. The content of the modified polyester is more preferably 10.0% by mass to 45.0% by mass, and still more preferably 20.0% by mass to 40.0% by mass.

  The dispersing agent is required to be a resin having a portion a having high affinity to the modified polyester and a portion d having high affinity to the styrene acrylic resin of the binder resin. The site a is required to have a crystalline polyester having the same structure as that of the polyester site C or an aliphatic hydrocarbon site having a carbon number of 12 or more in order to have affinity with the polyester site C of the modified polyester. is there.

  The crystalline polyester has a unit represented by the above-mentioned formula (2), and the same one as the polyester part C already mentioned above is used.

  Examples of the aliphatic hydrocarbon having 12 or more carbon atoms include polyethylene wax, polypropylene wax, paraffin wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax, lauryl acrylate, stearyl acrylate, behenyl acrylate, lauryl methacrylate, stearyl metalate. Examples thereof include resins formed by polymerization as polymerizable monomers having an aliphatic hydrocarbon having 12 or more carbon atoms in a side chain such as rate and behenyl metallate. Preferably, they are aliphatic hydrocarbons having 20 or more carbon atoms.

  As the site d having high affinity to the styrene acrylic resin, it is necessary that the resin whose absolute value (ΔSP value) of the difference from the solubility parameter (SP) value of the styrene acrylic resin is 0.10 or less . The site d is preferably a vinyl-based resin containing a styrene unit. The vinyl-based resin containing a styrene unit is obtained by polymerizing the following polymerizable monomers.

As a polymerizable monomer which produces | generates the resin used as site | part d, Styrene, alpha-methylstyrene, beta-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene P-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-Methoxystyrene and styrene derivatives such as p-phenylstyrene;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate Acrylic polymerizable monomers such as n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate And n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate. Two or more of the above monomers may be used in combination so that the absolute value (ΔSP value) of the difference from the solubility parameter (SP) value of the styrene acrylic resin is 0.10 or less.

  The mass-based ratio (a / d ratio) of the part a to the part d of the dispersant is required to be in the range of 2/98 to 30/70. If it is smaller than 2/98, the affinity with the polyester portion can not be obtained, and the dispersibility is reduced, and it becomes difficult to obtain an in-plane uniform gloss. If it is greater than 30/70, the affinity to the vinyl polymer site is lowered, and the dispersibility is also lowered, making it difficult to obtain an in-plane uniform gloss. Preferably, it is in the range of 4/96 to 25/75.

  The content ratio of the modified polyester to the dispersant in the toner is preferably in the range of 1.0: 1.0 to 10.0: 1.0. By controlling the content ratio in the range of 1.0: 1.0 to 10.0: 1.0, the dispersion of the modified polyester is controlled, and the in-plane uniform gloss which is the effect of the present invention can be easily obtained.

  As a polymerizable monomer which produces | generates a styrene acrylic resin, it is possible to use the vinyl-type polymerizable monomer in which radical polymerization is possible. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a multifunctional polymerizable monomer can be used.

As the monofunctional polymerizable monomer, styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n- Butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, And styrene derivatives such as p-phenylstyrene;
Methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate Acrylic polymerizable monomers such as n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate And n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene Glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Methacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxydiethoxy) phenyl) propane, Examples include 2,2′-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinyl naphthalene, and divinyl ether.

  Monofunctional polymerizable monomers may be used alone or in combination of two or more, or a combination of a monofunctional polymerizable monomer and a polyfunctional polymerizable monomer, or a multifunctional polymerizable The monomers may be used alone or in combination of two or more. Among the polymerizable monomers, it is preferable to use styrene or a styrene derivative alone or as a mixture, or by mixing them with other polymerizable monomers from the viewpoint of the developing characteristics and durability of the toner. .

  The production method for producing the toner particles according to the present invention may be any production method, but polymerization is carried out in an aqueous medium such as suspension polymerization, emulsion polymerization and suspension granulation. It is preferable to obtain by the method of producing toner particles for granulating the functional monomer composition.

  Hereinafter, the method for producing toner particles will be described using the most preferable suspension polymerization method among the methods for producing toner particles used in the present invention.

  A polymerizable monomer that produces the above-mentioned styrene acrylic resin, a specific block polymer, and, if necessary, other additives such as a colorant, a wax, etc., as in a homogenizer, ball mill, colloid mill, ultrasonic dispersion machine The polymer is uniformly dissolved or dispersed by a dispersing machine, and the polymerization initiator is dissolved therein to prepare a polymerizable monomer composition. Next, toner particles are produced by suspending the polymerizable monomer composition in an aqueous medium containing a dispersion stabilizer to carry out polymerization.

  The polymerization initiator may be added simultaneously with the addition of the other additive to the polymerizable monomer, or may be mixed just before suspending in the aqueous medium. Further, immediately after granulation, a polymerization initiator dissolved in a polymerizable monomer or a solvent may be added before starting the polymerization reaction.

  In the case of a polymerization method using an aqueous medium such as a suspension polymerization method, it is preferable to add a polar resin to the above mixed solution. By adding a polar resin, it is possible to promote the inclusion of modified polyester and wax.

  When the polar resin is present in the colorant dispersion suspended in the aqueous medium, the polar resin is easily transferred to the vicinity of the interface between the aqueous medium and the colorant dispersion because of the difference in affinity to water. Polar resin will be unevenly distributed on the surface. As a result, the toner particles have a core-shell structure.

  In addition, if the polar resin used for the shell is selected to have a high melting temperature, even if the binder resin is designed to be melted at a lower temperature for the purpose of low temperature fixation, the occurrence of blocking during storage of the toner It can be suppressed.

  The polar resin is preferably a polyester resin or a carboxyl-containing styrene resin. By using a polyester resin or a carboxyl-containing styrenic resin as the polar resin, when the resin is unevenly distributed on the surface of the toner particles to form a shell, the lubricity of the resin itself can be expected.

  As polyester resin, resin which carried out condensation polymerization of the acid ingredient monomer and alcohol ingredient monomer which are mentioned below can be used. As an acid component monomer, terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, camphoric acid Examples include acids, cyclohexanedicarboxylic acid, and trimellitic acid.

  As an alcohol component monomer, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) And the alkylene glycols and polyalkylene glycols of cyclohexane, bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane and pentaerythritol.

  As the carboxyl group-containing styrene resin, a styrene-based acrylic acid copolymer, a styrene-based methacrylic acid copolymer, a styrene-based maleic acid copolymer and the like are preferable, and in particular, a styrene-acrylic acid ester-acrylic acid-based copolymer A polymer is preferable because the charge amount can be easily controlled. The carboxyl group-containing styrenic resin more preferably contains a monomer having a primary or secondary hydroxyl group. As a specific polymer composition, styrene-2-hydroxyethyl methacrylate-methacrylic acid-methyl methacrylate copolymer, styrene-n-butyl acrylate-2-hydroxyethyl methacrylate-methacrylic acid-methacrylic acid methyl copolymer And styrene-α-methylstyrene-2-hydroxyethyl methacrylate-methacrylic acid-methacrylic acid methyl methacrylate copolymer and the like. A resin containing a monomer having a primary or secondary hydroxyl group has high polarity, and the long-term storage stability is better.

  The content of the polar resin is 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin (styrene acrylic resin (or polymerizable monomer for producing styrene acrylic resin) and block polymer) Is preferable, and 2.0 parts by mass or more and 10.0 parts by mass or less are more preferable.

  In the present invention, known wax components may be used as the wax. Specifically, paraffin wax, microcrystalline wax, petroleum wax and its derivative of petrolactam, montan wax and its derivative, hydrocarbon wax and its derivative by the Fischer-Tropsch method, polyolefin wax represented by polyethylene and its derivative, Carnauba wax, natural waxes of candelilla wax and derivatives thereof may be mentioned, and derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. In addition, alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid or compounds thereof; acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes and the like. These can be used alone or in combination.

  Among these, when using a polyolefin, a hydrocarbon wax by a Fischer-Tropsch method, or a petroleum wax, the effect of improving the developability and the transferability is further enhanced. In addition, an antioxidant may be added to these wax components as long as the charging properties of the toner are not affected. Moreover, it is preferable to use 1.0 to 30.0 parts by mass of these wax components with respect to 100 parts by mass of the binder resin.

  The melting point of the wax component used in the present invention is preferably in the range of 30 ° C. or more and 120 ° C. or less, more preferably in the range of 60 ° C. or more and 100 ° C. or less.

  By using the wax component exhibiting the thermal characteristics as described above, not only the good fixability of the obtained toner but also the releasing effect by the wax component is efficiently exhibited, and a sufficient fixing area is secured.

  In the present invention, the following organic pigments, organic dyes and inorganic pigments may be used as colorants.

  Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, the following may be mentioned. C. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, and 66.

  Examples of the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following may be mentioned. C. I. Pigment red 2, 3, 5, 6, 7, 1923, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221 and 254.

  Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following may be mentioned. C. I. Pigment yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185, 191 and 194.

  Examples of the black colorant include carbon black, and those toned in black using the above-mentioned yellow colorant, magenta colorant, and cyan colorant.

  These colorants can be used alone, in a mixture, or even in the form of a solid solution. The colorant used in the present invention is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner particles.

  The colorant is preferably used in an amount of 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

  When toner particles are obtained using a suspension polymerization method, it is preferable to use a colorant that has been subjected to a hydrophobization treatment with a substance that does not inhibit polymerization, in consideration of the polymerization inhibition property of the colorant and the aqueous phase migration property. . As a preferable method of hydrophobizing the dye, there is mentioned a method of polymerizing a polymerizable monomer in the presence of the dye in advance to obtain a colored polymer, and the obtained colored polymer can be used as a polymerizable monomer. Add to the composition.

  The carbon black may be treated with a substance (polyorganosiloxane) that reacts with the surface functional group of the carbon black, in addition to the hydrophobization treatment similar to the above-mentioned dye.

  Moreover, you may use a charge control agent as needed. As the charge control agent, known agents can be used, and in particular, a charge control agent that has a high triboelectric charging speed and can stably maintain a constant triboelectric charge amount is preferable. Furthermore, when the toner particles are produced by suspension polymerization, a charge control agent having low polymerization inhibition and substantially free of a soluble matter in an aqueous medium is particularly preferable.

  The charge control agent may be one that controls the toner to be negatively chargeable or one that controls to be positively chargeable. Examples of the toner that controls the toner to be negatively chargeable include the following. Monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, metal compounds of oxycarboxylic acids and dicarboxylic acids, aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and metal salts thereof, Anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarenes, and charge control resins can be mentioned.

  On the other hand, examples of charge control agents that control the toner to be positively chargeable include the following. Guanidine compounds; imidazole compounds; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts that are analogs thereof And their lake pigments; triphenylmethane dyes and their lake pigments (as lakeing agents, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, and Ferrocyanides); metal salts of higher fatty acids; charge control resins.

  These charge control agents may be added alone or in combination of two or more.

  Among these charge control agents, metal-containing salicylic acid type compounds are preferable, and those in which the metal is aluminum or zirconium are particularly preferable.

  The addition amount of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the binder resin. It is.

  Further, as the charge control resin, it is preferable to use a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group. As a polymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group, it is particularly preferable to contain a sulfonic acid group-containing acrylamide monomer or a sulfonic acid group-containing methacrylamide monomer in a copolymerization ratio of 2% by mass or more More preferably, it is contained 5 mass% or more. The charge control resin has a glass transition temperature (Tg) of 35 ° C. to 90 ° C., a peak molecular weight (Mp) of 10,000 to 30,000, and a weight average molecular weight (Mn) of 25,000 to 50,000. Some are preferred. When this is used, preferable triboelectric charging characteristics can be imparted without affecting the thermal characteristics required for toner particles. Furthermore, since the charge control resin contains a sulfonic acid group, the dispersibility of the charge control resin itself in the dispersion of the colorant and the dispersibility of the colorant are improved, and the coloring power, transparency, and The triboelectric charging characteristics can be further improved.

  A polymerization initiator may be used to polymerize the polymerizable monomer. Examples of the polymerization initiator that can be used in the present invention include organic peroxide initiators and azo polymerization initiators. Examples of the organic peroxide initiator include the following. Benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1-bis (t-butylperoxy) cyclododecane, t-butylperoxymaleic acid, bis (t-butylperoxy) isophthalate, methyl ethyl ketone peroxide, tert-butyl peroxy-2-ethylhexanoate, diisopropyl Peroxy carbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and tert-butyl-peroxypivalate.

  As an azo polymerization initiator, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile) And 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobismethylbutyronitrile and the like.

  Further, as a polymerization initiator, a redox initiator in which an oxidizing substance and a reducing substance are combined can also be used. Examples of the oxidizing substance include hydrogen peroxide, inorganic peroxides of persulfates (sodium salt, potassium salt and ammonium salt) and oxidizing metal salts of tetravalent cerium salt. As the reducing substance, reducing metal salts (divalent iron salts, monovalent copper salts, and trivalent chromium salts), ammonia, lower amines (methylamines, and methylamines, and having 1 to 6 carbon atoms such as ethylamine) ), Amino compounds such as hydroxylamine, sodium thiosulfate, sodium hydrosulfite, sodium bisulfite, sodium sulfite, and reducible sulfur compounds of sodium formaldehyde sulfoxylate, lower alcohols (with 1 to 6 carbon atoms) And ascorbic acid or salts thereof, and lower aldehydes (having 1 to 6 carbon atoms).

  The polymerization initiator is selected with reference to a 10-hour half-life temperature, and is used alone or in combination. Although the addition amount of the said polymerization initiator changes with the polymerization degree made into the objective, generally 0.5 mass part or more and 20.0 mass parts or less are added with respect to 100 mass parts of polymerizable monomers.

  It is also possible to further add and use known chain transfer agents and polymerization inhibitors in order to control the degree of polymerization.

  When the polymerizable monomer is polymerized, various crosslinking agents can also be used. As a crosslinking agent, divinylbenzene, 4,4'-divinylbiphenyl, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, glycidyl acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and trimethylol Polyfunctional compounds such as propane and methacrylate are included.

  As a dispersion stabilizer used when preparing an aqueous medium, the dispersion stabilizer of a well-known inorganic compound and the dispersion stabilizer of an organic compound can be used. As a dispersion stabilizer for inorganic compounds, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate And barium sulfate, bentonite, silica and alumina. On the other hand, dispersion stabilizers for organic compounds include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and salts thereof, and starch. The use amount of these dispersion stabilizers is preferably 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

  Among these dispersion stabilizers, when a dispersion stabilizer of an inorganic compound is used, a commercially available product may be used as it is, but in order to obtain a dispersion stabilizer having a finer particle size, the inorganic compound is preferably contained in an aqueous medium. It may be generated. For example, in the case of tricalcium phosphate, it can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high stirring.

  To the toner particles, an external additive may be externally added to impart various properties to the toner. Examples of external additives for improving the flowability of toner include fine particles of silica, fine particles of titanium oxide, and fine inorganic particles such as fine particles of double oxides thereof. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferable. For example, the toner of the present invention can be obtained by externally adding and mixing inorganic fine particles to toner particles and adhering them to the surface of the toner particles. A known method may be adopted as the method of externally adding the inorganic fine particles. For example, the method of performing a mixing process using Mitsui Henschel mixer (made by Mitsui Miike Kako Co., Ltd.) is mentioned.

Fine silica particles include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine particles, it is preferable to use a dry silica having a small amount of silanol groups on the surface and the inside of the silica fine particles and a small amount of Na ₂ O and SO ₃ ^2- . In addition, the dry silica may be composite fine particles of silica and other metal oxides by using a metal halogen compound such as aluminum chloride, titanium chloride or the like together with a silicon halogen compound in the production process.

  By subjecting the surface of the inorganic fine particles to a hydrophobization treatment with a treating agent, it is possible to achieve adjustment of the triboelectric charge of the toner, improvement of environmental stability, and improvement of fluidity under high temperature and high humidity. It is preferable to use a hydrophobicized inorganic fine particle. When the inorganic fine particles externally added to the toner absorb moisture, the triboelectric charge amount and the fluidity of the toner are reduced, and the developability and the transferability are easily reduced.

  As a treating agent for hydrophobizing inorganic fine particles, unmodified silicone varnish, various modified silicone varnish, unmodified silicone oil, various modified silicone oil, silane compound, silane coupling agent, other organosilicon compounds, and And organic titanium compounds. Among them, silicone oil is preferred. These treating agents may be used alone or in combination.

  The total addition amount of the inorganic fine particles is preferably 1.0 to 5.0 parts by mass, and more preferably 1.0 to 2.5 parts by mass with respect to 100 parts by mass of the toner particles. is there. The external additive preferably has a particle diameter of 1/10 or less of the average particle diameter of the toner particles from the viewpoint of durability when added to the toner.

  Below, the calculation method and measurement method of each physical property value prescribed | regulated by this invention are described.

<Method of calculating solubility parameter (SP value)>
The SP value in the present invention was determined using Fedors' equation (1). Here, the values of Δei and Δvi are “Fundamental Science of Coatings”, pp. 54-57, 1986 (槇), Tables 3 to 9 for evaporation energy and molar volume of atoms and group (25 ° C.) ” Was referred to.
δi = [Ev / V] ^1/2 = [Δei / Δvi] ^1/2 equation (1)
Ev: evaporation energy V: molar volume Δei: evaporation energy of atom or group of component i Δvi: molar volume of atom or group of component i

<Measuring method of molecular weight>
The peak top molecular weight (Mp) of the wax dispersant is measured by gel permeation chromatography (GPC) as follows.

  First, the block polymer and the toner are dissolved in tetrahydrofuran (THF) at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Misholy Disc" (manufactured by Tosoh Corp.) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. It measures on condition of the following using this sample solution.

Device: High-speed GPC device "HLC-8220GPC" (manufactured by Tosoh Corp.)
Column: LF-604, 2 stations [Showa Denko KK]
Eluent: THF
Flow rate: 0.6 ml / min
Oven temperature: 40 ° C
Sample injection volume: 0.020 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "(manufactured by Tosoh Co., Ltd.) are used to obtain molecular weight calibration curves.

<Method of measuring weight average particle diameter (D4), number average particle diameter (D1)>
The weight average particle size (D4) and the number average particle size (D1) of the toner are calculated as follows. As a measuring apparatus, a precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube and using a pore electrical resistance method is used. The setting of measurement conditions and the analysis of measurement data use the attached special software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with 25,000 channels of effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, a solution in which special grade sodium chloride is dissolved in ion exchange water so that the concentration is 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  In addition, before performing measurement and analysis, the setting of the dedicated software is performed as follows.

  In the "Change Standard Measurement Method (SOM)" screen of the dedicated software, set the total count number in the control mode to 50000 particles, set the number of measurements once, and the Kd value "standard particle 10.0 μm" (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the "Threshold / noise level measurement button". Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Aperture tube flush after measurement”.

  In the dedicated soft “pulse to particle size conversion setting” screen, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Put 200 ml of the electrolytic aqueous solution into a 250 ml round bottom beaker for Multisizer 3 dedicated to a glass, set it on a sample stand, and stir the stirrer rod at 24 rotations / second counterclockwise. Then, dirt and air bubbles in the aperture tube are removed by the "aperture flush" function of special software.
(2) Into a 100 ml flat bottom beaker made of glass, 30 ml of the electrolytic aqueous solution is placed. Among them, “contaminone N” (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH 7 precision measuring instrument cleaning consisting of organic builders as a dispersing agent, Wako Pure Chemical Industries, Ltd. 0.3 ml of a diluted solution obtained by diluting 3 times) with deionized water.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with 180 degrees of phase shift, and an ultrasonic dispersion device “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared. Put 3.3 l of ion exchange water into the water tank of the ultrasonic disperser, and add 2 ml of Contaminone N into this water tank.
(4) The beaker of said (2) is set to the beaker fixing hole of the said ultrasonic dispersion device, and an ultrasonic dispersion device is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added little by little to the aqueous electrolytic solution and dispersed. Then, ultrasonic dispersion processing is continued for another 60 seconds. In addition, in ultrasonic dispersion, the water temperature of the water tank is appropriately adjusted so as to be 10 ° C. or more and 40 ° C. or less.
(6) In the round bottom beaker of (1) placed in the sample stand, the aqueous electrolyte solution of (5) in which the toner is dispersed using a pipette is dropped to adjust the measurement concentration to 5%. Then, measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device to calculate the weight average particle diameter (D4) and the number average particle diameter (D1). The “average diameter” on the “analysis / volume statistical value (arithmetic mean)” screen when the graph / volume% is set in the dedicated software is the weight average particle diameter (D4). The "average diameter" on the "Analysis / number statistics (arithmetic mean)" screen when the graph / number% is set by the dedicated software is the number average particle diameter (D1).

<Method of measuring C / A ratio of modified polyester, d / a ratio of dispersant>
The ratio of mass-based ratio (C / A ratio) of the polyester part C to the vinyl polymer part A of the modified polyester and the mass-based ratio (a / d ratio) of the part a to the part d of the dispersant are nuclear magnetic resonance spectroscopy (1H -NMR) [400 MHz, CDCl3, room temperature (25 [deg.] C.)] was used.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by Nippon Denshi Co., Ltd.)
Measurement frequency: 400 MHz
Pulse condition: 5.0 μs
Frequency range: 10500 Hz
Integration count: 64 times

  Based on the integral value of the obtained spectrum, the mass basis ratio (C / A ratio) of the polyester part C and the vinyl polymer part A of the modified polyester and the mass basis ratio (a / d ratio) of the part a and the part d of the dispersant Was calculated.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. In addition, Examples 1-7 and 10-31 are reference examples among Examples 1-31.

<Production of Modified Polyester 1>
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing pipe, and a pressure reducing device, 100.0 parts by mass of xylene was heated while replacing with nitrogen, and the solution was refluxed at a temperature of 140 ° C. A mixture of 100.0 parts by mass of styrene and 15.9 parts by mass of Dimethyl 2,2'-azobis (2-methylpropionate) was added dropwise over 3 hours, and after completion of the addition, the solution was stirred for 3 hours . Thereafter, xylene and residual styrene were distilled off at 160 ° C. and 1 hPa to obtain a vinyl polymer (1).

  Next, 100.0 parts by mass of the vinyl polymer (1) obtained above in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing pipe, a dehydrating pipe and a decompression device, 80.0 parts by mass of xylene as an organic solvent, 1 As an esterification catalyst, 0.43 parts by mass of titanium (IV) isopropoxide was added to 85,5 parts by mass of 10-decanediol, and the mixture was reacted at 150 ° C. for 4 hours under a nitrogen atmosphere. Thereafter, 90.5 parts by mass of sebacic acid was added, and the mixture was reacted at 150 ° C. for 3 hours and at 180 ° C. for 4 hours. Thereafter, the mixture was further reacted at 180 ° C. and 1 hPa until desired Mw was obtained, to obtain a modified polyester 1 having a polyester portion C and a vinyl polymer portion A. Physical properties of the resulting modified polyester 1 are shown in Table 1. The resulting Modified Polyester 1 was found to have a clear endothermic peak (melting point) in the measurement of differential scanning calorimetry (DSC).

<Production of Modified Polyesters 2, 4 to 5 and 9 to 15>
The monomer species and reaction conditions were changed using the method for producing modified polyester 1 to obtain modified polyesters 2, 4 to 5 and 9 to 15, respectively. The physical properties of the resulting modified polyesters 2, 4 to 5 and 9 to 15 are shown in Table 1. The resulting modified polyesters 2, 4 to 5 and 9 to 15 were found to have a clear endothermic peak (melting point) in the measurement of differential scanning calorimetry (DSC).

<Production of Modified Polyester 3>
100.0 parts by mass of sebacic acid and 93.5 parts by mass of 1,10-decanediol are added to a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introducing pipe, a dehydrating pipe, and a pressure reducing device and stirred While heating, the temperature was raised to 130.degree. After 0.7 part by mass of titanium (IV) isopropoxide is added, the temperature is raised to 160 ° C., and condensation polymerization is performed over 5 hours. 5.0 parts by mass of acrylic acid and 30.0 parts by mass of styrene were dropped over 1 hour. Stirring was continued for 1 hour while maintaining at 160 ° C., and then the monomer of the styrene resin component was removed at 8.3 kPa for 1 hour. Thereafter, the temperature was raised to 210 ° C., and the reaction was carried out until the desired molecular weight was obtained, to obtain a modified polyester 3. Physical properties of the resulting modified polyester ester 3 are shown in Table 1. The resulting Modified Polyester 3 was found to have a clear endothermic peak (melting point) in the measurement of differential scanning calorimetry (DSC).

<Production of Modified Polyesters 6 to 8 and 16>
Modified monomers 6 and reaction conditions were changed using a method for producing modified polyester 3 to obtain modified polyesters 6 to 8 and 16. The physical properties of the resulting modified polyesters 6 to 8 and 16 are shown in Table 1. The resulting modified polyesters 6 to 8 and 16 were found to have a clear endothermic peak (melting point) in the measurement of differential scanning calorimetry (DSC).

<Production of Dispersant 1>
440.0 parts by mass of dehydrated chloroform and 100.0 parts by mass of terminal hydroxyl group-containing polyethylene (Mw: 3000) were completely dissolved in a reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube After that, 5.0 parts by mass of triethylamine was added, and 15.0 parts by mass of 2-bromoisobutyryl bromide was gradually added while cooling with ice. Then, it stirred at room temperature (25 degreeC) overnight.

  The resin solution was gradually dropped in a container containing 550.0 parts by mass of methanol to reprecipitate the resin component, and then filtered, purified, and dried to obtain a precursor 1.

  Next, 100.0 parts by mass of the precursor 1 obtained above, 300.0 parts by mass of styrene, 3.5 (parts by mass) copper (I) bromide in a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introducing pipe. The polymerization reaction was carried out at a temperature of 98 ° C. while stirring with the addition of parts by mass and 8.5 parts by mass of pentamethyldiethylene triamine. When the desired molecular weight was achieved, the reaction was stopped, reprecipitated with 250.0 parts by mass of methanol, filtered and purified to remove unreacted styrene and catalyst. Then, it dried with the vacuum dryer set to 50 degreeC, and obtained the dispersing agent 1. Physical properties of the resulting dispersant 1 are shown in Table 2.

<Production of Dispersant 2, 4 to 6, 8 to 10>
The raw material and reaction conditions were changed using the manufacturing method of the dispersing agent 1, and the dispersing agents 2-10 were obtained. Physical properties of the obtained dispersants 2 to 10 are shown in Table 2.

<Production of Dispersant 3>
100.0 parts by mass of xylene, 2.0 parts by mass of ethyl 2-bromoisobutyrate, and 70.0 parts by mass of behenyl acrylate monomer are added to a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introducing pipe. Solution was completely dissolved at 50.degree. C., and then 0.5 parts by mass of copper (I) bromide and 1.0 parts by mass of pentamethyldiethylene triamine were added and the polymerization reaction was carried out at a temperature of 80.degree. . When the desired molecular weight was achieved, the reaction was stopped, reprecipitated with 250.0 parts by mass of methanol, filtered and purified to remove unreacted behenyl acrylate monomer and catalyst. Thereafter, a vacuum dryer set at 50 ° C. was used to obtain a precursor 2.

  Next, 100.0 parts by mass of the precursor 2 obtained above, 600.0 parts by mass of styrene, copper (I) bromide 5.5 in a reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube The polymerization reaction was carried out at a temperature of 98 ° C. while stirring with the addition of parts by mass and 11.0 parts by mass of pentamethyldiethylene triamine. When the desired molecular weight was achieved, the reaction was stopped, reprecipitated with 250.0 parts by mass of methanol, filtered and purified to remove unreacted styrene and catalyst. Then, it dried with the vacuum dryer set to 50 degreeC, and obtained the dispersing agent 3. Physical properties of the resulting dispersant 3 are shown in Table 2.

<Production of Dispersant 7>
The raw material was changed using the manufacturing method of the dispersing agent 3, and the dispersing agent 7 was obtained. Physical properties of the resulting dispersant 7 are shown in Table 2.

<Production of Toner 1>
9.0 parts by mass of tricalcium phosphate is added to 1300.0 parts by mass of ion exchange water heated to a temperature of 60 ° C. K. The mixture was stirred at a stirring speed of 15,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare an aqueous medium.

Further, the following binder resin material was mixed by a propeller type stirring device at a stirring speed of 100 rpm to prepare a solution.
Styrene 70.0 parts by mass n-butyl acrylate 20.0 parts by mass Next, after heating the solution to a temperature of 65 ° C.,
-Modified polyester 1 10.0 parts by mass-Cyan colorant (CI pigment blue 15: 3) 6.5 parts by mass-Negative charge control agent (Bontron E-88, manufactured by Orient Chemical Co.) 0.5 parts by mass Hydrocarbon wax (Tm = 78 ° C.) 9.0 parts by mass Dispersant 1 2.0 parts by mass Polar resin 5.0 parts by mass (Styrene-2-hydroxyethyl methacrylate-methacrylic acid-methacrylic acid methyl copolymer , Acid value 10 mg KOH / g, Tg = 80 ° C., Mw = 15,000)
, T. K. The mixture was stirred with a homomixer (manufactured by Tokushu Kika Kogyo) at a stirring speed of 10,000 rpm, and dissolved and dispersed to prepare a polymerizable monomer composition.

Subsequently, the polymerizable monomer composition is charged into the aqueous medium, and 6.0 parts by mass of perbutyl PV (10-hour half-life temperature 54.6 ° C. (made by NOF Corporation)) is added as a polymerization initiator. At a temperature of 70 ° C. K. Using a homomixer, the mixture was stirred for 20 minutes at a stirring speed of 15,000 rpm for granulation.

  Transfer to a propeller-type stirring device, and while stirring at a stirring speed of 200 rpm, the polymerization monomer of styrene and n-butyl acrylate in the polymerizable monomer composition are polymerized for 5 hours at a temperature of 85 ° C. A slurry containing particles was produced. After completion of the polymerization reaction, the slurry was cooled. Hydrochloric acid was added to the cooled slurry to adjust the pH to 1.4, and stirring was performed for 1 hour to dissolve the calcium phosphate salt. Thereafter, the slurry was washed with an amount of water 10 times that of the slurry, and after filtration and drying, the particle size was adjusted by classification to obtain toner particles.

  In the toner particles, 90.0 parts by mass of styrene-acrylic resin, 10.0 parts by mass of modified polyester, 6.5 parts by mass of cyan colorant, 9.0 parts by mass of wax, a negatively chargeable control agent 0.5 parts by mass, 2.0 parts by mass of dispersant 1 and 5.0 parts by mass of polar resin were contained.

Hydrophobic silica fine particles (primary particle diameter: 7 nm, BET specific surface area: 130 m) treated with 20% by mass of dimethyl silicone oil with respect to silica fine particles as an external additive with respect to 100.0 parts by mass of the above toner particles Toner 1 was obtained by mixing 1.5 parts by mass of ² / g) with Mitsui Henschel Mixer (manufactured by Mitsui Miike Kako Co., Ltd.) for 15 minutes at a stirring speed of 3000 rpm. Physical properties of Toner 1 are shown in Table 3.

<Manufacture of toner 2 to 35>
Toners 2 to 35 were obtained by the same manufacturing method as that of Toner 1 except that the raw materials and the number of added parts were changed. Physical properties of Toners 2 to 35 are shown in Table 3.

<Production of Toner 36>
Styrene-acrylic resin 90.0 parts by mass (copolymer of styrene: n-butyl acrylate = 80: 20 (mass ratio)) (Mw = 30,000, Tg = 55 ° C.)
-Modified polyester 1 10.0 parts by mass-Dispersant 1 2.0 parts by mass-Methyl ethyl ketone 100.0 parts by mass-Ethyl acetate 100.0 parts by mass-Hydrocarbon wax (Tm = 78 ° C) 9.0 parts by mass-Cyan Colorant (C.I. Pigment Blue 15: 3) 6.5 parts by mass · Negative charge control agent (Bontron E-88, manufactured by Orient Chemical Co., Ltd.) 0.5 parts by mass Attritor (Mitsui Miike KIKO) The mixture was dispersed for 3 hours using Co., Ltd.) to obtain a colorant dispersion.

  On the other hand, 27.0 parts by mass of calcium phosphate is added to 3000.0 parts by mass of ion-exchanged water heated to a temperature of 60 ° C. K. The aqueous medium was prepared by stirring with a homomixer (manufactured by Tokushu Kika Kogyo) at a stirring speed of 10,000 rpm. The above colorant dispersion is charged into the above aqueous medium, and a temperature of 65 ° C. in an N 2 atmosphere is used. K. The colorant particles were granulated by stirring with a homomixer at a stirring speed of 12,000 rpm for 15 minutes. Then, T.S. K. Change from a homomixer to a normal propeller stirring device, maintain the stirring speed of the stirring device at 150 rpm, raise the internal temperature to 95 ° C and hold for 3 hours to remove the solvent from the dispersion, and disperse the toner particles The solution was prepared.

  Hydrochloric acid was added to the obtained dispersion of toner particles to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve calcium phosphate. The above dispersion was filtered and washed by a pressure filter to obtain toner aggregates. Thereafter, toner aggregates were crushed and dried to obtain toner particles.

  The toner particles include 90.0 parts by mass of styrene-acrylic resin, 10.0 parts by mass of modified polyester, 6.5 parts by mass of cyan colorant, 9.0 parts by mass of wax, and 0.5 of negative charge control. Parts by mass were included.

Hydrophobic silica fine particles (primary particle diameter: 7 nm, BET specific surface area treated with 20% by mass of dimethyl silicone oil with respect to silica fine particles as an external additive with respect to 100.0 parts by mass of the obtained toner particles Toner 36 was obtained by mixing 1.5 parts by mass of 130 m ² / g) with Mitsui Henschel Mixer (manufactured by Mitsui Miike Kako Co., Ltd.) for 15 minutes at a stirring speed of 3000 rpm. Physical properties of the toner 36 are shown in Table 3.

<Examples 1-31, Comparative Examples 1-5>
The performance of each of the obtained toners was evaluated according to the following method. In each evaluation, the criteria C are the levels at which the effects of the present invention are obtained. The results are shown in Table 4.

[Dispersibility of Modified Polyester]
The dispersibility of the modified polyester in the toner was evaluated by observing the cross section of the toner with a transmission electron microscope, and measuring the domain size and number of the modified polyester.

Specifically, the toner is embedded in a visible light curable embedding resin (D-800, manufactured by Nisshin EM Co., Ltd.), cut to a thickness of 60 nm with an ultrasonic ultramicrotome (EM5, manufactured by Leica Co., Ltd.), and a vacuum dyeing apparatus Ru staining was performed using (manufactured by Filgen). Thereafter, observation was performed with a transmission electron microscope (H7500, manufactured by Hitachi, Ltd.) at an acceleration voltage of 120 kV. (Toner to be observed, 100 particles within ± 2.0 μm from weight average particle diameter are selected.) For the domain size of modified polyester, the average value of the circle equivalent diameter of the cross-sectional area is defined as the domain size.
A: Circle equivalent diameter of domain is less than 200 nm B: Circle equivalent diameter of domain is 200 nm or more and less than 500 nm C: Circle equivalent diameter of domain is 500 nm or more and less than 1000 nm, or the number of domains is 5 or more and less than 10 D: Domain Circle equivalent diameter is 1000 nm or more and less than 1500 nm, or the number of domains is 2 or more and less than 5 E: Circle equivalent diameter of domain is 1500 nm or more, or the number of domains is 1

〔blocking〕
5 g of each toner was taken in a 50 cc poly cup and left at a temperature of 55 ° C./humidity 10% RH for 3 days to check for the presence or absence of aggregates and evaluated according to the following criteria.

(Evaluation criteria)
A: No clumps are generated B: Slight clumps are generated, Crushed when lightly pressed with a finger C: Clumps are generated, Crushed with a light finger D: Clumped completely

<Image evaluation>
The image evaluation was performed by partially modifying a commercially available color laser printer (HP Color LaserJet 3525 dn). Modifications have been made to work with only one process cartridge installed. In addition, the fuser was remodeled so that it could be changed to any temperature.

  Remove the toner from the process cartridge for black toner installed in this color laser printer, clean the inside with air blow, introduce each toner (300 g) to the process cartridge, and refill the toner The process cartridge was mounted on a color laser printer, and the following image evaluation was performed. Specific image evaluation items are as follows.

Low temperature fixability
A solid image (toning amount: 0.9 mg / cm ² ) was printed on a transfer material while changing the fixing temperature, and evaluated according to the following criteria. The fixing temperature is a value obtained by measuring the surface of the fixing roller using a non-contact thermometer. As the transfer material, plain paper of LETTER size (XEROX 4200, manufactured by XEROX, 75 g / m ² ) was used.

(Evaluation criteria)
A: No offset at 100 ° C B: Offset at 100 ° C C: Offset at 110 ° C D: Offset at 120 ° C

〔gross〕
A solid image (toning amount: 0.6 mg / cm ² ) is printed at a fixing temperature of 130 ° C., and the upper three points, the middle three points, and the lower three points are totaled using PG-3D (manufactured by Nippon Denshoku Kogyo) The gross value was measured at 9 points and the average value was taken. As a transfer material, LETTER size plain paper (XEROX 4200 paper, manufactured by XEROX, 75 g / m ² ) was used.

(Evaluation criteria)
A: Gloss value 30 or more B: Gloss value 20 or more and less than 30 C: Gloss value 15 or more and less than 20 D: Gloss value less than 15

[Gross in-plane uniformity]
A solid image (toning amount: 0.6 mg / cm ² ) is printed at a fixing temperature of 130 ° C. and gloss is obtained at the upper three points, the middle three points, and the lower three points using PG-3D (made by Nippon Denshoku Kogyo) The values were measured and evaluated as the difference between the highest part and the lowest part. As a transfer material, LETTER size plain paper (XEROX 4200 paper, manufactured by XEROX, 75 g / m ² ) was used.
A: Difference of gloss value less than 1.0 B: Difference of gloss value 1.0 or more and less than 2.0 C: Difference of gloss value 2.0 or more and less than 3.0 D: Difference of gloss value is 3. 0 or more

Claims (8)

Binder resin containing styrene acrylic resin and modified polyester, and
A toner having toner particles containing a dispersant for dispersing the modified polyester,
The modified polyester is a crystalline polyester having a polyester moiety C and a vinyl polymer moiety A,
The polyester portion C has a unit represented by the following formula (1),
The mass ratio (C / A ratio) of the polyester portion C to the vinyl polymer portion A is 40/60 to 95/5,
The dispersant is a resin having the following site a and the following site d ,
Part position a: polyester portion having a unit represented by the following formula (2),
Part position d: the absolute value of the difference between the SP value of the styrene-acrylic resin (whose ASP value), the site to be 0.10 or less,
A toner characterized in that a mass ratio (a / d ratio) between the portion a and the portion d is 2/98 to 30/70.

[In the formula (1), m represents an integer of 6 or more and 14 or less. n represents an integer of 6 or more and 16 or less. In Formula (2), o shows 6 or more and 14 or less integer. p represents an integer of 6 or more and 16 or less. ] Content ratio of mass of the modified polyester and the dispersing agent in the toner is 1.0: 1.0 to 10.0: toner according to 1.0 der Ru請 Motomeko 1. The modified polyester, the toner of claim 1 or 2 is a block polymer having a polyester portion C and the vinyl polymer moiety A. The toner according to any one of claims 1 to 3, wherein a weight average molecular weight (Mw) of the vinyl polymer portion A in the modified polyester is 3,000 or more and 14,000 or less. The toner according to any one of claims 1 to 4, wherein a weight average molecular weight (Mw) of the modified polyester is 15000 or more and 45000 or less. The toner according to any one of claims 1 to 5 , wherein a content of the modified polyester is 2.0% by mass or more and 50.0% by mass or less with respect to the binder resin. The site d of the dispersant, the toner according to any one of 請 Motomeko 1-6 Ru vinyl resins sites der containing styrene units. The toner according to any one of claims 1 to 7 , wherein the melting point (Tm) of the modified polyester is 50C or more and 90C or less.