JP6855262B2 - toner - Google Patents

Description

The present invention relates to toners used in electrophotographic methods, electrostatic recording methods, electrostatic printing methods, and toner jet methods.

In recent years, electrophotographic full-color copiers have become widespread and have begun to be applied to the printing market. In the printing market, high speed, high image quality, and high productivity are required while supporting a wide range of media (paper types).
For example, even if the paper type is changed from thick paper to thin paper, continuous printing is required without changing the process speed or the set temperature of the fuser according to the paper type. From the viewpoint of media constant velocity, toner is required to properly complete fixing in a wide fixing temperature range from low temperature to high temperature.
In order to fix the toner at a wide range of fixable temperatures, there is a method of containing wax in the toner to make the toner releasable. In this case, the dispersed state of the wax in the toner has a significant effect on the properties of the toner, so that it is desired to be fine and uniform.
In order to control the dispersion state of the wax in the toner, a technique of incorporating a wax dispersant in the toner (Patent Document 1) and a technique of controlling the solubility parameter of the wax dispersant and the resin (Patent Document 2) have been proposed. Has been done. It has also been proposed to improve the dispersibility of wax and suppress image deterioration by using a toner binder composed of a high-viscosity resin, a low-viscosity resin, and a dispersant (Patent Document 3). However, even if the dispersion state of the wax in the toner is controlled, if the toner is left in a high temperature and high humidity, the wax dissolves on the surface of the toner and the fluidity of the toner deteriorates, so that the chargeability may be inferior. ..
Further, various toners have been proposed in which a crystalline resin having a sharp melt property is added to the toner to improve the low temperature fixing performance in order to fix the toner at a wide range of fixable temperatures (Patent Document 4). However, in high-speed machines such as those compatible with the printing market, the fixability at low temperatures is still insufficient, and blocking may occur when left at high temperatures. Further, since the toner shape is not controlled, the transfer efficiency may be insufficient.
On the other hand, in order to improve the transfer efficiency, it has been proposed to control the shape by heat-treating the toner to reduce the adhesive force of the toner (Patent Document 5). However, it is known that in the heat-treated toner, the shape of the toner is controlled, while the highly adhesive wax elutes in the vicinity of the toner surface. Therefore, the fluidity of the toner may be deteriorated due to the influence of the wax eluted near the surface of the toner, and the chargeability may be deteriorated.
As described above, there is still room for study in order to control the dispersed state of the wax in the toner and satisfy the chargeability, fixability, and blocking resistance.

Japanese Unexamined Patent Publication No. 2011-13548 Japanese Unexamined Patent Publication No. 2012-063559 JP-A-2007-264349 Japanese Unexamined Patent Publication No. 2011-123352 Japanese Unexamined Patent Publication No. 2013-15830

An object of the present invention is to provide a toner that solves the above problems. Specifically, a toner that controls the wax in the toner to a high degree of dispersion, satisfies low temperature fixability, hot offset resistance, and blocking resistance, and can exhibit sufficient chargeability even under severe chargeability. Is to provide.

The present invention is a toner containing an amorphous resin, a crystalline resin, a wax and a wax dispersant.
The wax dispersant, Ri graft polymer der styrene acrylic polymer hydrocarbon wax is bound,
The styrene acrylic polymer
(I) A unit derived from cycloalkyl acrylate or a unit derived from cycloalkyl methacrylate , and
(Ii) It has a methacrylic acid unit and
The present invention relates to a toner characterized in that the solubility parameter SP1 of the crystalline resin and the solubility parameter SP2 of the wax dispersant satisfy the relationship of the following formula (1).
0 ≦ SP1-SP2 ≦ 1.3 Equation (1)

According to the present invention, the wax in the toner is controlled to be highly dispersed, and while satisfying low temperature fixability, hot offset resistance, and blocking resistance, sufficient chargeability can be exhibited even under severe chargeability. Toner can be provided.

It is a figure of the thermosphere processing apparatus used in this invention.

The composition of the preferable toner in the present invention will be described in detail below.

The toner of the present invention, an amorphous resin, a crystalline resin, a toner containing a wax and a wax dispersant, the wax dispersant is a graph preparative polymer styrene acrylic polymer is bonded to a polyolefin, The styrene acrylic polymer has a unit derived from cycloalkyl acrylate or cycloalkyl methacrylate (hereinafter, also referred to as cycloalkyl (meth) acrylate), and dissolves the solubility parameter SP1 of the crystalline resin and the wax dispersant. and sex parameter SP2 is characterized by satisfying the relation of the following formula (1).
0 ≦ SP1-SP2 ≦ 1.3 Equation (1)

The polymer of the present invention is a resin composition, which is a styrene acrylic resin having an aliphatic hydrocarbon compound graft-modified and having a unit derived from cycloalkyl (meth) acrylate. This is very important.

In the dispersant of the present invention, the styrene acrylic resin having a unit derived from cycloalkyl (meth) acrylate has an affinity with the binder resin in the toner, and the graft-modified polyolefin has an affinity with the wax in the toner. .. Therefore, the wax can be finely dispersed in the toner.

In the present invention, since the wax dispersant has a unit derived from cycloalkyl (meth) acrylate, the wax in the toner is finely dispersed in the same manner as the conventional wax dispersant, and at the same time, the toner is left in a high temperature and high humidity. However, it was found that the chargeability was maintained.

As a result of the examination by the present inventors, the following mechanism is presumed.

When the toner is left at high temperature and high humidity, the wax is transferred to the toner surface. In the present invention, since the toner contains the wax dispersant, it is presumed that when the wax is transferred to the toner surface, the wax dispersant is also transferred to the toner surface together with the wax.

In the present invention, since the wax dispersant has a bulky cyclohexyl group as compared with the conventional wax dispersant, when the wax dispersant migrates to the toner surface, the elution of the wax is suppressed and the temperature and humidity are high. It is considered that the chargeability does not deteriorate even if left unattended. Further, it is considered that when the wax dispersant of the present invention is transferred to the toner surface, the hydrophobicity of the toner is improved and the chargeability is not deteriorated even if the toner is left in a high temperature and high humidity.

However, as the hydrophobicity of the polymer is increased, the affinity of the polymer for the resin tends to deteriorate. As a result of diligent studies by the present inventors to improve the affinity with the resin, it was possible to improve the affinity with the resin by bringing the SP value of the wax dispersant closer to that of the crystalline resin. As a result, we succeeded in further improving the low temperature fixability and wax dispersibility.

As a result of the examination by the present inventors, the following mechanism is presumed. By improving the affinity between the polymer and the crystalline resin, the crystalline resin can be finely dispersed, the low-temperature fixability can be improved, and the crystallinity is finely dispersed. It is considered that the surrounding wax dispersant is also finely dispersed, and as a result, the wax is also considered to be able to improve the fine dispersibility.

As described above, by having a unit derived from cycloalkyl (meth) acrylate and further bringing the solubility parameter closer to that of a crystalline resin, the present invention has been made in which low temperature fixability can be improved while maintaining a high level of hydrophobicity. It was.

In the present invention, the solubility parameter SP1 of the crystalline resin and the solubility parameter SP2 of the wax dispersant are 0≤SP1-SP2≤1.3 (1).
It is important to satisfy the relationship. When both solubility parameters are in this range, the affinity between the wax dispersant and the crystalline resin is improved, and the dispersibility of the wax and the crystalline resin is improved. The hot offset property is improved by improving the dispersibility of the wax, and the low temperature fixability is improved by improving the dispersibility of the crystalline resin. When SP1-SP2 becomes negative, the solubility parameter of the wax dispersant becomes too large, and the wax dispersibility deteriorates. When SP1-SP2 is larger than 1.3, the difference in solubility parameter becomes large, the affinity between the crystalline resin and the wax dispersant does not increase, and the effect of the present invention does not appear.

The dissolution parameter of the present invention is calculated by the Fedors method. The evaporation energy (Δei [cal / mole]) and molar volume (Δvi [cal / mole]) used in the calculation are described in Chapter 5, R.M. F. Fedors, Polym. Eng. Sci. The numerical values described in 14, 147 (1974) are used. In the present invention, the calculation is performed based on the structure of the polymer constituent unit.

The composition of the wax dispersant and the toner preferable in the present invention will be described in detail below.

<Wax dispersant>
In the present invention, a graph preparative polymer styrene acrylic polymer is bonded to a polyolefin, said styrene-acrylic polymer having units derived from cycloalkyl (meth) acrylate, a solubility parameter of the crystalline resin SP1 A polymer characterized by satisfying the relationship of the above formula (1) with the solubility parameter SP2 of the wax dispersant was used as the wax dispersant.

The wax dispersant of the present invention preferably has a weight average molecular weight (Mw) of 5000 or more and 70,000 or less in the molecular weight distribution of the styrene acrylic resin by GPC. When the wax dispersant of the present invention is in the above range, the dispersibility of the wax is improved, and at the same time, the blocking resistance and the hot offset resistance are improved.

When the weight average molecular weight (Mw) is 5000 or more, the wax dispersant stays in the toner, elution of the wax to the toner surface due to leaving at high temperature and high humidity is suppressed, and the blocking resistance of the toner is improved. Further, when the weight average molecular weight (Mw) is 70,000 or less, the wax finely dispersed in the toner can be rapidly transferred to the surface of the molten toner at the time of fixing and melting, the releasability at the time of fixing is improved, and a high temperature offset occurs. It becomes difficult.

The polyolefin is not particularly limited, but may be selected from the waxes used in the toner of the present invention, which will be described later, from the viewpoint of affinity with the wax in the toner particles.

The polyolefin preferably has a peak temperature of 70 ° C. or higher and 90 ° C. or lower, which is the highest thermal peak measured by a differential scanning calorimeter (DSC).

In the present invention, it can be preferably exemplified that the polyolefin is a hydrocarbon wax such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, microcrystalline wax, paraffin wax, and Fishertropch wax.

Further, from the viewpoint of reactivity of the wax dispersant during production, it is preferable to have a branched structure like polypropylene.

In the present invention, the method for graft-modifying a styrene-acrylic polymer to polyolefin is not particularly limited, and a conventionally known method can be used.

In the polymer of the present invention, the styrene acrylic polymer is not particularly limited as long as it has a unit derived from cycloalkyl (meth) acrylate.

As the unit derived from cycloalkyl (meth) acrylate, a saturated alicyclic hydrocarbon group is preferable, a saturated alicyclic hydrocarbon group having 3 or more and 18 or less carbon atoms is more preferable, and a saturated alicyclic hydrocarbon group having 4 or more and 12 or less carbon atoms is more preferable. It is a saturated alicyclic hydrocarbon group. Saturated alicyclic hydrocarbon groups include cycloalkyl groups, condensed polycyclic hydrocarbon groups, bridging ring hydrocarbon groups, spirohydrocarbon groups and the like.

Examples of such a saturated alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecanyl group, and a decahydro-2-naphthyl group. , Tricyclo [5.2.1.02,6] decane-8-yl group, pentacyclopentadecanyl group, isobornyl group, adamantyl group, dicyclopentanyl group, tricyclopentanyl group and the like. ..

Further, the saturated alicyclic group may also have an alkyl group, a halogen atom, a carboxy group, a carbonyl group, a hydroxy group or the like as a substituent. As the alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable.

Among these saturated alicyclic groups, a cycloalkyl group, a condensed polycyclic hydrocarbon group, and a bridged ring hydrocarbon group are preferable, a cycloalkyl group having 3 to 18 carbon atoms, and a substituted or unsubstituted dicyclopentanyl. A group, substituted or unsubstituted tricyclopentanyl group is more preferable, a cycloalkyl group having 6 or more and 10 or less carbon atoms is further preferable, and a cyclohexyl group having 6 carbon atoms is particularly preferable.

The position and number of the substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different.

The styrene-acrylic polymer may be a homopolymer of a vinyl-based monomer (a) having a structural moiety derived from a saturated alicyclic compound, or may be a copolymer with another monomer (b).

Examples of the vinyl-based monomer (a) include cyclopropyl acrylate, cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, cyclopropyl methacrylate, cyclobutyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, and cycloheptyl methacrylate. Examples thereof include monomers such as cyclooctyl methacrylate, dihydrocyclopentadiethyl acrylate, dicyclopentanyl acrylate, and dicyclopentanyl methacrylate, and a combination thereof.

Among these, cyclohexyl acrylate, cycloheptyl acrylate, cyclooctyl acrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, and cyclooctyl methacrylate are preferable from the viewpoint of hydrophobicity.

Examples of the other monomer (b) include styrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, benzylstyrene and the like. Styrene-based monomer; alkyl ester of unsaturated carboxylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate (the alkyl has 1 to 18 carbon atoms). (Hereinafter); Vinyl ester-based monomers such as vinyl acetate; Vinyl ether-based monomers such as vinyl methyl ether; Halogen element-containing vinyl-based monomers such as vinyl chloride; Diene-based monomers such as butadiene and isobutylene, and combinations thereof.

Further, in order to adjust the polarity, a monomer to which an acid group or a hydroxyl group is added may be added. Examples of the monomer to which an acid group or a hydroxyl group is added include acrylic acid, methacrylic acid, maleic anhydride, maleic acid half ester, and diethylhexyl acrylate. The acid value is preferably 5 mgKOH / g or more and 50 mgKOH / g or less.

In the present invention, it is preferable that the styrene acrylic resin has a monomer unit represented by the following formula (2) from the viewpoint of low temperature fixability of the toner.

When the styrene acrylic resin has a monomer unit represented by the formula (2), the glass transition temperature (Tg) of the polymer tends to decrease. As a result, when the wax dispersant is contained in the toner particles, the chargeability does not decrease even if the toner is left under high temperature and high humidity, and the low temperature fixability is further improved.

［式（２）中、Ｒ₃は水素原子又はメチル基を表し、ｎは１以上１８以下の整数を表す。（ｎは、２以上７以下の整数であることが好ましい。この範囲にあるときガラス転移温度（Ｔｇ）を効率よく下げることができる。２未満のときはガラス転移温度（Ｔｇ）を下げる効果が得られず、７より大きい場合は入れ目に対してガラス転移温度（Ｔｇ）が下がりすぎ、調整ができなくなる。）］

[In formula (2), R ₃ represents a hydrogen atom or a methyl group, and n represents an integer of 1 or more and 18 or less. (N is preferably an integer of 2 or more and 7 or less. When it is in this range, the glass transition temperature (Tg) can be efficiently lowered. When it is less than 2, the effect of lowering the glass transition temperature (Tg) is effective. If it is not obtained and is larger than 7, the glass transition temperature (Tg) is too low with respect to the joint, and adjustment is not possible.)]]

When the toner is produced using the polymer of the present invention, the binder resin for toner is not particularly limited, but the wax dispersant of the present invention is sufficiently effective as the polyester as the binder resin. This is the case when resin is used.

The compatibility between the polyester resin used as the binder resin in the present invention and the hydrocarbon wax is originally poor. Therefore, when the wax is added as it is to form a toner, the wax segregates and exists in the toner, and free wax and the like are also generated. As a result, problems such as poor charging may occur. There is.

Further, the polymer is preferably contained in an amount of 1.0 part by mass or more and 10.0 parts by mass or less with respect to 100 parts of the binder resin.

In the present invention, in the molecular weight distribution of the polymer by gel permeation chromatography (GPC), the weight average molecular weight (Mw) is preferably 5,000 or more and 70,000 or less, and more preferably 10,000 or more and 50,000 or less. When the weight average molecular weight (Mw) of the polymer is in the above range, the dispersibility of the wax in the toner particles is improved, and at the same time, the blocking resistance and the hot offset resistance are improved.

When the weight average molecular weight (Mw) of the polymer is less than 5000, the wax dispersant becomes easy to move in the toner particles. As a result, the wax tends to elute more on the surface of the toner particles when left under high temperature and high humidity, and the chargeability and blocking resistance of the toner tend to decrease. On the other hand, when the weight average molecular weight (Mw) of the polymer exceeds 70,000, the wax finely dispersed in the toner particles tends to be difficult to rapidly migrate to the surface of the toner particles at the time of fixing and melting. Therefore, the releasability at the time of fixing tends to decrease, and the high temperature offset tends to occur easily.

<Bundling resin>
As the binder resin used for the toner of the present invention, an amorphous polyester resin is preferably used. The monomers used in the polyester unit of the polyester resin include polyhydric alcohol (dihydric or trihydric or higher alcohol), polyvalent carboxylic acid (divalent or trivalent or higher carboxylic acid), its acid anhydride or its lower grade. Alkyl esters are used. Here, when producing a branched polymer, it is effective to partially crosslink the binder resin in the molecule, and for that purpose, it is preferable to use a polyfunctional compound having a valence of 3 or more. Therefore, it is preferable that the raw material monomer of the polyester unit contains a carboxylic acid having a valence of trivalent or higher, an acid anhydride thereof or a lower alkyl ester thereof, and / or an alcohol having a valence of trivalent or higher.

As the polyhydric alcohol monomer used in the polyester unit of the polyester resin, the following polyhydric alcohol monomer can be used.

The divalent alcohol component includes ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-Hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol represented by the formula (A) and derivatives thereof;

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ及びｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０以上１０以下である。）
式（Ｂ）で示されるジオール類；

(In the formula, R is an ethylene or propylene group, x and y are integers of 0 or more, and the average value of x + y is 0 or more and 10 or less.)
Diols represented by the formula (B);

が挙げられる。

Can be mentioned.

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. , 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene Can be mentioned. Of these, glycerol, trimethylolpropane, and pentaerythritol are preferably used. These divalent alcohols and trihydric or higher alcohols can be used alone or in combination of two or more.

The following polyvalent carboxylic acid monomers can be used as the polyvalent carboxylic acid monomer used in the polyester unit of the polyester resin.

Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, and malonic acid. n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids and Examples thereof include these lower alkyl esters. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenyl succinic acid are preferably used.

Examples of the trivalent or higher valent carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalentricarboxylic acid and 1,2,4-naphthalenetricarboxylic acid. , 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra ( Methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimeric acid, acid anhydrides thereof or lower alkyl esters thereof. Of these, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or a derivative thereof is preferably used because it is inexpensive and reaction control is easy. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination of two or more.

If the main component is a polyester resin, it may be a hybrid resin containing another resin component. For example, a hybrid resin of a polyester resin and a vinyl resin can be mentioned. As a method for obtaining a reaction product of a vinyl-based resin or a vinyl-based copolymerization unit and a polyester resin such as a hybrid resin, a monomer component capable of reacting with each of the vinyl-based resin, the vinyl-based copolymerization unit and the polyester resin is included. A method of polymerizing one or both resins in the presence of the polymer is preferable.

For example, among the monomers constituting the polyester resin component, those capable of reacting with the vinyl-based copolymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Be done. Among the monomers constituting the vinyl-based copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, acrylic acids or methacrylic acid esters.

Further, in the present invention, if the polyester resin is the main component of the binder resin, various resin compounds conventionally known as the binder resin can be used in combination in addition to the vinyl-based resin described above. Examples of such resin compounds include phenol resin, natural resin modified phenol resin, natural resin modified malein resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, and epoxy. Examples thereof include resins, xylene resins, polyvinyl butyral, terpene resins, kumaroinden resins, petroleum resins and the like.

Further, the binder resin of the present invention may be used by mixing the low molecular weight binder resin L and the high molecular weight binder resin H. The content ratio (H / L) of the high molecular weight binder resin H and the low molecular weight binder resin L is 10/90 or more and 60/40 or less on a mass basis from the viewpoint of low temperature fixability and hot offset resistance. Is preferable.

The peak molecular weight of the high molecular weight binder resin A is preferably 10,000 or more and 20,000 or less from the viewpoint of hot offset resistance. Further, the acid value of the high molecular weight binder resin is preferably 2 mgKOH / g or more and 20 mgKOH / g or less from the viewpoint of charge stability in a high temperature and high humidity environment.

The number average molecular weight of the low molecular weight binder resin B is preferably 3000 or more and 7000 or less from the viewpoint of low temperature fixability. Further, the acid value of the low molecular weight binder resin is preferably 10 mgKOH / g or less from the viewpoint of charge stability in a high temperature and high humidity environment.

<Crystalline resin>
The toner of the present invention preferably contains a crystalline resin. The inclusion of crystalline resin improves low temperature fixability.

It is important that the crystalline resin is a crystalline ester compound or a crystalline ether compound. By using a crystalline ester compound or a crystalline ether compound, it is possible to plasticize the polyester resin of the binder resin and improve the low temperature fixability. Further, in order to fully exert the plasticizing effect, it is preferable to use polyester as the crystalline resin.

In the toner of the present invention, the crystalline polyester contained in the toner particles is obtained by polycondensing a monomer composition containing an aliphatic diol and an aliphatic dicarboxylic acid as main components. The aliphatic diol and the aliphatic dicarboxylic acid preferably have 6 to 12 carbon atoms.

The aliphatic diol is not particularly limited, but is preferably a chain (more preferably linear) aliphatic diol, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1 , 3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene Glycol Neopentyl glycol can be mentioned. Among these, linear aliphatics such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, α, ω-diol are preferably exemplified. Of the above alcohol components, preferably 50% by mass or more, more preferably 70% by mass or more is an alcohol selected from an aliphatic diol having 6 to 12 carbon atoms.

In the present invention, a polyhydric alcohol monomer other than the above aliphatic diol can also be used. Examples of the divalent alcohol monomer among the polyhydric alcohol monomers include aromatic alcohols such as polyoxyethylene bisphenol A and polyoxypropylene bisphenol A; 1,4-cyclohexanedimethanol and the like. Among the polyhydric alcohol monomers, the trihydric or higher polyhydric alcohol monomer includes aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, and tripentaerythritol. , 1,2,4-Butantriol, 1,2,5-Pentantriol, Glycerin, 2-Methylpropantriol, 2-Methyl-1,2,4-Butantriol, Trimethylolethane, Trimethylolpropane and other fats Triol alcohol and the like can be mentioned.

Further, in the present invention, monovalent alcohol may be used to the extent that the characteristics of the crystalline polyester are not impaired. Examples of the monohydric alcohol include monofunctionals such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol and dodecyl alcohol. Examples include sex alcohol.

On the other hand, the aliphatic dicarboxylic acid is not particularly limited, but is preferably a chain-like (more preferably linear) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, undecandicarboxylic acid, dodecandicarboxylic acid, Examples thereof include maleic acid, fumaric acid, mesaconic acid, citraconic acid and itaconic acid, and those obtained by hydrolyzing these acid anhydrides or lower alkyl esters are also included.

In the present invention, preferably 50% by mass or more, more preferably 70% by mass or more of the carboxylic acid components are carboxylic acids selected from aliphatic dicarboxylic acids having 6 to 12 carbon atoms.

In the present invention, a polyvalent carboxylic acid other than the aliphatic dicarboxylic acid can also be used. Among other polyvalent carboxylic acid monomers, the divalent carboxylic acid includes aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids of n-dodecylsuccinic acid and n-dodecenylsuccinic acid; cyclohexanedicarboxylic acids. Examples thereof include alicyclic carboxylic acids such as acids, and these acid anhydrides or lower alkyl esters are also included. Among other carboxylic acid monomers, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1, Aromatic carboxylic acids such as 2,4-naphthalentricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2 Examples thereof include aliphatic carboxylic acids such as methylenecarboxypropane and the like, and derivatives such as these acid anhydrides or lower alkyl esters are also included.

Further, in the present invention, a monovalent carboxylic acid may be contained to such an extent that the characteristics of the crystalline polyester are not impaired. Examples of the monovalent carboxylic acid include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, and decanoic acid. Examples thereof include monocarboxylic acids such as dodecanoic acid and stearic acid.

The crystalline polyester in the present invention can be produced according to a conventional polyester synthesis method. For example, it is desired to carry out an esterification reaction or a transesterification reaction between the carboxylic acid monomer and the alcohol monomer described above, and then carry out a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. Crystalline polyester can be obtained.

The esterification or transesterification reaction can be carried out using a usual esterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, magnesium acetate, or a transesterification catalyst, if necessary.

Further, the polycondensation reaction can be carried out using a usual polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. .. The polymerization temperature and the amount of catalyst are not particularly limited and may be appropriately determined.

In the esterification or transesterification reaction or polycondensation reaction, all the monomers may be charged in a batch in order to increase the strength of the obtained crystalline polyester. Further, in order to reduce the amount of low molecular weight components, a method such as first reacting a divalent monomer and then adding a trivalent or higher valent monomer to cause the reaction may be used.

The crystalline polyester is preferably contained in an amount of 1.0 part by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the amorphous resin. If the amount of crystalline resin is small, the plasticizing effect cannot be sufficiently obtained and the low temperature fixability is not improved. Further, if it is added too much, water is easily adsorbed, so that the color stability is impaired.

From the viewpoint of suppressing water adsorption, the acid value is preferably 2 mgKOH / g or more and 20 mgKOH / g or less.

<Wax>
Examples of the wax used for the toner of the present invention include the following. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystallin wax, paraffin wax, Fishertropch wax; oxides of hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof; Waxes containing fatty acid esters as the main component, such as carnauba wax; deoxidized waxes, which are partially or wholly deoxidized fatty acid esters such as carnauba wax. In addition, the following can be mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brushzic acid, eleostearic acid, and valinaphosphate; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol, ceryl alcohol, and meli Saturated alcohols such as syl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid and montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol, ceryl alcohol and meli Esters with alcohols such as silalic acid; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid Saturated fatty acid bisamides such as acid amides; unsaturated fatty acid amides such as ethylene bisoleic acid amides, hexamethylene bisoleic acid amides, N, N'diorail adipic acid amides, N, N'diorail sebasic acid amides; m -Aromatic bisamides such as xylene bisstearate amide, N, N'distearyl isophthalic acid amide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally referred to as metal soap). ); Waxes grafted on aliphatic hydrocarbon wax using vinyl monomer such as styrene or acrylic acid; partial esterified product of fatty acid and polyhydric alcohol such as behenic acid monoglyceride; hydrogen of vegetable fats and oils A methyl ester compound having a hydroxyl group obtained by addition.

Among these waxes, hydrocarbon waxes such as paraffin wax, Fishertropch wax, or carnauba wax from the viewpoint of improving the interaction of the wax of the present invention with the wax dispersant, low temperature fixability, and hot offset resistance. A fatty acid ester wax such as the above is preferable. In the present invention, a hydrocarbon wax is more preferable in that the hot offset resistance is further improved.

In the present invention, the wax is preferably used in an amount of 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the binder resin.

Further, in the endothermic curve at the time of temperature rise measured by the differential scanning calorimetry (DSC) device, the peak temperature of the maximum endothermic peak of the wax is preferably 45 ° C. or higher and 140 ° C. or lower. It is preferable that the peak temperature of the maximum endothermic peak of the wax is within the above range because both the storage stability of the toner and the hot offset resistance can be achieved at the same time.

<Colorant>
Examples of the colorant that can be contained in the toner include the following.

Examples of the black colorant include carbon black; a color toned black using a yellow colorant, a magenta colorant, and a cyan colorant. A pigment may be used alone as the colorant, but it is more preferable to use a dye and a pigment in combination to improve the sharpness from the viewpoint of the image quality of a full-color image.

Examples of the magenta toner pigment include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment Violet 19; C.I. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. Disperse thread 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the cyan toner pigment include the following. C. I. Pigment Blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalocyanine methyl groups are substituted in the phthalocyanine skeleton.

Examples of the cyan toner dye include C.I. I. There is Solvent Blue 70.

Examples of the pigment for yellow toner include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C.I. I. Bat Yellow 1, 3, 20.

Examples of the dye for yellow toner include C.I. I. There is Solvent Yellow 162.

The amount of the colorant used is preferably 0.1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

<Charge control agent>
The toner may also contain a charge control agent, if necessary. As the charge control agent contained in the toner, known ones can be used, but in particular, a metal compound of an aromatic carboxylic acid which is colorless, has a high charge speed of the toner, and can stably maintain a constant charge amount is preferable.

The negative charge control agent has a metal salicylate compound, a metal naphthoate compound, a metal dicarboxylic acid compound, a polymer compound having a sulfonic acid or a carboxylic acid in the side chain, a sulfonate or a sulfonic acid esterified product in the side chain. Examples thereof include a high molecular weight compound, a high molecular weight compound having a carboxylate or a carboxylic acid esterified product in a side chain, a boron compound, a urea compound, a silicon compound, and a calix array. The charge control agent may be added internally or externally to the toner particles. The amount of the charge control agent added is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

<Inorganic fine particles>
If necessary, the toner of the present invention may contain inorganic fine particles. The inorganic fine particles may be internally added to the toner particles or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine powder such as silica, titanium oxide, and aluminum oxide is preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

As an external additive for improving fluidity, ^{an inorganic fine powder having a specific surface area of 50 m 2} / g or more and 400 m ² / g or less is preferable, and for stabilizing durability, a specific surface area of 10 m ² / g or more and 50 m or more is preferable. It is preferably an inorganic fine powder of ^{2 / g or less.} In order to improve the fluidity and stabilize the durability, an inorganic fine powder having a specific surface area in the above range may be used in combination.

The external additive is preferably used in an amount of 0.1 part by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the toner particles. A known mixer such as a Henschel mixer can be used for mixing the toner particles and the external additive.

<Developer>
The toner of the present invention can also be used as a one-component developer, but in order to further improve dot reproducibility, it is possible to mix it with a magnetic carrier and use it as a two-component developer, and an image that is stable for a long period of time. Is preferable in that

Examples of the magnetic carrier include iron powder whose surface has been oxidized, unoxidized iron powder, and metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth. A magnetic material such as alloy particles, oxide particles, ferrite, etc., or a magnetic material-dispersed resin carrier (so-called resin carrier) containing the magnetic material and a binder resin that holds the magnetic material in a dispersed state is generally known. You can use things.

When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the carrier mixing ratio at that time is preferably 2% by mass or more and 15% by mass or less as the toner concentration in the two-component developer. When it is 4% by mass or more and 13% by mass or less, good results are usually obtained.

<Manufacturing method>
The toner of the present invention is preferably produced through a step of melt-kneading a mixture containing a binder resin, a colorant, a wax, and a wax dispersant. In the process in which the toner is melt-kneaded and then pulverized, the wax and the domain of the wax dispersant are easily exposed on the toner surface. As a result, the hydrophobicity of the toner is promoted, and the chargeability in a high temperature and high humidity environment is improved.

By producing the toner of the present invention through a melt-kneading step, the dispersibility of the wax is improved. This is because the toner produced by the melt-kneading method has the raw materials of the toner (especially the binder resin, the wax dispersant, and the wax) mixed firmly by the heat and shear during kneading, and when it becomes the toner, it is contained in the toner. It is presumed that this is because the dispersibility of the wax is improved. The fine dispersion of the wax in the toner reduces the elution of the wax on the toner surface due to leaving it at high temperature and high humidity, and improves the blocking resistance of the toner.

The toner of the present invention is preferably produced through a step of cooling the kneaded product obtained by melt-kneading and pulverizing the obtained cooled product to heat-treat the toner particles obtained. By producing the toner of the present invention through a heat treatment step, chargeability and blocking resistance are improved as compared with the case where a conventional wax dispersant is used.

Usually, in a heat-treated toner, wax having high adhesiveness is eluted in the vicinity of the toner surface, so that the blocking resistance of the toner is lowered and charging failure occurs due to the lowered fluidity.

However, when the toner using the wax dispersant of the present invention is heat-treated, the hydrophobic wax dispersant is transferred to the surface of the toner at the same time as the wax, so that the fluidity of the toner does not deteriorate even under high temperature and high humidity, and the toner becomes chargeable. Does not get worse. Further, since the wax dispersant of the present invention has a bulky cyclohexyl group, exudation of wax during heat treatment is suppressed as compared with the case where a conventional wax dispersant is used. Therefore, the deterioration of the blocking resistance of the toner is suppressed.

The procedure for manufacturing the toner in the present invention will be described.

First, in the raw material mixing step, an amorphous polyester resin, a hydrocarbon wax, a wax dispersant and the like are weighed and mixed in a predetermined amount as a toner raw material and mixed. As an example of a mixing device, Henschel mixer (manufactured by Nippon Coke Co., Ltd.); Super mixer (manufactured by Kawata Co., Ltd.); Ribocorn (manufactured by Okawara Seisakusho Co., Ltd.); Mixer (manufactured by Pacific Kiko Co., Ltd.); Ladyge mixer (manufactured by Matsubo Co., Ltd.), etc.

Further, the mixed toner raw materials are melt-kneaded in a melt-kneading step to melt the resins and disperse the colorants and the like in the resins. As an example of the kneading machine, TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Japan Steel Works); PCM kneader (manufactured by Ikekai Iron Works); Kneedex (manufactured by Mitsui Mining Co., Ltd.) However, a continuous kneader such as a single-screw or twin-screw extruder is preferable to a batch kneader because of its superiority such as continuous production.

The colored resin composition obtained by melt-kneading the toner raw material is melt-kneaded, rolled by two rolls or the like, and cooled through a cooling step of cooling by water cooling or the like.

The cooled product of the colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the crushing process, first, it is roughly crushed by a crusher, a hammer mill, a feather mill, etc., and then finely crushed by a Cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), etc. to obtain toner fine particles. ..

The obtained toner fine particles are classified into toner powder particles having a desired particle size in a classification step. Classifiers include turboplex, faculty, TSP, TTSP (manufactured by Hosokawa Micron); elbow jet (manufactured by Nittetsu Mining Co., Ltd.) and the like.

Subsequently, it is preferable that the obtained powder particles for toner are sphericalized in the heat treatment step using a heat treatment apparatus as shown in FIG.

The mixture quantitatively supplied by the raw material quantitative supply means 1 is guided to the introduction pipe 3 installed on the vertical line of the raw material supply means by the compressed gas adjusted by the compressed gas adjusting means 2. The mixture that has passed through the introduction pipe is uniformly dispersed by the conical protruding member 4 provided in the central portion of the raw material supply means, and is guided to the supply pipe 5 in eight directions that spread radially to perform heat treatment. Guided to.

At this time, the flow of the mixture supplied to the treatment chamber is regulated by the regulating means 9 for regulating the flow of the mixture provided in the treatment chamber. Therefore, the mixture supplied to the treatment chamber is heat-treated while swirling in the treatment chamber, and then cooled.

The heat for heat-treating the supplied mixture is supplied from the hot air supply means 7, distributed by the distribution member 12, and introduced by spirally swirling the hot air into the processing chamber by the swirling member 13 for swirling the hot air. Will be done. As its configuration, the swirling member 13 for swirling the hot air has a plurality of blades, and the swirling of the hot air can be controlled by the number and angles thereof. The temperature at the outlet of the hot air supply means 7 is preferably 100 ° C. or higher and 300 ° C. or lower, and more preferably 130 ° C. or higher and 170 ° C. or lower. If the temperature at the outlet of the hot air supply means is within the above range, it is possible to uniformly spheroidize the toner particles while preventing fusion and coalescence of the toner particles due to overheating of the mixture. Become. Hot air is supplied from the hot air supply means outlet 11.

Further, the heat-treated heat-treated toner particles are cooled by the cold air supplied from the cold air supply means 8, and the temperature supplied from the cold air supply means 8 is preferably −20 ° C. or higher and 30 ° C. or lower. When the temperature of the cold air is within the above range, the heat-treated toner particles can be efficiently cooled, and fusion and coalescence of the heat-treated toner particles are prevented without hindering the uniform spheroidizing treatment of the mixture. be able to. The absolute water content of the cold air ^{is preferably 0.5 g / m 3} or more and 15.0 g / m ³ or less.

Next, the cooled heat-treated toner particles are recovered by the recovery means 10 at the lower end of the processing chamber. A blower (not shown) is provided at the tip of the collecting means, and the suction is conveyed by the blower (not shown).

Further, the powder particle supply port 14 is provided so that the swirling direction of the supplied mixture and the swirling direction of the hot air are in the same direction, and the recovery means 10 of the surface treatment device is a swirling powder particle. It is provided on the outer peripheral portion of the processing chamber so as to maintain the turning direction. Further, the cold air supplied from the cold air supply means 8 is configured to be supplied horizontally and tangentially from the outer peripheral portion of the apparatus to the peripheral surface of the processing chamber. The swirling direction of the toner particles before heat treatment supplied from the powder supply port, the swirling direction of the cold air supplied from the cold air supply means, and the swirling direction of the hot air supplied from the hot air supply means are all in the same direction. Therefore, turbulent flow does not occur in the processing chamber, the swirling flow in the apparatus is strengthened, a strong centrifugal force is applied to the toner particles before heat treatment, and the dispersibility of the toner particles before heat treatment is further improved, so that the number of coalesced particles is small. , Heat-treated toner particles having a uniform shape can be obtained.

In the method for producing a toner of the present invention, inorganic fine particles or the like may be added to the obtained powder particles for toner before the heat treatment step, if necessary. As a method of adding inorganic fine particles or the like to toner powder particles, a predetermined amount of toner powder particles and various known external additives are mixed, and Henshell mixer, mechano hybrid (manufactured by Nippon Coke Co., Ltd.), super mixer, novirta. A high-speed stirrer (manufactured by Hosokawa Micron) or the like that applies shearing force to the powder is used as an external mixer to stir and mix.

In the method for producing a toner of the present invention, if coarse particles are present after heat treatment, a step of removing the coarse particles by classification may be provided, if necessary. Examples of the classifier for removing coarse particles include turboplex, TSP, TTSP, Cliffis (manufactured by Hosokawa Micron Co., Ltd.), and elbow jet (manufactured by Nittetsu Mining Co., Ltd.).

Further, after the heat treatment, in order to sieve coarse particles and the like as necessary, for example, Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona Sheave, Gyro Shifter (manufactured by Tokuju Kosakusho Co., Ltd.); Turbo Screener (manufactured by Turbo Industries, Ltd.) ); A sieving machine such as a high bolter (manufactured by Toyo Hi-Tech) may be used.

The heat treatment step of the present invention may be performed after the above-mentioned fine pulverization.

The average circularity of the toner of the present invention is preferably 0.960 or more, more preferably 0.965 or more. When the average circularity of the toner is in the above range, the transfer efficiency of the toner is improved.

The methods for measuring various physical properties of toner and raw materials will be described below.

<Measurement of DSC heat absorption (ΔH) of wax>
The peak temperature (Tp) of the maximum endothermic peak of wax or the like in the present invention is measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.
Temperature rise rate: 10 ° C / min Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C

The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.

Specifically, about 5 mg of the sample is precisely weighed, placed in a silver pan, and measured once. An empty silver pan is used as a reference.

When the toner is used as a sample and the maximum endothermic peak (maximum endothermic peak derived from the binder resin) does not overlap with the endothermic peak of a resin other than wax and crystalline resin, the amount of endothermic peak obtained is the maximum endothermic peak. Is treated as it is as the endothermic amount of the maximum endothermic peak derived from wax and crystalline resin. On the other hand, when the toner is used as a sample and the endothermic peak of the resin other than the wax and the binder resin overlaps with the maximum endothermic peak of the binder resin, the endothermic amount derived from the resin other than the wax and the binder resin is determined. , It is necessary to subtract from the endothermic amount of the obtained maximum endothermic peak.

The maximum endothermic peak means a peak having the maximum endothermic amount when there are a plurality of peaks. The endothermic amount (ΔH) of the maximum endothermic peak is calculated from the area of the peak using the analysis software attached to the device.

<Measurement of weight average molecular weight by GPC>
The column is stabilized in a heat chamber at 40 ° C., THF is flowed through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected for measurement. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count value of the calibration curve prepared from several types of monodisperse polystyrene standard samples. As the standard polystyrene sample for preparing the calibration curve, for example, a sample manufactured by Tosoh Corporation or Showa Denko Corporation having a molecular weight of ^{about 10 2} to 10 ⁷ is used, and it is appropriate to use a standard polystyrene sample having at least about 10 points. An RI (refractive index) detector is used as the detector. As a column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, a combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko Corporation or Tosoh Co., Ltd. TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ), G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), TSKgrd volume be able to.

The sample is prepared as follows.

The sample is placed in THF, left at 25 ° C. for several hours, shaken sufficiently, mixed well with THF (until the sample is no longer integrated), and allowed to stand for another 12 hours or more. At that time, the leaving time in THF is set to 24 hours. Then, a sample that has passed through a sample processing filter (a pore size of 0.2 μm or more and 0.5 μm or less, for example, Myshori Disc H-25-2 (manufactured by Tosoh Corporation) can be used) is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 mg / ml or more and 5.0 mg / ml or less.

<Measuring method of weight average particle size (D4) of toner particles>
The weight average particle size (D4) of the toner particles is measured with a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter) equipped with a 100 μm aperture tube by the pore electric resistance method. Using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting conditions and analyzing measurement data, the measurement data is measured with 25,000 effective measurement channels. Is analyzed and calculated.

As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

Before performing measurement and analysis, the dedicated software is set as follows.

In the "Standard measurement method (SOM) change screen" of the dedicated software, the total count number in the control mode is set to 50,000 particles, the number of measurements is one, and the Kd value is "Standard particle 10.0 μm" (Beckman Coulter). Set the value obtained using (manufactured by the company). By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flush of the aperture tube after measurement.

In the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) Approximately 200 ml of the electrolytic aqueous solution is placed in a 250 ml round bottom beaker made of glass dedicated to Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flash" function of the analysis software.
(2) Approximately 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat-bottomed beaker made of glass, and "Contaminone N" (nonionic surfactant, anionic surfactant, and organic builder) as a dispersant is used as a dispersant for precise measurement of pH 7. Add about 0.3 ml of a diluted solution obtained by diluting a 10% by mass aqueous solution of a neutral detergent for cleaning a vessel, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and are installed in the water tank of the ultrasonic disperser "Ultrasonic Dispension System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is added, and about 2 ml of the Contaminone N is added into the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the aqueous electrolyte solution of (5) in which toner is dispersed is dropped onto the round-bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to about 5%. .. Then, the 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, and the weight average particle size (D4) is calculated. The "average diameter" of the analysis / volume statistical value (arithmetic mean) screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measuring method of average circularity>
The average circularity of the toner particles is measured by the flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex) under the measurement and analysis conditions at the time of calibration work.

The specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids and the like have been removed in advance is placed in a glass container. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted about 3 times by mass with ion-exchanged water, and about 0.2 ml of the diluted solution is added. Further, about 0.02 g of the measurement sample is added, and the dispersion treatment is performed for 2 minutes using an ultrasonic disperser to prepare a dispersion liquid for measurement. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion is 10 ° C. or higher and 40 ° C. or lower. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (“VS-150” (manufactured by Vervocreer)) with an oscillation frequency of 50 kHz and an electrical output of 150 W is used, and a predetermined amount of ions are contained in the water tank. Exchange water is added, and about 2 ml of the contaminanton N is added into the water tank.

For the measurement, the flow type particle image analyzer equipped with a standard objective lens (10 times) was used, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion liquid adjusted according to the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the total count mode in the HPF measurement mode. Then, the binarization threshold value at the time of particle analysis is set to 85%, the diameter of the analyzed particle is limited to 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

In the measurement, automatic focus adjustment is performed using standard latex particles (“RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before the start of the measurement. After that, it is preferable to perform focus adjustment every 2 hours from the start of measurement.

In the embodiment of the present application, a flow-type particle image analyzer for which a calibration work was performed by Sysmex Corporation and a calibration certificate issued by Sysmex Corporation was issued was used. The measurement was performed under the measurement and analysis conditions at the time of receiving the calibration certificate, except that the diameter of the analysis particle was limited to 1.985 μm or more and less than 39.69 μm in equivalent circle diameter.

<Measuring method of melting point of polymer>
The melting point of the polymer is measured using a constant load extrusion type thin tube rheometer "Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve showing the relationship between and temperature can be obtained.

In the present invention, the softening point is the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation device flow tester CFT-500D". The melting temperature in the 1/2 method is calculated as follows. First, 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time when the outflow starts is obtained (this is defined as X. X = (Smax-Smin) / 2). Then, the temperature of the flow curve when the amount of descent of the piston becomes X in the flow curve is the melting temperature in the 1/2 method.

As a measurement sample, about 1.0 g of resin was compression-molded in an environment of 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) at about 10 MPa for about 60 seconds. Use a columnar one with a diameter of about 8 mm.

The measurement conditions of CFT-500D are as follows.
Test mode: Hot compress start temperature: 50 ° C
Achieved temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature rise rate: 4.0 ° C / min Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0 mm

Examples 12 to 14 in the examples are reference examples.
<Production example of polymer 1>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 300 parts by mass of xylene and 10 parts by mass of hydrocarbon wax (softening point 90 ° C.) were placed and sufficiently dissolved. After nitrogen substitution, 68.0 parts by mass of styrene and methacrylic acid A mixed solution of 5.0 parts by mass, 5.0 parts by mass of cyclohexyl methacrylate, 12.0 parts by mass of butyl acrylate and 250 parts by mass of xylene was added dropwise at 180 ° C. for 3 hours for polymerization, and further maintained at this temperature for 30 minutes. .. Then, the solvent was removed to obtain polymer 1. Table 1 shows various physical characteristics of the obtained polymer 1.

<Production example of polymers 2 to 15>
In the production example of the polymer 1, the same operations as in the production example of the polymer 1 were carried out except that the conditions were appropriately changed so as to be shown in Table 1, to obtain polymers 2 to 15. Table 1 shows various physical properties of the obtained polymers 2 to 15.

<Production example of polyester resin L>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 72.0 parts by mass (0.20 mol; 100.0 mol% with respect to the total number of moles of polyhydric alcohol)
-Terephthalic acid: 28.0 parts by mass (0.17 mol; 100.0 mol% with respect to the total number of moles of polyvalent carboxylic acid)
-Tin 2-ethylhexanoate (esterification catalyst): 0.5 parts by mass The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C.

Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180 ° C., and returned to atmospheric pressure.

Trimellitic anhydride: 3 parts by mass (0.01 mol; 4.0 mol% based on the total number of moles of polyvalent carboxylic acid)
-Tert-Butylcatechol (polymerization inhibitor): 0.1 parts by mass After that, the above material was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 1 hour while maintaining the temperature at 180 ° C., ASTM D36. After confirming that the softening point measured according to −86 reached 90 ° C., the temperature was lowered to stop the reaction, and an amorphous polyester resin L was obtained.

<Production example of polyester resin H>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 72.3 parts by mass (0.20 mol; 100.0 mol% based on the total number of moles of polyhydric alcohol)
-Terephthalic acid: 18.3 parts by mass (0.11 mol; 65.0 mol% with respect to the total number of moles of polyvalent carboxylic acid)
Fumaric acid: 2.9 parts by mass (0.03 mol; 15.0 mol% with respect to the total number of moles of polyvalent carboxylic acid)
-Tin 2-ethylhexanoate (esterification catalyst): 0.5 parts by mass The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C.

Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, and returned to atmospheric pressure.

Trimellitic anhydride: 6.5 parts by mass (0.03 mol; 20.0 mol% with respect to the total number of moles of polyvalent carboxylic acid)
-Tert-Butylcatechol (polymerization inhibitor): 0.1 parts by mass Then, the above material was added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160 ° C., ASTM D36. After confirming that the softening point measured according to −86 reached 137 ° C., the temperature was lowered to stop the reaction, and an amorphous polyester resin H was obtained.

<Crystalline resin (Crystalline polyester resin C)>
1,6-Hexanediol: 34.5 parts by mass (0.29 mol; 100.0 mol% based on the total number of moles of polyhydric alcohol)
Dodecanedioic acid: 65.5 parts by mass (0.28 mol; 100.0 mol% based on the total number of moles of polyvalent carboxylic acid)
-Tin 2-ethylhexanoate: 0.5 parts by mass The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. After replacing the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140 ° C.

Next, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200 ° C.

Further, after gradually releasing the pressure in the reaction vessel and returning it to normal pressure, one or more aliphatic compounds selected from the group consisting of aliphatic monocarboxylic acids and aliphatic monoalcohols shown in Table 2 Was added in an amount of 7.0 mol% based on 100.0 mol% of the raw material monomer, and the mixture was reacted at 200 ° C. for 2 hours under normal pressure.

Then, the inside of the reaction vessel was reduced to 5 kPa or less and reacted at 200 ° C. for 3 hours to obtain a crystalline polyester resin C. The SP value (SP1) of the crystalline polyester resin C is 11.3.

<Manufacturing example of toner 1>
・ Amorphous polyester resin L 50 parts by mass ・ Amorphous polyester resin H 50 parts by mass ・ Crystalline polyester resin C 5 parts by mass ・ Polymer 15 parts by mass ・ Fisher tropche wax (hydrocarbon wax, peak of maximum heat absorption peak Temperature 90 ° C) 5 parts by mass · C.I. I. Pigment Blue 15:37 parts by mass, 3,5-di-t-butylsalicylate aluminum compound (Bontron E88, manufactured by Orient Chemical Industry Co., Ltd.) 0.3 parts by mass Henschel mixer (FM-75 type, Mitsui Mine Co., Ltd.) ) Was mixed at a rotation speed of 20 s ^-1 and a rotation time of 5 minutes, and then kneaded with a twin-screw kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.). The barrel temperature during kneading was set so that the outlet temperature of the kneaded product was 115 ° C. The outlet temperature of the kneaded product was directly measured using a handy type thermometer HA-200E manufactured by Anritsu Meter Co., Ltd.

The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed product. The obtained pyroclastic material was finely pulverized with a mechanical crusher (T-250, manufactured by Turbo Industries, Ltd.). Further, using Faculty F-300 (manufactured by Hosokawa Micron Co., Ltd.), classification was performed to obtain toner particles 1. The operating conditions were a classification rotor rotation speed of 130s ^-1 and a distributed rotor rotation speed of 120s ^-1 .

Using the obtained toner particles 1, heat treatment was performed by the surface treatment apparatus shown in FIG. 1 to obtain heat-treated toner particles. The operating conditions are feed amount = 5 kg / hr, hot air temperature = 150 ° C, hot air flow rate = 6 m ³ / min, cold air temperature = -5 ° C, cold air flow rate = 4 m ³ / min, blower air volume = 20 m ³ / min, The injection air flow rate was 1 m ³ / min.

The heat treatment the particles 100 parts by weight of the resulting toner, the hydrophobic silica (BET: 200m ² /g)1.0 parts by mass of titanium oxide fine particles surface-treated with isobutyl trimethoxysilane (BET: a 80m ² / g) 1 Toner 1 was obtained by mixing 0.0 parts by mass with a Henschel mixer (FM-75 type, manufactured by Mitsui Mine Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 minutes.

<Manufacturing example of toners 2 to 22>
In the toner 1 production example, the same operations as in the toner 1 production example were performed except that the polymer, kneading conditions, and heat treatment method were appropriately changed so as to be shown in Table 2, to obtain toners 2 to 22. Table 2 shows the manufacturing conditions and the physical characteristics of the toner.

<Production example of magnetic core particle 1>
・ Process 1 (weighing / mixing process):
Fe ₂ O ₃ 62.7 parts by mass MnCO ₃ 29.5 parts by mass Mg (OH) ₂ 6.8 parts by mass SrCO ₃ 1.0 part by mass The ferrite raw material was weighed so as to have the above composition ratio. Then, it was pulverized and mixed for 5 hours with a dry vibration mill using stainless beads having a diameter of 1/8 inch.
-Step 2 (temporary firing step):
The obtained pulverized product was made into pellets of about 1 mm square by a roller compactor. Coarse powder was removed from the pellets with a vibrating sieve having an opening of 3 mm, and then fine powder was removed with a vibrating sieve having an opening of 0.5 mm. It was calcined at a temperature of 1000 ° C. for 4 hours at 01% by volume) to prepare a calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393
-Step 3 (crushing step):
After crushing to about 0.3 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and the mixture was crushed with a wet ball mill for 1 hour. The slurry was pulverized with a wet ball mill using alumina beads having a diameter of 1/16 inch for 4 hours to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).
・ Process 4 (granulation process):
To 100 parts by mass of calcined ferrite, 1.0 part by mass of ammonium polycarboxylic acid as a dispersant and 2.0 parts by mass of polyvinyl alcohol as a binder were added to the ferrite slurry, and a spray dryer (manufacturer: Okawara Kakoki) was used. It was granulated into spherical particles. After adjusting the particle size of the obtained particles, the particles were heated at 650 ° C. for 2 hours using a rotary kiln to remove organic components of the dispersant and the binder.
-Step 5 (firing step):
In order to control the firing atmosphere, the temperature was raised from room temperature to a temperature of 1300 ° C. in 2 hours under a nitrogen atmosphere (oxygen concentration 1.00% by volume) in an electric furnace, and then firing was performed at a temperature of 1150 ° C. for 4 hours. Then, over 4 hours, the temperature was lowered to 60 ° C., the nitrogen atmosphere was returned to the atmosphere, and the mixture was taken out at a temperature of 40 ° C. or lower.
・ Process 6 (sorting process):
After crushing the agglomerated particles, the low magnetic force product is cut by magnetic force beneficiation and sieved with a sieve having a mesh size of 250 μm to remove coarse particles. Magnetic core particles 1 were obtained.

<Preparation of coating resin 1>
Cyclohexyl methacrylate monomer 26.8% by mass
Methyl methacrylate monomer 0.2% by mass
Methyl methacrylate macromonomer 8.4% by mass
(Macromonomer having a methacryloyl group at one end and having a weight average molecular weight of 5000)
Toluene 31.3% by mass
Methyl ethyl ketone 31.3% by mass
Azobisisobutyronitrile 2.0% by mass
Of the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone are added to a four-port separable flask equipped with a reflux condenser, a thermometer, a nitrogen introduction tube, and a stirrer, and nitrogen gas is added. Was introduced to give a sufficient nitrogen atmosphere, the mixture was heated to 80 ° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate and precipitate a copolymer, and the precipitate was separated by filtration and then vacuum dried to obtain a coating resin 1. The obtained coating resin 1 was dissolved in 30 parts by mass, 40 parts by mass of toluene, and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content: 30% by mass).

<Preparation of coating resin solution 1>
Polymer solution 1 (resin solid content concentration 30%) 33.3% by mass
Toluene 66.4% by mass
Carbon black (Regal330; manufactured by Cabot) 0.3% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption 75 ml / 100 g)
Was dispersed in a paint shaker for 1 hour using zirconia beads having a diameter of 0.5 mm. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Manufacturing example of magnetic carrier 1>
(Resin coating process):
The coating resin solution 1 was added to a vacuum degassing type kneader maintained at room temperature so as to be 2.5 parts by mass as a resin component with respect to 100 parts by mass of the packed core particles 1. After the addition, the mixture was stirred at a rotation speed of 30 rpm for 15 minutes, the solvent was volatilized above a certain level (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure, toluene was distilled off over 2 hours, and then the mixture was cooled. The obtained magnetic carrier is separated into low magnetic force products by magnetic force beneficiation, passed through a sieve having an opening of 70 μm, and then classified by a wind power classifier. I got 1.

^{With the above toners 1 to 22 and the magnetic carrier 1, 0.5 s -1} and rotation time 5 minutes with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) so that the toner concentration becomes 8.0% by mass. To obtain a two-component developer 1 to 22.

[Examples 1 to 16, Comparative Examples 1 to 6]
<Evaluation 1: Low temperature fixability>
As an image forming apparatus, Canon's digital commercial printing printer imageRUNNER ADVANCE C5051 was used and modified so that the fixing temperature and process speed could be set freely. A two-component developer is placed in the developer at the cyan position of this modified machine, and the DC voltage _VDC and electrostatic of the developer carrier so that the amount of toner on the electrostatic latent image carrier or paper is desired. The charging voltage V _D and laser power of the latent image carrier were adjusted and evaluated later. The results are shown in Table 4.
Paper: CS-680 (68.0 g / m ² )
(Sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 1.20 mg / cm ^{2
Evaluation image: An image of 10 cm 2} is placed in the center of the above A4 paper. Fixing test environment: Low temperature and low humidity environment: Temperature 15 ° C / Humidity 10% RH (hereinafter “L / L”)

_{After adjusting the DC voltage V DC} of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power so that the amount of toner loaded on the paper is as described above, the process speed is 450 mm / sec. The fixing temperature was set to 130 ° C. and the low temperature fixing property was evaluated. The value of the image density reduction rate was used as an evaluation index for low temperature fixability. The image density reduction rate is determined by first measuring the image density at the center using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). ^{Next, a load of 4.9 kPa (50 g / cm 2} ) is applied to the portion where the image density is measured, and the fixed image is rubbed (5 reciprocations) with Sylbon paper, and the image density is measured again. Then, the rate of decrease in image density (%) before and after rubbing was measured.

(Evaluation criteria)
A: Concentration reduction rate less than 1.5% B: Concentration reduction rate 1.5% or more and less than 2.0% C: Concentration reduction rate 2.0% or more and less than 2.5% D: Concentration reduction rate 2.5 % Or more and less than 3.0% E: Concentration reduction rate 3.0% or more The smaller the value of the concentration reduction rate, the better.

<Evaluation 2: High temperature and high humidity chargeability>
^{The electrostatic latent image carrier was adjusted to be loaded at 0.35 mg / cm 2 in a} high temperature and high humidity environment (32.5 ° C., 80% RH), and was collected by suction with a metal cylindrical tube and a cylindrical filter. .. At that time, the amount of charge Q stored in the condenser and the mass M of the collected toner are measured through a metal cylindrical tube, the amount of charge Q / M (mC / kg) per unit mass is calculated, and the electrostatic latent image is carried. The body was Q / M (mC / kg).

(Evaluation criteria)
A: Q / M on the electrostatic latent image carrier is 36.0 mC / kg or more B: Q / M on the electrostatic latent image carrier is 33.0 mC / kg or more and less than 36.0 mC / kg C: Electrostatic latent image Q / M on the image carrier is 31.0 mC / kg or more and less than 33.0 mC / kg D: Q / M on the electrostatic latent image carrier is 29.0 mC / kg or more and less than 31.0 mC / kg E: Static Q / M on the electro-latent image carrier is less than 29.0 mC / kg

The larger the Q / M value on the electrostatic latent image carrier, the better.

<Evaluation 3: High temperature and high humidity charge retention>
^{The electrostatic latent image carrier was adjusted to be loaded at 0.35 mg / cm 2 in a} high temperature and high humidity environment (32.5 ° C., 80% RH), and was collected by suction with a metal cylindrical tube and a cylindrical filter. .. At that time, the amount of charge Q stored in the condenser and the mass M of the collected toner are measured through a metal cylindrical tube, the amount of charge Q / M (mC / kg) per unit mass is calculated, and the electrostatic latent image is carried. The body was Q / M (mC / kg).

After performing the above evaluation, the developer was removed from the machine, left in an environment of 32.5 ° C. and 80% RH for 72 hours, the developer was mounted again in the machine, and the same DC voltage V _{DC as the initial evaluation was performed.} The amount of charge Q / M per unit mass on the electrostatic latent image carrier was measured.

The Q / M on the electrostatic latent image carrier was set to 100%, and the maintenance rate of the Q / M on the photoconductor after being left for 24 hours was calculated and judged according to the following criteria.

(Evaluation criteria)
A: Q / M retention rate on the electrostatic latent image carrier is 90% or more B: Q / M retention rate on the electrostatic latent image carrier is 85% or more and less than 90% C: Q on the electrostatic latent image carrier / M retention rate is 83% or more and less than 85% D: Q / M retention rate on the electrostatic latent image carrier is 80% or more and less than 83% E: Q / M retention rate on the electrostatic latent image carrier is 80 %Less than

The larger the value of the Q / M maintenance rate on the electrostatic latent image carrier, the better.

<Evaluation 4: Wax dispersibility evaluation method (hot offset resistance)>
Paper: CS-680 (68.0 g / m ² )
(Sold by Canon Marketing Japan Inc.)
Toner loading amount: 0.08 mg / cm ^{2
Evaluation image: 10 cm 2} images are placed on both ends of the above A4 paper Fixing test environment: Room temperature and low humidity environment: Temperature 23 ° C / Humidity 5% RH (hereinafter "N / L")

After producing the unfixed image, the process speed was set to 450 mm / sec, the fixing temperature was raised by 5 ° C. in order from 150 ° C., and the hot offset resistance was evaluated. As a procedure, first, 10 plain postcards were passed through the center position of the fixing belt, and then the unfixed image was passed. The fog value was used as an evaluation index for hot offset. For fog, the average reflectance Dr (%) of the evaluation paper before drawing and the reflectance Ds (%) of the white background after the fixing test by the reflect meter (“REFLEC TIMETER MODEL TC-6DS” manufactured by Tokyo Deniro Co., Ltd.) ) Was measured and calculated using the following formula. The obtained fog was evaluated according to the following evaluation criteria.
Fog (%) = Dr (%) -Ds (%)

(Evaluation criteria)
A: Less than 0.2% B: 0.2% or more, less than 0.5% C: 0.5% or more, less than 1.0% D: 1.0% or more

The smaller the value, the better.

The toner of Comparative Example 1 is a toner that does not contain a crystalline material. By including a crystalline material in the toner, the binder resin can plasticize the amorphous resin to improve the low temperature fixability, but since this toner does not contain the crystalline material, the low temperature fixability is inferior. It has become.

The toner of Comparative Example 2 uses a polymer having an SP value different from that of the resin. If a polymer having an SP value different from that of the crystalline material is used, the affinity with the resin is inferior, so that the fine dispersion of the wax or the crystalline material is deteriorated. Therefore, the hot offset resistance, which is sensitive to wax dispersion, and the chargeability and charge retention under high temperature and high humidity are inferior.

The toner of Comparative Example 3 is a toner that does not contain a unit derived from cycloalkyl (meth) acrylate. When the polymer contains a unit derived from a hydrophobic cycloalkyl (meth) acrylate, the hydrophobicity of the toner is improved, and the chargeability and charge retention under high temperature and high humidity are improved. However, since this toner does not contain a unit derived from cycloalkyl (meth) acrylate, the result is that the chargeability and charge retention under high temperature and high humidity are inferior.

The toner of Comparative Example 4 is a toner that does not contain a crystalline material or a unit derived from cycloalkyl (meth) acrylate. As described above, the low temperature fixability and the chargeability and charge retention under high temperature and high humidity are inferior.

The toner of Comparative Example 5 does not contain a unit derived from cycloalkyl (meth) acrylate, and uses a polymer having an SP value distant from the resin. If a polymer having an SP value different from that of the crystalline material is used, the affinity with the resin is inferior, so that the fine dispersion of the wax or the crystalline material is deteriorated. Therefore, the hot offset resistance, which is sensitive to wax dispersion, and the chargeability and charge retention under high temperature and high humidity are inferior.

The toner of Comparative Example 6 uses a polymer that does not contain a crystalline material, does not contain a unit derived from cycloalkyl (meth) acrylate, and does not contain a polar group unit. Therefore, not all evaluations meet the criteria.

1. 1. Raw material quantitative supply means, 2. Compressed gas flow rate adjusting means, 3. Introductory tube, 4. Protruding member, 5. Supply pipe, 6. Processing room, 7. Hot air supply means, 8. Cold air supply means, 9. Regulatory means, 10. Recovery means, 11. Hot air supply means outlet, 12. Distributor, 13. Swivel member, 14. Powder particle supply port

Claims (3)

Toner containing amorphous resin, crystalline resin, wax and wax dispersant.
The wax dispersant is a graft polymer in which a styrene acrylic polymer is bonded to a hydrocarbon wax.
The styrene acrylic polymer
(I) A unit derived from cycloalkyl acrylate or a unit derived from cycloalkyl methacrylate , and
(Ii) It has a methacrylic acid unit and
A toner characterized in that the solubility parameter SP1 of the crystalline resin and the solubility parameter SP2 of the wax dispersant satisfy the relationship of the following formula (1).
0 ≦ SP1-SP2 ≦ 1.3 Equation (1) The toner according to claim 1, wherein the acid value of the graft polymer is 5 mgKOH / g or more and 50 mgKOH / g or less. The toner according to claim 1 or 2 , wherein the styrene acrylic polymer has a unit derived from cyclohexyl methacrylate.

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