JP2014178618A - Toner, developer, image forming apparatus, and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which is excellent in low-temperature fixability and hot-offset resistance even when a resin containing a polylactic acid skeleton is used as a substantial main ingredient, which shows little changes in physical properties even after long-term storage, and which can output a stable image.SOLUTION: The toner comprises at least a binder resin and a release agent. The binder resin comprises a polyester resin having at least a structural unit of dehydrated and condensed lactic acid. An optical purity X (%) defined by an expression of X (%)=|X(L-form)-X(D-form)| in the structural unit comprising dehydrated and condensed lactic acid is 80% or less in terms of monomer components; and in the above expression, X(L-form) represents a ratio (%) of L-forms in terms of lactic monomers and X(D-form) represents a ratio (%) of D-forms in terms of lactic monomers. The toner further contains a monocarbodiimide compound by 0.1 to 5 wt.% relative to the toner weight.

Description

  The present invention relates to a toner, a developer using the toner, an image forming apparatus, and a process cartridge.

Due to the rise of recent environmentally friendly products, etc., a technology that uses plant-derived raw materials and fixes toner with low energy is desired.
As a means for utilizing a resin using a plant-derived raw material as a toner material, there is an example of using a biodegradable microbial-produced aliphatic polyester as a binder resin (for example, Patent Document 1). When used as a resin, the softening temperature of the toner is high, so the fixing temperature must be set high, which is unsuitable from the viewpoint of energy saving.
As a technique for lowering the fixing temperature, a method of lowering the softening temperature by adding a large amount of plant wax to a naturally derived resin (for example, Patent Document 2) has been proposed. However, the toner often tends to aggregate due to the wax component, resulting in problems such as poor productivity and poor toner transportability due to poor toner fluidity.

In order to obtain low-temperature fixability and fixing stability, a method using a binder resin containing two kinds of resins having different softening points and a naturally-derived resin has also been proposed (for example, Patent Documents 3 to 4). In this method, a resin having a low softening point serves as a bridge between a resin having a high softening point and a naturally derived resin, and the biodegradable resin is uniformly dispersed in the binder resin. However, if the blending ratio of the naturally-derived resin is set high, poor dispersion of the naturally-derived resin occurs, leading to a decrease in developability due to variations in charging performance, and the durability deteriorates. The blending ratio is as low as about 20% by weight.
On the other hand, as a means for lowering the toner fixing temperature, a technique for lowering the glass transition point of the binder resin is generally used. This glass transition point is a design point of the toner binder, and the fixing characteristics can be controlled by the glass transition point. However, amorphous polylactic acid, which is a typical naturally-derived resin, is composed only of lactic acid units. Therefore, the means for controlling the glass transition point is limited, and in a toner containing a polylactic acid resin at a high concentration, it has not been possible to obtain a toner that can be fixed at a low temperature more than before, and moreover than a conventional toner. Even high temperature was necessary.

A toner using a polylactic acid resin has not only a minimum fixing temperature but also a high temperature hot offset resistance. Since the polylactic acid resin has a resin design range limited by its synthesis method, it is difficult to introduce a branched structure or a crosslinked structure as in the conventional toner binder, and it is difficult to provide high temperature offset resistance.
Further, although not clearly specified in any of the prior arts, systems using these naturally-derived resins are more easily hydrolyzed than conventional toner binders, resulting in a decrease in glass transition point and heat distortion temperature. When transported, stored, etc., the particles or the formed images are stuck together and have the disadvantage that they cannot be used.
As described above, there are many problems in using a naturally-derived resin as a main resin component of a toner binder resin, and even when a part of the binder resin is replaced with a naturally-derived resin, the blending amount is limited. Therefore, more natural-derived resins are expected to be blended while maintaining the properties as a binder resin.

  The present invention provides a toner that is excellent in low-temperature fixability and hot offset resistance even when a resin containing a polylactic acid skeleton is used as a main component, and that can output a stable image with little change in physical properties even after long-term storage. For the purpose of provision.

The above problem is solved by the following invention 1).
1) A toner containing at least a binder resin and a release agent, wherein the binder resin includes a polyester resin having a structural unit in which at least lactic acid is dehydrated and condensed, and the lactic acid is dehydrated and condensed in the structural unit. A toner having an optical purity X (%) in terms of a monomer component represented by the following formula of 80% or less, and further containing a monocarbodiimide compound in an amount of 0.1 to 5% by weight based on the toner weight.
Optical purity X (%) = | X (L form) -X (D form) |
[However, X (L form) represents the L form ratio (%) in terms of lactic acid monomer, and X (D form) represents the D form ratio (%) in terms of lactic acid monomer. ]

  According to the present invention, even when a resin containing a polylactic acid skeleton is used as a substantial main component, it has excellent low-temperature fixability and hot offset resistance, and can output a stable image with little change in physical properties even after long-term storage. Toner can be provided.

Hereinafter, the present invention 1) will be described in detail, but the following 2) to 7) are also included in the embodiments of the present invention, and these will be described together.
2) The toner according to 1), wherein the monocarbodiimide compound has an aromatic ring.
3) The toner according to 1) or 2), wherein the polyester resin contains an aliphatic crystalline polyester segment.
4) The toner according to 1) or 2), wherein the polyester resin contains an amorphous polyester segment.
5) A developer comprising the toner according to any one of 1) to 4).
6) An electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, and exposure means for exposing the charged surface of the electrostatic latent image carrier to form an electrostatic latent image. Developing means for developing the electrostatic latent image with toner to form a visible image; transfer means for transferring the visible image to a recording medium; and fixing the transferred image transferred to the recording medium. An image forming apparatus having at least a fixing unit to be used, wherein the toner is the toner according to any one of 1) to 4).
7) An image forming apparatus having at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image A process cartridge detachably attached to a main body, wherein the toner is the toner according to any one of 1) to 4).

[toner]
The toner of the present invention contains a polyester resin having a structural unit obtained by dehydration condensation of lactic acid and a monocarbodiimide compound.
The present inventors have excellent low-temperature fixability and hot offset resistance by including a monocarbodiimide compound even when polylactic acid is used as a substantial main component as a binder resin, and physical properties even after long-term storage. The present inventors have found that it is possible to provide a toner that can output a stable image with less fluctuation.

  By including a monocarbodiimide compound, even when a large amount of a resin having a polylactic acid skeleton, which has been difficult to fix at low temperatures, is incorporated, it is possible to fix the toner at a low temperature by the plasticizing effect of the monocarbodiimide compound. It was. At the same time, a part of the monocarbodiimide compound is bonded to the carbodialkyl group of the resin component to become an acyl urea group. Due to the hydrogen bond of the acylurea group, the viscoelasticity in the high temperature region was appropriately maintained, and the hot offset resistance could be improved while maintaining the low temperature fixing effect. Further, as described above, a part of the monocarbodiimide compound is bonded to the carboxyl group, so that the resin acid value is eliminated, the hydrolysis resistance is improved, and the property change of the toner is small even after long-term storage in a high temperature and high humidity environment. A stable output image can be obtained. The remaining monocarbodiimide compound that does not bind to the carboxyl group is contained in the toner in an unreacted state, contributes to low-temperature fixing, and immediately traps the carboxyl group that is formed over time by hydrolysis, and autocatalytic hydrolysis by the carboxyl group. Since decomposition is prevented, quality stability over time during long-term storage can be improved.

Furthermore, it is preferable that the monocarbodiimide compound has an aromatic ring because it has an effect of improving pigment dispersibility. This is because an acylurea group having an aromatic ring with a carboxyl group as a starting point is introduced into a polylactic acid resin having a low affinity with the pigment, and the functional group having this aromatic ring increases the affinity with the pigment. The present inventors are thinking.
If a polycarbodiimide having two or more carbodiimide groups in the molecule is used instead of a monocarbodiimide, not only a plasticizing effect can be obtained, but also chain extension and cross-linking occur, resulting in significant deterioration in low-temperature fixability. May invite. In addition, since polycarbodiimide deteriorates the uniform diffusibility and dispersibility in the molecule, it becomes difficult to react with the carboxyl group, and the physical property fluctuation after long-term storage may not be suppressed.

The monocarbodiimide compound used in the present invention is a compound having one carbodiimide group in the molecule.
Specific examples thereof include N, N′-di-2,6-diisopropylphenylcarbodiimide, N, N′-di-o-tolylcarbodiimide, N, N′-diphenylcarbodiimide, N, N′-dioctyldecylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N-tolyl-N'-cyclohexylcarbodiimide, N, N'-di-2,6-di-tert-butylphenylcarbodiimide, N-tolyl-N ' -Phenylcarbodiimide, N, N'-di-p-nitrophenylcarbodiimide, N, N'-di-p-aminophenylcarbodiimide, N, N'-di-p-hydroxyphenylcarbodiimide, N, N'-dicyclohexylcarbodiimide N, N'-di-p-tolylcarbodiimide, p-phenylenebisdi-o-to L-carbodiimide, p-phenylenebisdicyclohexylcarbodiimide, hexamethylenebisdicyclohexylcarbodiimide, ethylenebisdiphenylcarbodiimide, N, N'-benzylcarbodiimide, N-octadecyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N -Octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N-phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenyl Carbodiimide, N, N′-di-p-ethylphenylcarbodiimide, N, N′-di-o-isopropylphenylcarbodiimide, N, N′-di-p-isopropylphenylcarbodiimide, , N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N, N'-di-2,6-diethylphenylcarbodiimide, N, N'-di-2-ethyl -6-isopropylphenylcarbodiimide, N, N'-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N'-di-2,4,6-trimethylphenylcarbodiimide, N, N'-di-2, 4,6-triisopropylphenylcarbodiimide, N, N′-di-2,4,6-triisobutylphenylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, di-β-naphthyl Carbodiimide, di-t Such as butyl carbodiimide, and the like.

As described above, among the monocarbodiimide compounds, those having an aromatic ring are preferable from the viewpoint of pigment dispersibility, and among them, N, N'-di-2,6 is preferable from the viewpoint of plasticizing effect and hydrolysis resistance. -Diisopropylphenylcarbodiimide is particularly preferred.
These monocarbodiimide compounds may be used alone or in combination of two or more.
Furthermore, commercially available products may be used as the monocarbodiimide compound, such as “STABACKZOL I” “STABACKZOL I-LF” manufactured by Rhein Chemie, “EN160”, “NCN” manufactured by Matsumoto Yushi Co., Ltd., and the like. It is done.
The content of the monocarbodiimide compound in the toner needs to be 0.1 to 5% by weight, preferably 0.2 to 4% by weight, and more preferably 0.5 to 3% by weight. If it is less than 0.1% by weight, a low-temperature fixability and a stable output image after long-term storage cannot be obtained, and if it exceeds 5% by weight, other physical properties such as heat-resistant storage property and charging characteristics of the toner are adversely affected.
The method for measuring the content of the monocarbodiimide compound in the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the toner is dissolved in a suitable solvent, and then solids such as pigments, mold release agents, and external additives are removed by filtration to obtain a solution containing a carbodiimide compound. This solution is measured with a high performance liquid chromatograph (HPLC), and content is quantified from the peak area originating in a carbodiimide compound.
The blending method of the carbodiimide compound is not particularly limited, and may be melt-kneaded with a toner component such as a binder resin, or may be mixed with a toner component such as a binder resin in an organic solvent.

As the polyester resin having a structural unit (polylactic acid skeleton) obtained by dehydration condensation of lactic acid, polylactic acid and a copolymer thereof can be used.
The manufacturing method of the said polylactic acid is not specifically limited, A conventionally well-known method can be used. For example, after fermenting starch such as corn as a raw material to obtain lactic acid, a method of directly dehydrating and condensing from lactic acid monomer, a method of synthesizing from lactic acid via cyclic dimer lactide by ring-opening polymerization in the presence of a catalyst Etc. Among them, the method by ring-opening polymerization is preferable from the viewpoint of productivity such that the molecular weight can be controlled by the initiator amount and the reaction can be completed in a short time.
The copolymer preferably contains an aliphatic crystalline polyester segment or an amorphous polyester segment. As such a copolymer, a copolymer obtained by ring-opening polymerization of a lactide from a terminal hydroxyl group of an aliphatic crystalline polyester polyol or an amorphous polyester polyol, or a diisocyanate such as diphenylmethane diisocyanate using polyester polyol and polylactic acid is used. Any known copolymer such as a copolymer modified with urethane can be appropriately selected and used.

Among the copolymers, a copolymer with an aliphatic crystalline polyester is particularly preferable from the viewpoint of low-temperature fixability and heat-resistant storage stability. As a copolymerization method for producing a copolymer with the aliphatic crystalline polyester, a method of ring-opening polymerization of lactide from a terminal hydroxyl group of the aliphatic crystalline polyester polyol is used when a uniform structure is obtained as a toner. This is preferable because there is little variation in composition and the best low-temperature fixability and heat-resistant storage stability can be exhibited.
A copolymer with an amorphous polyester is particularly preferred from the viewpoint of not only low-temperature fixability and heat-resistant storage stability but also excellent charging characteristics and pigment dispersibility. By using a copolymer with amorphous polyester, pigment dispersibility is improved and good color reproducibility is obtained, and deterioration of fixing characteristics due to pigment segregation can be suppressed. In addition, the resistance of the toner increases and good charging characteristics can be obtained. As a copolymerization method for producing a copolymer with the amorphous polyester, a method of ring-opening polymerization of lactide from a terminal hydroxyl group of an amorphous polyester polyol is used when a toner having a uniform structure is obtained. It is preferable because it has little variation and can exhibit excellent charging characteristics and pigment dispersibility while having low-temperature fixability and heat-resistant storage stability.

The optical purity X (%) in terms of a monomer component represented by the following formula in the polylactic acid skeleton is 80% or less. Within this range, the solvent solubility and transparency of the polyester resin are improved. On the other hand, when the optical purity X exceeds 80%, the polylactic acid segment in the polylactic acid and the copolymer is crystallized, so that the softening temperature and melt viscosity of the toner are greatly increased, and the low-temperature fixability is significantly impaired.
X (%) = | X (L-form) -X (D-form) |
[However, X (L form) represents the L form ratio (%) in terms of lactic acid monomer, and X (D form) represents the D form ratio (%) in terms of lactic acid monomer. ]

There is no restriction | limiting in particular in the measuring method of the said optical purity X, According to the objective, it can select suitably. For example, a polymer or toner having a polyester skeleton is added to a mixed solvent of pure water, a 1N aqueous sodium hydroxide solution and isopropyl alcohol, and is heated and stirred at 70 ° C. to be hydrolyzed. Subsequently, after filtering and removing the solid content in a liquid, it neutralizes by adding a sulfuric acid, The aqueous solution containing L- and / or D-lactic acid produced | generated by decomposition | disassembly of a polyester resin is obtained. This aqueous solution was measured by a high performance liquid chromatograph (HPLC) using a chiral ligand exchange type column SUMICHILAR OA-5000 (manufactured by Sumika Chemical Analysis Co., Ltd.), and a peak area S (L) derived from L-lactic acid. And the peak area S (D) derived from D-lactic acid is calculated. And the optical purity X can be calculated | required from this peak area by the following formula.
X (L body)% = 100 × S (L) / [S (L) + S (D)]
X (D-form)% = 100 × S (D) / [S (L) + S (D)]
Optical purity X% = | X (L form) -X (D form) |

  The X (L form) and X (D form) of the monomer forming the polylactic acid skeleton are equal to the ratio of the L form and D form of the monomer used to form the polylactic acid skeleton. Therefore, in order to control the optical purity X (%) in terms of the monomer component of the polylactic acid skeleton of the binder resin, an appropriate amount of L and D monomers may be used in combination. For example, when a polylactic acid resin or copolymer is obtained by ring-opening polymerization of lactide, a desired amount can be obtained by adjusting the amount of lactide selected from at least two of L-lactide, D-lactide, and meso-lactide. Optical purity X (%) can be obtained. D-lactide is more expensive than L-lactide or meso-lactide, and it is preferable that the charged weight% of D-lactide is small.

Although the weight average molecular weight of the said polyester resin can be suitably selected according to the objective, 10000-60000 are preferable and 20000-50000 are more preferable. If the molecular weight is too low, the toner may be inferior in heat-resistant storage and durability against stress such as stirring in the developing device, and if the molecular weight is too high, the viscoelasticity at the time of melting of the toner will increase and low temperature fixability will result. May be inferior. The weight average molecular weight of the polyester resin can be measured by, for example, gel permeation chromatography (GPC).
The molecular structure of the polyester resin can be confirmed by GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid.

  The aliphatic crystalline polyester is obtained by a reaction between a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester. In the present invention, the polyester resin modified is not included in the aliphatic crystalline polyester.

-Polyhydric alcohol component-
There is no restriction | limiting in particular as said polyhydric alcohol component, According to the objective, it can select suitably, For example, diol and trihydric or more alcohol are mentioned.
Examples of the diol include saturated aliphatic diol. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear chains having 4 to 12 carbon atoms are preferred. Type saturated aliphatic diols are more preferred. In the case of a branched saturated aliphatic diol, the crystallinity of the aliphatic crystalline polyester may decrease, and the melting point may decrease. On the other hand, when the main chain portion has less than 4 carbon atoms, the melting temperature becomes high in the case of polycondensation with an aromatic dicarboxylic acid, and low-temperature fixing may be difficult. On the other hand, when the number of carbon atoms in the main chain portion exceeds 12, it is difficult to obtain a practical material.

Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, Examples thereof include 18-octadecanediol and 1,14-eicosandecanediol. Among these, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1 is preferable in that the crystalline polyester has high crystallinity and excellent sharp melt properties. , 12-dodecanediol is preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
The said polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

-Polycarboxylic acid component-
There is no restriction | limiting in particular as said polyvalent carboxylic acid component, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Examples thereof include saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, and further anhydrides and lower alkyl esters thereof.
These may be used individually by 1 type and may use 2 or more types together.

The melting point of the aliphatic crystalline polyester is preferably 50 ° C to 80 ° C. When the melting point is less than 50 ° C, the heat-resistant storage stability is deteriorated, and when it exceeds 80 ° C, the low-temperature fixability is deteriorated. The melting point can be measured, for example, by differential scanning calorimetry (DSC method).
The weight average molecular weight of the aliphatic crystalline polyester can be appropriately selected according to the purpose, but is preferably 5000 to 30000, more preferably 7000 to 20000.
Further, the content of the aliphatic crystalline polyester in the copolymer is preferably 10 to 40% by weight. When the content is less than 10%, the polylactic acid skeleton is dominant and sufficient low-temperature fixability is not exhibited. On the other hand, if it exceeds 40% by weight, it tends to flow at a lower temperature, but it tends to be offset, so the fixing temperature range becomes narrower.
The molecular structure of the aliphatic crystalline polyester can be confirmed by GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid.

The amorphous polyester is obtained by reacting a polyhydric alcohol component with a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester.
The alcohol component used in the amorphous polyester is a divalent alcohol (diol), specifically, an alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol). 1,4-butylene glycol and 1,6-hexanediol); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polybutylene glycol, etc.); carbon C6-C36 alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); C2-C4 alkylene oxide of the above alicyclic diol [ethylene oxide (hereinafter abbreviated as EO)] ), Propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition moles 1-30); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) And C 2-4 alkylene oxide (EO, PO, BO, etc.) adducts (addition mole number 2-30).

  Moreover, in addition to the diol, a trivalent or higher (3 to 8 or higher) alcohol component may be contained. Specifically, an aliphatic polyhydric alcohol having 3 to 36 or more carbon atoms having 3 to 8 or more carbon atoms (an alkane polyol and an intramolecular or intermolecular dehydrate thereof such as glycerin, triethylolethane, trimethylolpropane, pentane). Erythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; saccharides and derivatives thereof such as sucrose and methyl glucoside; ) Adduct (addition mole number 1-30); Trisphenols (trisphenol PA etc.) C2-C4 alkylene oxide (EO, PO, BO etc.) addition product (addition mole number 2-30); Novolak Resin (phenol novolak and cresol novolak, etc .: average degree of polymerization Two to four alkylene oxide carbon of ~60) (EO, PO, BO, etc.) adducts (added mole number 2 to 30), and the like.

  As the carboxylic acid component used for the amorphous polyester, a divalent carboxylic acid (dicarboxylic acid), specifically, an alkanedicarboxylic acid having 4 to 36 carbon atoms (succinic acid, apidic acid, sebacic acid, etc.), and Alkenyl succinic acid (such as dodecenyl succinic acid); C4-C36 alicyclic dicarboxylic acid [dimer acid (dimerized linoleic acid), etc.]; C4-C36 alkene dicarboxylic acid (maleic acid, fumaric acid, citraconic acid) And aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid or derivatives thereof, and naphthalenedicarboxylic acid). Of these, alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable. In addition, as a polycarboxylic acid, you may use the acid anhydride of the above-mentioned thing, or a lower alkyl (C1-C4) ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

The glass transition temperature of the amorphous polyester can be appropriately selected according to the purpose, but is preferably 0 ° C to 70 ° C. If the glass transition temperature is less than 0 ° C., it may lead to a decrease in heat-resistant storage stability and a decrease in durability against stress such as stirring in the developing device, and if it exceeds 70 ° C., the low-temperature fixability is deteriorated. There is. The glass transition temperature can be measured by, for example, differential scanning calorimetry (DSC method).
The amorphous polyester preferably has a weight average molecular weight of 5,000 to 30,000, more preferably 7,000 to 20,000.
The molecular structure of the amorphous polyester can be confirmed by GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid.

<Release agent>
There is no restriction | limiting in particular as a mold release agent mix | blended with a toner, Although it can select suitably according to the objective, A low melting-point release agent with a melting | fusing point of 50 to 120 degreeC is preferable. The low melting point release agent, when dispersed together with the binder resin, effectively acts as a release agent at the interface between the fixing roller and the toner. Even if the agent is not applied), the hot offset property is good.

  Suitable release agents include, for example, waxes and waxes. Examples of the waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin and micro wax And natural waxes such as petroleum waxes such as crystallin and petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; poly-n-stearyl methacrylate and poly-n-lauryl which are low molecular weight crystalline polymer resins A homopolymer or copolymer of polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, or the like may be used. These may be used alone or in combination of two or more.

The melting point of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 ° C to 120 ° C, more preferably 60 ° C to 90 ° C. When the melting point is less than 50 ° C., the wax may adversely affect the heat resistant storage stability. When the melting point exceeds 120 ° C., a cold offset tends to occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.
There is no restriction | limiting in particular in content in the toner of a mold release agent, Although it can select suitably according to the objective, 40 weight% or less is preferable and 3 to 30 weight% is more preferable. When the content exceeds 40% by weight, the fluidity of the toner may be deteriorated.

<Colorant>
There is no restriction | limiting in particular as a coloring agent mix | blended with a toner, According to the objective, it can select suitably from well-known dyes and pigments. Examples include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, isoindolinone yellow, bengara, red lead, red lead, cadmium red, cadmium mercurial red, antimony red, permanent red 4R, para red, phise red, parachlor ortho nitroaniline red, risor fast scarlet G Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzigi Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo , Ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese violet, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridiane, emerald green, pigment green B, naphthol green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Oxidized Titanium, zinc white, litbon, etc. are mentioned.
These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular in content in the said toner of a coloring agent, Although it can select suitably according to the objective, 1 to 15 weight% is preferable and 3 to 10 weight% is more preferable. When the content is less than 1% by weight, the coloring power of the toner is decreased. When the content exceeds 15% by weight, poor dispersion of the pigment in the toner occurs, resulting in a decrease in coloring power and a decrease in electrical characteristics of the toner. Sometimes.

  The colorant may be used as a master batch combined with a resin. There is no restriction | limiting in particular as this resin, According to the objective, it can select suitably from well-known things. Examples include polyesters, styrene or substituted polymers thereof, styrene copolymers, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resins, epoxy polyol resins, polyurethanes. , Polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading a masterbatch resin and a colorant with a high shear force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. The so-called flushing method is also preferable in that the wet cake of the colorant can be used as it is and does not need to be dried. This flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

<Other ingredients>
There are no particular limitations on the other components to be blended in the toner, and it can be appropriately selected according to the purpose. Examples thereof include a charge control agent, inorganic fine particles, a fluidity improver, a cleaning property improver, and a magnetic material. .

-Charge control agent-
There is no restriction | limiting in particular as a charge control agent, According to the objective, it can select suitably from well-known things. Examples include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkyls. Examples thereof include amides, phosphorus simple substances or compounds thereof, tungsten simple substances or compounds thereof, fluorine-based activators, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. These may be used individually by 1 type and may use 2 or more types together.

  As the charge control agent, commercially available products may be used. Examples of the commercially available products include bontron 03, a nigrosine dye, bontron P-51, a quaternary ammonium salt, bontron S-34, a metal-containing azo dye, oxy Naphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (both manufactured by Orient Chemical Industries); quaternary ammonium salt molybdenum complex TP-302, TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.); quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (Both manufactured by Hoechst); LRA-901, LR-14 which is a boron complex 7 (manufactured by Nippon Carlit Co., Ltd.); copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

  The content of the charge control agent in the toner differs depending on the kind of the resin, the presence or absence of the additive, the dispersion method, and the like, and cannot be generally specified. 1-10 weight part is preferable and 0.2-5 weight part is more preferable. If the content is less than 0.1 part by weight, the charge controllability may not be obtained. If the content exceeds 10 parts by weight, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced, and development is performed. The electrostatic attraction force with the roller may increase, leading to a decrease in developer fluidity and a decrease in image density.

-Inorganic fine particles-
The inorganic fine particles can be used as an external additive for imparting fluidity, developability, chargeability and the like to the toner particles.
There is no restriction | limiting in particular as an inorganic fine particle, According to the objective, it can select suitably from well-known things. Examples include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide. Cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, more preferably 5 to 500 nm.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by weight, and more preferably 0.01 to 2.0% by weight.

-Fluidity improver-
The fluidity improver increases the hydrophobicity by surface treatment so that the flow characteristics and charging characteristics do not deteriorate even under high humidity. For example, a silane coupling agent, a silylating agent, a fluorinated alkyl group Examples include silane coupling agents having an organic group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. The inorganic fine particles of silica and titanium oxide are particularly preferably subjected to surface treatment with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

-Cleaning improver-
The cleaning property improving agent is added to the toner in order to remove the transferred developer remaining on the photoreceptor or the primary transfer medium. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
-Magnetic material-
There is no restriction | limiting in particular as a magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

  The method for producing the toner of the present invention is not particularly limited, but a method of granulating the toner after preparing an emulsion or dispersion by emulsifying or dispersing a dispersion or dispersion of a toner material in an aqueous medium is preferable. It is preferable to comprise steps (1) to (6).

(1) Dissolution or Dispersion Preparation of Toner Material A dissolution or dispersion is prepared by dissolving or dispersing the toner material in an organic solvent.
As the toner material, a toner material containing at least a binder resin and a release agent and, if necessary, other components such as a colorant and a charge control agent is used. The organic solvent is removed during or after the toner granulation.
The organic solvent is not particularly limited as long as it can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. However, it has a boiling point of less than 150 ° C. in terms of ease of removal. Is preferred. Examples thereof include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Examples thereof include methyl isobutyl ketone, and ester solvents are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular in the usage-amount of an organic solvent, According to the objective, it can select suitably, For example, 40-300 weight part is preferable with respect to 100 weight part of toner materials, 60-140 weight part is more preferable, 80-120 weight part is still more preferable.

(2) Preparation of aqueous medium There is no restriction | limiting in particular as an aqueous medium, It can select suitably from well-known things, For example, water, a solvent miscible with water, these mixtures etc. are mentioned, Especially water Is preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.
For the preparation of the aqueous medium, for example, resin fine particles may be dispersed in the aqueous medium.
There is no restriction | limiting in particular in the addition amount in the aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5 to 10 weight% is preferable.

  The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin. Examples thereof include vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin is preferable in that an aqueous dispersion of fine spherical resin particles can be easily obtained. The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

  Further, as the resin fine particles, a copolymer containing a monomer having at least two unsaturated groups can be used. There is no restriction | limiting in particular as a monomer which has at least 2 unsaturated group, According to the objective, it can select suitably, For example, the sodium salt of a methacrylic acid ethylene oxide adduct sulfate ("Eleminol RS-30"; Sanyo Kasei Kogyo Co., Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles.
Examples of the method for preparing the aqueous dispersion of the resin fine particles include the following (i) to (viii).
(I) In the case of the vinyl resin, the aqueous dispersion of resin fine particles is directly performed by any polymerization reaction selected from a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method using a vinyl monomer as a starting material. (Ii) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., the precursor (monomer, oligomer, etc.) or its solvent solution is aqueous in the presence of a suitable dispersant. A method of producing an aqueous dispersion of resin fine particles by dispersing in a medium and then heating or adding a curing agent (iii) polyaddition or condensation system of the polyester resin, polyurethane resin, epoxy resin, etc. In the case of a resin, an appropriate emulsifier is added to a precursor (monomer, oligomer, etc.) or a solvent solution thereof (preferably a liquid. It may be liquefied by heating). After the dissolution, the method of phase inversion emulsification by adding water (iv) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) A method in which the resin is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles, which are then dispersed in water in the presence of an appropriate dispersant. Resin fine particles by spraying a resin solution prepared by a reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent. (Vi) A method of dispersing the resin fine particles in water in the presence of a suitable dispersant (vi) in advance by any polymerization reaction mode such as a polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization). Prepared by) After adding a poor solvent to the resin solution in which the fat is dissolved in the solvent, or cooling the resin solution previously dissolved in the solvent by heating, the resin fine particles are precipitated, and then the solvent is removed to obtain the resin particles. A method of dispersing the resin particles in water in the presence of a suitable dispersant (vii) A polymerization reaction in advance (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization may be used) (Viii) A method in which a resin solution prepared by dissolving the resin in a solvent in a solvent is dispersed in an aqueous medium in the presence of an appropriate dispersant and then the solvent is removed by heating or decompression, etc. (viii) (Any polymerization reaction mode such as ring polymerization, polyaddition, addition condensation, condensation polymerization, etc. may be used.) A suitable emulsifier is dissolved in a resin solution prepared by dissolving a resin prepared in a solvent, followed by addition of water. Phase emulsification method

In addition, in the aqueous medium, if necessary, from the viewpoint of stabilizing the oil droplets of the dissolved or dispersed liquid during emulsification or dispersion described later, and obtaining a desired shape while sharpening the particle size distribution. It is preferable to use an agent.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a sparingly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned.
These may be used individually by 1 type and may use 2 or more types together. Of these, surfactants are preferred.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, anionic surfactants having a fluoroalkyl group, and those having a fluoroalkyl group are suitable. It is.
Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydro Ciethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like.
Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nippon Ink Chemical Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Neos) and the like.

Examples of the cationic surfactant include amine salt type surfactants, quaternary ammonium salt type cationic surfactants, and cationic surfactants having a fluoroalkyl group.
Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Examples of the cationic surfactant having a fluoroalkyl group include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, and the like. Aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like.
Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M); F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products);

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like.

  Examples of the (meth) acrylic monomer containing a hydroxyl group include acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, and methacrylic acid-β-hydroxypropyl. , Acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxypropyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol mono Examples include methacrylic acid ester, glycerin monoacrylic acid ester, glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide and the like.

Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like.
Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate.
Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds.
Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride.

Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine.
Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester.
Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In the preparation of the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
Further, when a modified polyester (prepolymer) capable of reacting with an active hydrogen group-containing compound is included as the binder resin of the solution or dispersion, for example, dibutyltin laurate, dioctyltin laurate, etc. in the aqueous medium A catalyst in the reaction can also be used.

(3) Emulsification or dispersion To dissolve or disperse the toner material in the aqueous medium, the toner material is preferably dissolved or dispersed in the aqueous medium with stirring.
The dispersion method is not particularly limited, but a batch type emulsifier such as a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), ), TK fill mix, TK pipeline homomixer (manufactured by Koki Kogyo Kogyo Co., Ltd.), colloid mill (manufactured by Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (manufactured by Mitsui Miike Chemical Co., Ltd.), Captron (Eurotech) ), Continuous flow emulsifiers such as Fine Flow Mill (manufactured by Taiheiyo Kiko Co., Ltd.), high-pressure emulsifiers such as microfluidizer (manufactured by Mizuho Kogyo), nanomizer (manufactured by Nanomizer), APV Gaurin (manufactured by Gaurin), Membrane emulsifiers such as membrane emulsifiers (manufactured by Chilling Industries Co., Ltd.), vibratory emulsifiers such as vibratory mixers (manufactured by Chilling Industries Co., Ltd.), ultrasonic homo Naiza (manufactured by Branson) ultrasonic emulsifier, etc. and the like. Among these, it is preferable to use APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fill mix, and TK pipeline homomixer from the viewpoint of uniform particle size.

(4) Removal of solvent The organic solvent is removed from the emulsified slurry obtained by the emulsification or dispersion.
The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed in a dry atmosphere, Examples thereof include a method in which the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation.

(5) Cleaning, drying classification, etc. When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying. When a dispersion stabilizer that is soluble in an acid / alkali such as calcium phosphate is used as the dispersion medium, the dispersion stabilizer is dissolved with an acid such as hydrochloric acid and removed from the toner particles by washing with water. can do.

(6) External Addition of Charge Control Agent / Releasing Agent, etc. In this way, to the obtained toner particles, particles such as a release agent, charge control agent and the like, which are inorganic fine particles such as silica fine particles and titanium oxide fine particles, if necessary. Or by applying a mechanical impact force, it is possible to prevent the particles such as the release agent from detaching from the surface of the toner particles.
As a method of applying the mechanical impact force, for example, a method of applying an impact force to the mixture by a blade rotating at high speed, an appropriate collision between particles or composite particles by introducing the mixture into a high-speed air stream and accelerating the mixture is accelerated. The method of making it collide with a board, etc. are mentioned. As an apparatus used in this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure is lowered, a hybridization system (manufactured by Nara Machinery Co., Ltd.) ), Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

  Various physical properties such as the shape and size of the toner of the present invention are not particularly limited and can be appropriately selected according to the purpose. The volume average particle diameter (Dv) and volume average particle diameter (Dv) are as follows. ) / Number average particle diameter (Dn), penetration, low temperature fixability, offset non-occurrence temperature, and the like.

The volume average particle diameter (Dv) of the toner is preferably 3 to 8 μm, for example. When the thickness is less than 3 μm, in the two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In addition, in the case of a one-component developer, toner filming on the developing roller and toner thinning are likely to occur, and toner fusion to a member such as a blade is likely to occur. On the other hand, when the thickness exceeds 8 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase.
The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner is preferably 1.00 to 1.25. When (Dv / Dn) is less than 1.00, in the case of a two-component developer, the toner is fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier is lowered or the cleaning property is deteriorated. Sometimes. In addition, in the case of a one-component developer, toner filming on the developing roller and toner thinning are likely to cause toner fusion to a member such as a blade. On the other hand, if it exceeds 1.30, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

When (Dv / Dn) is 1.00 to 1.25, the storage stability, low-temperature fixability, and hot offset resistance are all excellent, and the glossiness of an image particularly when used in a full-color copying machine. Excellent. In the two-component developer, even if the toner balance is performed over a long period of time, the toner particle diameter in the developer is little changed, and good and stable developability can be obtained even with long-term stirring in the developing device. In the case of a one-component developer, even if the balance of the toner is performed, fluctuations in the particle diameter of the toner are reduced, and the filming of the toner on the developing roller and the member to the blade or the like for thinning the toner are applied. There is no toner fusion, and good and stable developability can be obtained even during long-term use (stirring) of the developing device, so that a high-quality image can be obtained.
The volume average particle diameter and (Dv / Dn) can be measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter.

For example, the penetration measured by a penetration test (JIS K2235-1991) is preferably 6 mm or more, and more preferably 15 mm or more. If the penetration is less than 6 mm, the heat resistant storage stability may be deteriorated.
The penetration can be measured according to JIS K2235-1991. Specifically, a 50 mL glass container is filled with toner and left in a thermostatic bath at 50 ° C. for 20 hours. The penetration can be measured by cooling the toner to room temperature and performing a penetration test. In addition, it has shown that heat resistance preservability is excellent, so that the said penetration value is large.

As the low temperature fixability, from the viewpoint of achieving both a reduction in the fixing temperature and the occurrence of no offset, it is preferable that the lower limit temperature for fixing is lower, and more preferable that the temperature at which no offset is generated is higher. As a temperature range in which both can be achieved, the lower limit fixing temperature is less than 130 ° C., and the non-offset temperature is 180 ° C. or more.
The minimum fixing temperature here is, for example, an image forming apparatus, a transfer paper is set, a copy test is performed, and the remaining ratio of the image density after rubbing the obtained fixed image with a pad is 70% or more. Is the fixing roll temperature.
Further, the non-offset temperature is set by, for example, using an image forming apparatus, setting a transfer sheet, and each color of yellow, magenta, cyan, and black, and solid images of red, blue, and green in each color as intermediate colors. It can be determined by adjusting so that it is developed, adjusting the temperature of the fixing belt to be variable, and measuring the temperature at which no offset occurs.

  The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.

[Developer]
The developer of the present invention contains at least the toner of the present invention and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like corresponding to an improvement in information processing speed in recent years, the two-component developer is used in terms of improving the service life. preferable.
In the case of the one-component developer using the toner of the present invention, even if the toner is balanced, there is little fluctuation in the toner particle diameter, and the filming of the toner on the developing roller and the blade for thinning the toner The toner is not fused to a member such as the above, and good and stable developability and an image can be obtained even in the long-term use (stirring) of the developing device. Further, in the case of the two-component developer using the toner of the present invention, even if the toner balance is performed over a long period of time, the fluctuation of the toner particle diameter in the developer is small, and the long-term agitation in the developing device is good. And stable developability can be obtained.

There is no restriction | limiting in particular in the said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular in the material of the said core material, It can select suitably from well-known things. For example, 50-90 emu / g manganese-strontium (Mn-Sr) -based material, manganese-magnesium (Mn-Mg) -based material and the like are preferable, and in terms of ensuring image density, iron powder (100 emu / g or more), A highly magnetized material such as magnetite (75 to 120 emu / g) is preferred. In addition, weak magnetization such as copper-zinc (Cu-Zn) (30 to 80 emu / g) is advantageous in that it can weaken the hitting of the photoconductor in which the toner is in a spiked state, and is advantageous for high image quality. Material is preferred. These may be used individually by 1 type and may use 2 or more types together.
The core material has a volume average particle size (D50) of preferably 10 to 150 μm, more preferably 20 to 80 μm. When the volume average particle size is less than 10 μm, the fine particle system increases in the distribution of carrier particles, and the magnetization per particle may be lowered to cause carrier scattering. When the volume average particle size exceeds 150 μm, the specific surface area decreases, and Spattering may occur, and in the case of a full color with many solid parts, reproduction of the solid parts may be particularly poor.

  There is no restriction | limiting in particular in the material of the said resin layer, According to the objective, it can select suitably from well-known resin. Examples include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyester resins, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, poly Hexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, terpolymer of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomer And fluoroterpolymers such as silicone resins. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, polyacrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene-acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
For example, the resin layer is prepared by dissolving the resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. Can be formed. Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular in the said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited and may be an external heating method or an internal heating method, for example, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, a method using a microwave, or the like. Is mentioned.

The proportion of the resin layer in the carrier is preferably 0.01 to 5.0% by weight. If the ratio is less than 0.01% by weight, a uniform resin layer may not be formed on the surface of the core material. If the ratio exceeds 5.0% by weight, the resin layer becomes too thick and granulation of carriers occurs. , Uniform carrier particles may not be obtained.
When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected according to the purpose. For example, 90 to 98% by weight is preferable, and 93 -97 wt% is more preferred.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the examples, “part” means “part by weight”.

[Methods for measuring physical properties of components used in Examples and Comparative Examples]
<Measurement of molecular weight>
Apparatus: GPC (manufactured by Tosoh Corporation), detector: RI, measurement temperature: 40 ° C.
-Mobile phase: tetrahydrofuran, flow rate: 0.35 mL / min.
The molecular weight Mn and the molecular weight Mw are a number average molecular weight and a weight average molecular weight measured by GPC (gel permeation chromatography) using a calibration curve prepared from a polystyrene sample having a known molecular weight as a standard.

<Measurement of glass transition temperature (Tg)>
A DSC (TA Instruments, Q2000) was used as a measuring device, and 5 to 10 mg of a sample filled in an aluminum simple hermetic pan was subjected to the following measurement flow.
1st Heating: 30 ° C. to 220 ° C., 5 ° C./min. Hold for 1 minute after reaching 220 ° C. Cooling: Quench to -60 ° C. without temperature control, hold for 1 minute after reaching -60 ° C. 2nd Heating: −60 ° C. to 180 ° C., 5 ° C./min.
The glass transition temperature (Tg) was evaluated by determining the glass transition temperature at the midpoint in the 2nd Heating thermogram based on the method described in ASTM D3418 / 82. The melting point (Tm) was the peak top temperature of the endothermic peak.

<Synthesis of polylactic acid resin 1>
L-lactide and D-lactide were charged into a 2 L four-necked flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple at the ratios shown in Table 1 below, and dried under reduced pressure at 60 ° C. for 2 hours. Next, ethylene glycol was added in an amount of 0.63% by weight with respect to the charged amount of lactide and 200 ppm of tin 2-ethylhexanoate was added and polymerized at 190 ° C. for 2 hours in a nitrogen stream, and then decompressed at 170 ° C. for 1 hour. The monomer was distilled off to obtain polylactic acid resin 1.

<Synthesis of polylactic acid resins 2-8>
Polylactic acid resins 2 to 8 were obtained in the same manner as the synthesis of polylactic acid resin 1 except that the ratios of L-lactide and D-lactide were changed as shown in Table 1 below.

<Synthesis of Copolymer 1>
Into a 1 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,6-hexanediol as a diol, sebacic acid as a dicarboxylic acid, and OH / COOH = 1.15 were charged. 300 ppm of titanium tetraisopropoxide was added, the reaction was allowed to flow out under a nitrogen stream, and the reaction was continued until the temperature was raised to 230 ° C. and the resin acid value was 5 or less. Thereafter, the reaction was carried out at a vacuum degree of 10 mmHg or less for 2 hours to obtain aliphatic crystalline polyester 1. The obtained resin had an acid value of 0.42 mgKOH / g, a hydroxyl value of 35.8 mgKOH / g, and Tm of 67.2 ° C.
Next, the aliphatic crystalline polyester 1, L-lactide, and D-lactide were charged into a 2 L four-necked flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple at the ratios shown in Table 1 below. And dried under reduced pressure at 60 ° C. for 2 hours. Next, 200 ppm of tin 2-ethylhexanoate was added, the mixture was polymerized at 190 ° C. for 2 hours under a nitrogen stream, and then the pressure was reduced at 170 ° C. for 1 hour to distill off the monomer, whereby a copolymer 1 was obtained.

<Synthesis of Copolymer 2>
In a 1 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, propylene glycol as a diol, dimethyl terephthalate and dimethyl adipate as dicarboxylic acids in a molar ratio of 90/10, OH / COOH = Charge to 1.2, add 300 ppm of titanium tetraisopropoxide, react with methanol flowing out under a nitrogen stream, and finally raise the temperature to 230 ° C. until the resin acid value becomes 5 or less Reacted. Then, it was made to react at 20-30 mmHg pressure reduction for 2 hours, and the amorphous polyester 1 was obtained. The acid value of this resin was 0.5 mgKOH / g, the hydroxyl value was 23.3 mgKOH / g, and Tg was 59.2 ° C.
Next, the amorphous polyester 1, L-lactide, and D-lactide were introduced into the 2 L four-necked flask equipped with a nitrogen inlet tube, a stirrer, and a thermocouple at the ratios shown in Table 1 below. And dried under reduced pressure at 60 ° C. for 2 hours. Next, 200 ppm of tin 2-ethylhexanoate was added, and the mixture was polymerized at 190 ° C. for 2 hours under a nitrogen stream, and then the pressure was reduced at 170 ° C. for 1 hour to distill off the monomer, whereby Copolymer 2 was obtained.

なお、表中の光学純度Ｘ以外の数値は重量％である。

The numerical values other than the optical purity X in the table are weight percent.

<Preparation of resin composite 1>
20 parts of N, N′-di-2,6-diisopropylphenylcarbodiimide and 1580 parts of [polylactic acid resin 1] were kneaded at 150 ° C. for 30 minutes by two rolls, and then cooled by cooling, and a pulverizer (manufactured by Hosokawa Micron Co., Ltd.). ) To obtain [Resin Composite 1].

<Preparation of resin composite 2>
[Preparation of Resin Composite 1] except that 1580 parts of [Polylactic acid resin 1] is 1560 parts of [Polylactic acid resin 2] and 40 parts of N, N′-di-2,6-diisopropylphenylcarbodiimide are used. ] [Resin composite 2] was obtained in the same manner.

<Preparation of resin composite 3>
Except that the number of parts of [polylactic acid resin 2] was 1540 parts and the number of parts of N, N′-di-2,6-diisopropylphenylcarbodiimide was 60 parts, the same as [Preparation of resin composite 2], [Resin composite 3] was obtained.

<Preparation of resin composite 4>
Except that the number of parts of [Polylactic acid resin 2] is 1520 parts and the number of parts of N, N′-di-2,6-diisopropylphenylcarbodiimide is 80 parts, [Resin composite 4] was obtained.

<Preparation of resin composite 5>
Except that the number of parts of [Polylactic acid resin 2] was 1590 parts and the number of parts of N, N′-di-2,6-diisopropylphenylcarbodiimide was 90 parts, [Resin composite 5] was obtained.

<Preparation of resin composite 6>
[Polylactic acid resin 2] was the same as [Preparation of resin composite 2] except that the number of parts was changed to 1595 parts and the number of parts of N, N'-di-2,6-diisopropylphenylcarbodiimide was changed to 95 parts. [Resin composite 6] was obtained.

<Preparation of resin composite 7>
[Resin composite 7] was obtained in the same manner as [Preparation of resin composite 2] except that [Polylactic acid resin 2] was changed to [Polylactic acid resin 3].

<Preparation of resin composite 8>
[Resin composite 8] was obtained in the same manner as [Preparation of resin composite 2] except that [polylactic acid resin 2] was changed to [polylactic acid resin 4].

<Preparation of resin composite 9>
[Resin composite 9] was obtained in the same manner as [Preparation of resin composite 2] except that [Polylactic acid resin 2] was changed to [Polylactic acid resin 6].

<Preparation of resin composite 10>
[Resin composite 10] was obtained in the same manner as [Preparation of resin composite 2] except that [Polylactic acid resin 2] was changed to [Polylactic acid resin 7].

<Preparation of resin composite 11>
[Resin composite 11] was obtained in the same manner as [Preparation of resin composite 2] except that [Polylactic acid resin 2] was changed to [Polylactic acid resin 8].

<Preparation of resin composite 12>
[Resin composite 12] was obtained in the same manner as [Preparation of resin composite 2] except that [Polylactic acid resin 2] was changed to [Copolymer 1].

<Preparation of resin composite 13>
[Resin composite 13] was obtained in the same manner as [Preparation of resin composite 2] except that [Polylactic acid resin 2] was changed to [Copolymer 2].

<Preparation of resin composite 14>
[Resin composite 14] is obtained in the same manner as in [Preparation of resin composite 2] except that N, N'-di-2,6-diisopropylphenylcarbodiimide is changed to N, N'-diisopropylcarbodiimide. It was.

<Preparation of resin composite 15>
Except that the number of parts of [polylactic acid resin 2] is 1500 parts and the number of parts of N, N′-di-2,6-diisopropylphenylcarbodiimide is 100 parts, the same as [Preparation of resin composite 2], [Resin composite 15] was obtained.

<Preparation of resin composite 16>
Except that the number of parts of [Polylactic acid resin 2] was 1600 parts and the number of parts of N, N′-di-2,6-diisopropylphenylcarbodiimide was 0 parts, the same as [Preparation of resin composite 2], [Resin composite 16] was obtained.

<Preparation of resin composite 17>
[Resin composite 17] was obtained in the same manner as [Preparation of resin composite 2] except that [polylactic acid resin 2] was changed to [polylactic acid resin 5].

<Preparation of resin composite 18>
[Resin composite 18] [Resin composite 18] in the same manner as [Preparation of resin composite 2] except that N, N'-di-2,6-diisopropylphenylcarbodiimide was replaced with LA-1 (Nisshinbo Chemical Co., Ltd .; polycarbodiimide). ] Was obtained.

<Example 1> (Preparation of toner 1)
~ Preparation of styrene / acrylic resin fine particles ~
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 16 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid Then, 110 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, whereby a white emulsion was obtained. The mixture was further heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to form a vinyl resin (a copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate). An aqueous dispersion [styrene / acrylic resin fine particle dispersion] was obtained. [Styrene / acrylic resin fine particle dispersion] had a volume average particle size (measured with LA-920, manufactured by Horiba, Ltd.) of 14 nm, an acid value of 45 mgKOH / g, a molecular weight Mw of 300,000, and a Tg of 60 ° C.

-Preparation of acrylic resin fine particles a-
In a reaction vessel equipped with a stir bar and thermometer, 683 parts of water, 10 parts of distearyldimethylammonium chloride (cation DS, manufactured by Kao Corporation), 176 parts of methyl methacrylate, 18 parts of butyl acrylate, 1 part of ammonium persulfate, ethylene When 2 parts of glycol dimethacrylate was added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was further heated to raise the system temperature to 65 ° C. and reacted for 10 hours. Subsequently, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to obtain an aqueous dispersion (acrylic resin fine particle dispersion a) of a vinyl resin (methyl methacrylate). [Acrylic resin fine particles a] had a volume average particle size (measured with LA-920 manufactured by Horiba, Ltd.) of 35 nm, an acid value of 2 mgKOH / g, a molecular weight Mw of 30,000, and a Tg of 82 ° C.

-Preparation of aqueous medium phase-
660 parts of water, 25 parts of the above-mentioned [styrene / acrylic resin fine particle dispersion], 25 parts of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and ethyl acetate 60 Then, 50 parts of [acrylic resin fine particle dispersion a] was added to obtain a milky white liquid [aqueous phase 1].

-Preparation of master batch-
Using Henschel mixer (Mitsui Mining Co., Ltd.), 1,000 parts of water, 530 parts of carbon black (Printex35, manufactured by Degussa) 530 parts of DBP oil absorption 42 mL / 100 g, and 1200 parts of polylactic acid resin 2 And mixed.
The resulting mixture was kneaded at 150 ° C. for 30 minutes using a two-roll, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to obtain a master batch.

-Production of Toner 1-
In a reaction vessel, 100 parts of [Resin Complex 1] and 100 parts of ethyl acetate were added and stirred to prepare Resin Solution 1.
Next, 5 parts of carnauba wax (molecular weight 1,800, acid value 2.7 mgKOH / g, penetration 1.7 mm (40 ° C.)) and 5 parts of master batch were charged into resin solution 1, and Ultravisco in a bead mill. Using a mill (manufactured by Imex Co., Ltd.), a toner material liquid is obtained by performing 3 passes under a condition in which 80% by volume of zirconia beads having a particle diameter of 0.5 mm is filled at a liquid feeding speed of 1 kg / hour, a disk peripheral speed of 6 m / second. It was.
Next, 150 parts of [Aqueous Phase 1] is put in a container, and 100 parts of toner material liquid is added while stirring at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Emulsified slurry was obtained by mixing for a minute.
Furthermore, 100 parts of the emulsified slurry was charged in a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 10 hours while stirring at a stirring peripheral speed of 20 m / min to obtain a dispersed slurry.
Next, 100 parts of the dispersion slurry was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the obtained filter cake, and the mixture was mixed for 10 minutes at 12,000 rpm using a TK homomixer, followed by filtration.

To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice.
To the obtained filter cake, 20 parts of a 10 wt% aqueous sodium hydroxide solution was added, mixed at 12,000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure.
To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed at 12,000 rpm for 10 minutes using a TK homomixer, and then filtered.
To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice.
After adding 20 parts of 10 wt% hydrochloric acid to the obtained filter cake and mixing for 10 minutes at 12,000 rpm using a TK type homomixer, a fluorinated quaternary ammonium salt compound: Fluorent F-310 (Neos Was added with a 5% methanol solution so that the fluorine-based quaternary ammonium salt was equivalent to 0.1 part with respect to 100 parts of the solid content of the toner, stirred for 10 minutes, and then filtered.
To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice to obtain a filter cake.
The obtained filter cake was dried at 40 ° C. for 36 hours using a circulating drier, and sieved with a mesh having an opening of 75 μm to obtain toner mother particles 1.
Next, 1.5 parts of hydrophobic silica (Cabot TS720) was added to 100 parts of toner base particles 1, and blended with a Henschel mixer at 3000 rpm for 5 minutes to obtain toner 1.

Examples 2 to 14 (Production of Toners 2 to 14)
Toner 2 of Examples 2 to 14 was prepared in the same manner as in Example 1 except that [Resin composite 1] in Example 1 was changed to [Resin composite 2] to [Resin composite 14]. 14 was obtained.

<Comparative Examples 1-4> (Production of Toners 15-18)
Toners 15 of Comparative Examples 1 to 4 are the same as Example 1 except that [Resin Composite 1] in Example 1 is changed to [Resin Composite 15] to [Resin Composite 18]. 18 was obtained.

-Fabrication of carrier-
To 100 parts of toluene, 100 parts of a silicone resin (SR2411 manufactured by Toray Dow Corning Silicone Co., Ltd.), 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black are added, and 20 parts are added with a homomixer. A coating layer forming solution was prepared by dispersing for a minute. The coating layer forming liquid was coated on the surface of 1,000 parts of spherical magnetite having a particle diameter of 50 μm using a fluid bed type coating apparatus to prepare a magnetic carrier.

  For each of the toners of Examples and Comparative Examples, (a) heat-resistant storage stability, (b) fixability, (c) charge after storage at high temperature and high humidity, and (d) pigment dispersibility were measured. The results are shown in Table 2.

(A) Heat-resistant storage stability (Penetration)
Each toner was filled in a 50 mL glass container and left in a constant temperature bath at 50 ° C. for 24 hours. Next, the toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K2235-1991) and evaluated based on the following criteria. In addition, heat resistance preservability is so excellent that the penetration value is large, and when it is less than 5 mm, there is a high possibility of problems in use.
〔Evaluation criteria〕
○: Needle penetration 15 mm or more △: Needle penetration 5 mm or more and less than 15 mm ×: Needle penetration less than 5 mm

(B) Fixability 5 parts of each toner and 95 parts of the carrier were mixed by a ball mill to prepare the two-component developers of Examples 1 to 11 and Comparative Examples 1 to 4. Using these developers and using a device in which the fixing unit of the Ricoh Copier MF-200 using a Teflon (registered trademark) roller as a fixing roller is modified, plain paper and cardboard transfer paper (manufactured by Ricoh) A solid image was printed with a toner adhesion amount of 0.85 ± 0.1 mg / cm ^{2 on} type 6200 and a copy printing paper <135> manufactured by NBS Ricoh Company, and the fixability was evaluated. The fixing test was conducted by changing the temperature of the fixing belt, and the upper limit temperature at which hot offset did not occur on plain paper was defined as the upper limit temperature for fixing. Further, the minimum fixing temperature was measured with a thick paper. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.
〔Evaluation criteria〕
○: Very good fixability △: Good fixability ×: Poor fixability

(C) Charge amount after high-temperature and high-humidity storage (1) Charge charged by stirring for 15 seconds Each toner after being filled in a 50 mL glass container and left in a constant temperature and humidity chamber adjusted to 40 ° C. and 70% RH for 7 days 10 g of ferrite carrier and 100 g of ferrite carrier are placed in a stainless steel pot up to 30% of the internal volume in an environment with a temperature of 28 ° C. and a humidity of 80%, stirred for 15 seconds at a stirring speed of 100 rpm, and the developer charge (μC / g ) Was measured with a blow-off device [Toshiba Chemical Co., Ltd .: TB-200].
(2) Charge amount for 60 seconds stirring Charge amount when stirring for 60 seconds was measured in the same manner as in (1).

(D) Pigment dispersibility After embedding the toner in a 30 minute curing type two-component mixed epoxy resin and curing it for 24 hours, the thickness of the epoxy resin embedding the toner using an ultra microtome is about 0.5 μm. After cutting, the cross section of the toner was observed with an optical microscope, and the pigment dispersion state inside the toner was evaluated according to the following criteria.
〔Evaluation criteria〕
○: Pigment particles are uniformly dispersed inside the toner.
Δ: Some pigments are unevenly distributed in the vicinity of the toner surface.
There is no.
×: Most pigments are unevenly distributed in the vicinity of the toner surface, causing a practical problem
It is.

JP-A-4-179967 Japanese Patent No. 2597452 JP 2006-91278 A JP 2006-285150 A

Claims (7)

A toner containing at least a binder resin and a release agent, wherein the binder resin includes a polyester resin having a structural unit in which at least lactic acid is dehydrated and condensed, and the following formula in the structural unit in which the lactic acid is dehydrated and condensed: The toner is characterized in that the optical purity X (%) in terms of monomer component is 80% or less, and further contains a monocarbodiimide compound in an amount of 0.1 to 5% by weight based on the toner weight.
Optical purity X (%) = | X (L form) -X (D form) |
[However, X (L form) represents the L form ratio (%) in terms of lactic acid monomer, and X (D form) represents the D form ratio (%) in terms of lactic acid monomer. ]   The toner according to claim 1, wherein the monocarbodiimide compound has an aromatic ring.   The toner according to claim 1, wherein the polyester resin includes an aliphatic crystalline polyester segment.   The toner according to claim 1, wherein the polyester resin includes an amorphous polyester segment.   A developer comprising the toner according to claim 1.   An electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, exposure means for exposing the charged surface of the electrostatic latent image carrier to form an electrostatic latent image, and A developing unit that develops the electrostatic latent image with toner to form a visible image, a transfer unit that transfers the visible image to a recording medium, and a fixing that fixes the transferred image transferred to the recording medium An image forming apparatus having at least means, wherein the toner is the toner according to claim 1.   The image forming apparatus main body includes at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A process cartridge that is detachable, wherein the toner is the toner according to claim 1.