JP2012078671A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which has excellent fixed image quality with respect to a fixing process at a high process speed, can suppress inside contamination even if the toner is frequently used, and can maintain excellent image quality for a long period of time.SOLUTION: In the toner having toner particles containing a binder resin, an amide wax and a colorant, when a component obtained by heating the amide wax at 200°C for 10 minutes and desorbing the heated amide wax with a heating and desorbing device is subjected to GC/MS analysis, the total amount (A) of the volatile component detected after a time when a peak of hydrocarbon having a carbon number of 16 is detected is 2,000 ppm or less (in terms of hexadecane), and the peak molecular weight of the amide wax measured by gel permeation chromatography is 3.5×10or more and 1.5×10or less.

Description

  The present invention relates to a toner used in a recording method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method, or a toner jet method.

  In recent years, an image forming apparatus such as a printer has (1) high definition, high image quality, (2) energy saving more than ever, (3) high speed, and (4) low running cost. It is rare. Along with this, the properties required for toners are becoming higher and more diverse, and developments are being made from various viewpoints. From the viewpoint of energy saving, it is desired to develop a toner that can be easily fixed on a transfer material such as paper at a low temperature. At the same time, as the resolution of the image is improved, it is required to control the glossiness of the image in order to approximate the image quality of a photograph or printing. Furthermore, in the case of a color machine, good color mixing and a wide range of color reproducibility are required.

  In Patent Document 1, in order to control the properties of the binder resin and the wax, by using a specific resin physical property and a specific wax, the releasability at the time of fixing of the low energy fixing toner is excellent, and an offset phenomenon is caused. A suppressed toner is disclosed. However, when the image formation is repeatedly performed using the toner described in Patent Document 1, a new problem has arisen that in-machine contamination of the image forming apparatus occurs due to the release agent contained in the toner. This was a particularly prominent tendency during high-speed image formation.

  Therefore, Patent Document 2 discloses a toner in which heat roller contamination does not occur during long-term use even in an apparatus having no heat roller cleaning mechanism by using three or more kinds of specific waxes in combination. In Patent Document 3, in the image forming method for flash fixing, the physical properties of the polyolefin wax of the black toner are specified, thereby preventing contamination of the flash lamp and the deodorizing filter due to volatilization / sublimation of low molecular weight components such as wax. Toner is disclosed.

JP 2000-330332 A JP 2001-249486 A JP 2006-078689 A

  However, although the toner described in Patent Document 2 can suppress contamination of the heat roller, it is not always sufficient with respect to in-machine contamination of the fixing member peripheral member. The image forming method described in Patent Document 3 is an invention limited to a specific image forming method. For example, a pressure heating method using a heat roller or a heat fixing method in which a pressure member is closely attached to a heating body via a film. However, a sufficient improvement effect is not obtained.

  The problem to be solved by the present invention is a toner that exhibits good fixing characteristics while suppressing in-machine contamination even during high-speed image formation, and that can stably obtain a uniform image with no uneven color density over a long period of time. Is to provide.

The present invention relates to a toner having toner particles containing a binder resin, an amide wax, and a colorant, and the amide wax is heated with a heat desorption apparatus at 200 ° C. for 10 minutes. The total amount (A) of volatile components detected after the peak detection time of the hydrocarbon having 16 carbon atoms is 2000 ppm or less (in terms of hexadecane), and the peak molecular weight of the amide wax measured by gel permeation chromatography is 3. The present invention relates to a toner that is 5 × 10 ² or more and 1.5 × 10 ³ or less.

  According to the present invention, it is possible to obtain a toner that exhibits good fixability in a copying machine or printer having a high process speed, suppresses internal contamination even in repeated use, and can provide a stable image over a long period of time.

  The present inventors have intensively studied in-machine contamination that causes image defects when an image is formed with a copying machine or a printer using toner containing an amide wax. As a result, it was found that there is a high correlation between the amount of volatile components having a high boiling point of the amide wax contained in the toner particles and the in-machine contamination state. Furthermore, by examining in detail the relationship between the composition ratio of volatile components and the deposition state of pollutants and the mechanism of occurrence of contamination under fixing process conditions, an amide wax that was extremely effective for the antifouling effect was found. Hereinafter, the action of amide wax and the mechanism of occurrence of internal contamination will be described, and then the toner of the present invention will be described in detail.

  When toner containing wax is used for image formation, when heat is supplied in the fixing process, the wax component melts at an appropriate temperature and can move through the binder resin as the viscosity decreases. Plasticization is promoted. Further, when the toner is melted, the fixing property of the toner is improved by the releasing effect and the releasing effect of the wax, and offset and contamination of the toner to the fixing member are prevented. In a fixing process having a high process speed, since the toner needs to be melted instantaneously in the fixing nip, an excessive amount of heat is often applied to the toner in order to set the fixing temperature high. According to the study by the present inventors, it has been found that when continuous printing is continued with an excessive amount of heat applied to the toner, the concentration of the high-boiling volatile component derived from the amide wax increases in the image forming apparatus. When the high boiling point volatile components come into contact with the components inside the machine, the high boiling point volatile components are instantly cooled and deposited, and these deposits cause internal contamination. As the in-flight contamination progresses, the sensitivity of various control sensors decreases, and further the capability of functional members decreases. As a result, the image quality gradually decreases, necessitating maintenance and member replacement, and the durable life of the machine is shortened.

  Since amide wax generally has polarity, it has high compatibility with styrene-acrylic resins and polyester resins mainly used as a binder resin for toner, and plasticizes the resin. Therefore, it is superior in fixability for a high-speed process machine that requires low-temperature fixing. Further, since amide wax is composed of carboxylic acid and amine having a certain distribution in carbon number, it has a distribution of volatile components peculiar to amide wax during heating in the fixing process. Therefore, the high boiling point volatile component that can be generated in the fixing process has a carbon number distribution unique to the wax. Since the toner of the present invention contains an amide wax having a specific volatile component amount and molecular weight controlled, it is possible to suppress in-machine contamination without deteriorating the fixing quality for long-term use in a high-speed process.

  As a result of detailed analysis of in-machine contaminating components derived from amide wax, the present inventors heated amide wax at 200 ° C. for 10 minutes with a heat desorption apparatus, and a peak when GC / MS analysis of the desorbed component was performed. It was found that there was a very high correlation between the pattern and the degree of in-flight contamination. The reason for setting the heating condition of 10 minutes at 200 ° C. in the above analysis is that such a heating condition is considered to be an approximate condition for the generation state of high boiling point volatile components in the image forming apparatus. It is.

  From the above examination, in order to prevent in-machine contamination, it is necessary that the total amount of high boiling point volatile components of the amide wax contained in the toner particles is small. Accordingly, the amide wax contained in the toner of the present invention is detected after the peak detection time of hydrocarbons having 16 carbon atoms in the GC / MS analysis of the desorbed components after heating at 200 ° C. for 10 minutes with a heat desorption apparatus. The total amount (A) of volatile components is 2000 ppm or less (hexadecane conversion).

  Since components corresponding to hydrocarbons having 16 or more carbon atoms precipitate as particles and contaminate the inside of the machine, the total amount (A) is a ratio of the total amount of high boiling point volatile components that are present in the amide wax and cause contamination in the machine. Represents. By setting the total amount (A) to 2000 ppm or less, the amount of high-boiling volatile components generated from the wax decreases, so that the amount of adhesion to the member can be suppressed. The total amount (A) is more preferably 1500 ppm or less.

  Further, the amide wax contained in the toner of the present invention is detected after the detection time of hydrocarbon having 30 carbon atoms in the GC / MS analysis of the desorbed component after heating at 200 ° C. for 10 minutes with a heat desorption apparatus. The relationship between the total amount of volatile components (B) and the total amount of volatile components detected after the detection time of hydrocarbons having 20 carbon atoms and before the detection time of hydrocarbons having 30 carbon atoms (C) , (B) / (C) ≧ 8.0 is preferable. Further, the total amount (C) is more preferably 100 ppm or less.

  Volatile components detected after the detection time of hydrocarbons having 30 carbon atoms have a relatively high boiling point among volatile components detected after the detection time of hydrocarbons having 16 carbon atoms. Therefore, in an actual fixing process, the component is relatively less volatile, and contributes less to in-machine contamination than a component having a low boiling point. On the other hand, in the analysis, the volatile components detected after the detection time of hydrocarbons having 20 carbon atoms and before the detection time of hydrocarbons having 29 carbon atoms are volatile components detected after the detection time of hydrocarbons having 16 carbon atoms. It has a medium boiling point among the components. The volatile component having a medium boiling point is relatively easy to deposit due to volatilization and cooling in an actual fixing process, and greatly contributes to in-machine contamination. Therefore, by satisfying the above relational expression that increases the number of high-boiling volatile components and decreases the medium-boiling volatile components, the generation amount and adhesion of volatile components generated in the actual fixing process can be suppressed, and long-term The inventors consider that the effect of suppressing the deposition of various pollutants increases.

  Furthermore, the amide wax contained in the toner of the present invention is heated at 200 ° C. for 10 minutes with a heat desorption apparatus, and the peak volatile component amount (D) detected as the maximum peak in the GC / MS analysis of the desorbed component. And the total amount (A) are preferably (D) / (A) ≧ 0.85. When (D) / (A) satisfies the above relationship, among the volatile components contributing to in-flight pollution, the amount of the component having a specific carbon number is high in the total amount of volatile components. Become. That is, it becomes close to a state in which volatile components contributing to in-flight contamination are composed of a single component. As a result, the adhesiveness of the deposited in-machine contaminant is lowered, and deterioration of the in-machine pollution is suppressed. On the other hand, if the value of (D) / (A) is low, the crystallinity of the deposited in-machine contaminant is low and the adhesiveness is increased, so that the in-machine contaminant is fused to the member.

  The GC / MS analysis by the heat desorption apparatus of amide wax was performed by the following method.

<Measurement of volatile component concentration of amide wax using heat desorption apparatus>
The volatile component concentration of the amide wax in the present invention is measured by the following method. The following measuring devices are used as measuring devices.

Thermal desorption device: TurboMatrixATD (manufactured by PerkinElmer)
GC / MS: TRACE DSQ (manufactured by Thermo Fisher Scientific)
(Production of glass tube with internal standard)
A glass tube for a heat desorption apparatus in which 10 mg of TenaxTA adsorbent is sandwiched between glass wools in advance is prepared, and a glass tube that has been conditioned at 300 ° C. for 3 hours in a state of flowing an inert atmosphere gas is prepared. Thereafter, 5 μL of a 100 ppm methanol solution of deuterated hexadecane (hexadecane D34) is adsorbed on TenaxTA to obtain a glass tube containing an internal standard.

(Measurement of amide wax)
About 1 mg of amide wax is wrapped in aluminum foil previously baked out at 300 ° C., and put in a special tube prepared in (Preparation of glass tube with internal standard). The sample is covered with a Teflon (registered trademark) cap for a heat desorption apparatus and set in the apparatus. This sample is measured under the following conditions, and the total peak area of the internal standard peak and the peak after deuterated hexadecane excluding the internal standard peak is calculated.

(Heat desorption equipment conditions)
Tube temperature: 200 ° C
Transfer temperature: 300 ° C
Valve temperature: 300 ° C
Column pressure: 150 kPa
Inlet split: 25 ml / min.
Outlet split: 10 ml / min.
Secondary adsorption tube material: TenaxTA
Holding time: 10 min.
Secondary adsorption tube temperature during desorption: -30 ° C
Secondary adsorption tube desorption temperature: 300 ° C
(GC / MS conditions)
Column: Ultra alloy (metal column) UT-5 (inner diameter 0.25 mm, liquid phase 0.25 μm, length 30 m)
Column heating conditions: 60 ° C. (3 min), 350 ° C. (20.0 ° C./min), 350 ° C. (10 min)
The transfer line of the heat desorption apparatus and the GC column are directly connected, and the GC inlet is not used.

(analysis)
Integrate all peaks after the retention time of deuterated hexadecane (excluding deuterated hexadecane peaks) among the peaks obtained by the above operation, and calculate the total value of all peaks. From this, the volatile component concentration of the amide wax is calculated. At this time, care should be taken not to add a noise peak or the like different from the peak to the integrated value.
Amide wax volatile component concentration (ppm)
= (A1 / B1 × 0.0005 × 0.77) / C1 × 1000000
A1: Total peak area after deuterated hexadecane (excluding deuterated hexadecane peaks) (excluding deuterated hexadecane peaks)
B1: Peak area of deuterated hexadecane (internal standard) C1: Weight of amide wax weighed (mg)
The value obtained by the above method is defined as the total amount (A) of volatile components detected after the peak detection time of hydrocarbons having 16 carbon atoms.

  The total amount (B) of the volatile components detected after the detection time of the hydrocarbon having 30 carbon atoms is detected after the detection time of the hydrocarbon having 30 carbon atoms identified by GC / MS analysis. A total value A2 obtained by integrating all the peaks is calculated, and A1 in the above equation is changed to A2 to obtain the value. In addition, the detection time of the hydrocarbon having 30 carbon atoms is obtained by interpolating or extrapolating the retention time using a hydrocarbon standard material (triacontane) having 30 carbon atoms in advance.

  The total amount of volatile components (C) detected after the detection time of hydrocarbons having 20 carbon atoms and before the detection time of hydrocarbons having 30 carbon atoms is the number of carbon atoms after the detection peak of hydrocarbons having 20 carbon atoms. It is a value obtained by calculating a total value A3 obtained by integrating all peaks before 30 detection peaks and changing A1 in the above equation to A3. In addition, the detection time of the hydrocarbon having 20 carbon atoms is obtained by interpolating or extrapolating the retention time using a hydrocarbon standard material (icosane) having 20 carbon atoms in advance.

  Furthermore, in the peak of the volatile component derived from the amide wax detected in the above analysis, the peak having the maximum integrated value is defined as the maximum peak. The integrated value of the maximum peak is A4, and the value obtained by changing A1 in the above equation to A4 is defined as the maximum peak volatile component concentration (D).

The amide wax contained in the toner of the present invention has a peak molecular weight of 3.5 × 10 ² or more and 1.5 × 10 ³ or less in gel permeation chromatography (GPC). When the peak molecular weight of the amide wax is 3.5 × 10 ² or more, generation of a high-boiling volatile component derived from the amide wax component inside the machine is suppressed, and the durability life can be extended. In addition, when the peak molecular weight of the amide wax is 1.5 × 10 ³ or less, a good release effect can be exhibited even in a fixing process with a high process speed, and a uniform image without unevenness in color density can be obtained. .

  The melting point of the amide wax contained in the toner of the present invention is preferably 50 ° C. to 150 ° C., and more preferably 60 ° C. to 100 ° C. A melting point of 50 ° C. or higher is preferable because the toner has good blocking resistance. When the melting point is 150 ° C. or lower, it is possible to uniformly mix with the binder resin with less energy in the toner production method by the pulverization method, while in the toner production method by the polymerization method, a high-boiling solvent or a pressure-resistant reaction vessel under high pressure is used. Since it is not necessary to use it, the apparatus becomes simple and preferable.

  The amide wax content is preferably 3.0 to 40.0 parts by mass and more preferably 5.0 to 30.0 parts by mass with respect to 100 parts by mass of the binder resin. By setting the content of the amide wax within the above range, it is possible to obtain a toner that exhibits effective fixing characteristics and sufficiently satisfies the durability development quality.

  As the amide wax used in the present invention, a compound using an unsaturated aliphatic monocarboxylic acid having 20 to 60 carbon atoms and ammonia or a monoamine compound having 1 to 60 carbon atoms as raw materials can be used. As the unsaturated aliphatic monocarboxylic acid having 20 to 60 carbon atoms used as a raw material of the amide wax of the present invention, either a linear aliphatic monocarboxylic acid or a branched aliphatic monocarboxylic acid can be used. . Specific examples include gondoleic acid, gadoleic acid, arachidonic acid, cetreic acid, erucic acid, crupanodonic acid, and ceracolonic acid. The unsaturated aliphatic monocarboxylic acid having 20 to 60 carbon atoms may be used alone or in combination of two or more.

  As the amine compound which is a raw material of the amide wax, either a saturated monoamine compound or an unsaturated monoamine compound can be used, and any of a linear monoamine compound and a monoamine compound having a branched chain can be used. Specific examples include methylamine, hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, aralkylamine, behenylamine, 2-ethylhexylamine, oleylamine, and erucylamine. Ammonia or a monoamine compound having 1 to 60 carbon atoms may be used alone or in combination of two or more.

  The method for synthesizing the amide wax used in the present invention is not particularly limited as long as the unsaturated aliphatic monocarboxylic acid having 20 to 60 carbon atoms and ammonia or the monoamine compound having 1 to 60 carbon atoms are used as raw materials. Specifically, a method in which the raw material is directly subjected to a dehydration condensation reaction and a method in which the aliphatic monocarboxylic acid is esterified and then reacted with the amine compound are exemplified.

  The amide wax synthesized using the above raw materials contains impurities such as unreacted carboxylic acid and amine and by-products during the reaction in addition to the main product. By performing a distillation operation for these waxes, the amount of high-boiling volatile components generated is reduced, and a remarkable in-machine contamination suppression effect is obtained. As the wax distillation method, a method in which short-path distillation and molecular distillation are combined is particularly preferable. For example, distillation is performed by the following method. The wax used as a raw material is subjected to short-path distillation under conditions of a pressure of 1 to 10 Pa and a temperature of 180 to 200 ° C., and the process of removing the initial distillation is repeated to fractionate the wax. Subsequently, molecular distillation is performed on the separated wax under conditions of a pressure of 0.1 to 0.5 Pa and a temperature of 190 to 220 ° C. According to the study by the present inventors, it has been found that if the distillation residue is removed in addition to the first-running component in advance by short-path distillation, the low boiling point volatile component can be efficiently removed by molecular distillation. A short path distillation apparatus particularly suitable for the present invention includes a wiped film evaporator.

  Examples of the amide wax used in the present invention include those obtained by subjecting an amide wax having the following structural formula as a main component obtained by reacting an unsaturated aliphatic monocarboxylic acid and an aliphatic monoamine compound to a vacuum distillation method.

  In the present invention, a nonpolar hydrocarbon wax may be used in combination in order to improve durability and offset resistance. As the nonpolar wax, those having a peak top temperature of 50 to 110 ° C. of the maximum endothermic peak are preferable. For example, the following wax is mentioned. Polyolefin obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefin; polyolefin polymerized using a catalyst such as Ziegler catalyst or metallocene catalyst; paraffin wax, Fischer-Tropsch wax; Synthetic hydrocarbon waxes synthesized by hydrocol method, age method, etc .; Synthetic waxes using a compound having one carbon atom as a monomer; Hydrocarbon waxes having functional groups such as hydroxyl groups and carboxyl groups; Hydrocarbon waxes and functional groups Mixtures with hydrocarbon waxes having groups. The content of these nonpolar waxes is preferably 4.0 to 35.0 parts by mass in total with the amide wax with respect to 100 parts by mass of the binder resin, and 7.0 to 25.0 parts by mass. More preferably, it is used.

  Examples of the binder resin used for the toner include the following. Polystyrene; homopolymer of styrene-substituted product such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic Acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer Styrene copolymers such as polymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenolic resins, natural modifications Phenolic resin, heaven Resin-modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin . Preferred binder resins include styrene copolymers or polyester resins.

  Examples of the comonomer for the styrene monomer of the styrene copolymer include the following compounds. Acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, methacryl A monocarboxylic acid having a double bond such as octyl acid, acrylonitrile, methacrylonitrile, acrylamide or its substitute; a dicarboxylic acid having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate, and Vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; Ethylene-based olefins such as ethylene, propylene and butylene; Bis such as vinyl methyl ketone and vinyl hexyl ketone Ketone like; vinyl methyl ether, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more. The styrenic homopolymer or styrenic copolymer may be cross-linked or used in admixture.

  As the crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds may be mainly used. Aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylate esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline and divinyl ether , Divinyl sulfide, divinyl sulfone and the like; and compounds having three or more vinyl groups. These crosslinking agents are used alone or as a mixture. As a synthesis method of the styrene copolymer, any of a bulk polymerization method, a solution polymerization method, a suspension polymerization method and an emulsion polymerization method may be used.

Next, the composition of the polyester resin that can be suitably used as the binder resin will be described. Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenol represented by formula (A) and derivatives thereof;

(Wherein R represents an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 to 10). Diols represented by formula (B);

(Wherein R ′ represents —CH 2 CH 2 — or the following formula, x ′ and y ′ are integers of 0 or more, and the average value of x ′ + y ′ is 0 to 10).

  Divalent acid components include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides or lower alkyl esters thereof; alkyls such as succinic acid, adipic acid, sebacic acid, and azelaic acid. Dicarboxylic acids, or anhydrides thereof, or lower alkyl esters thereof; alkenyl succinic acids or alkyl succinic acids such as n-dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides thereof, or lower alkyl esters thereof; fumaric acid, maleic acid , Unsaturated dicarboxylic acids such as citraconic acid and itaconic acid, or anhydrides thereof, or dicarboxylic acids such as lower alkyl esters thereof and derivatives thereof.

Moreover, it is preferable to use together the trihydric or more alcohol component and trivalent or more acid component which work also as a crosslinking component. Examples of the trihydric or higher polyhydric alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butane. Triol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene Can be mentioned. Examples of the trivalent or higher polyvalent carboxylic acid component include trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and 2,5,7-naphthalene. Tricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, Tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, empole trimer acid, and their anhydrides, lower alkyl esters;

  (Wherein X represents a C 1-30 alkylene group or alkenylene group having one or more side chains having 1 or more carbon atoms), an anhydride thereof, or a lower alkyl ester thereof. And multivalent carboxylic acids and derivatives thereof. Of the number of moles of all components, the alcohol component is preferably 40 to 60 mol%, more preferably 45 to 55 mol%, and the acid component is preferably 60 to 40 mol%, more preferably 55. -45 mol%. Moreover, it is preferable that the polyvalent component more than trivalence is 1-60 mol% in all the components. A polyester resin can be obtained by performing generally known condensation polymerization using the above alcohol component and acid component.

  The glass transition point (Tg) of the binder resin used in the toner of the present invention is preferably 45 to 65 ° C., more preferably 50 to 55 ° C.

  The toner of the present invention contains a colorant in order to impart coloring power. Examples of the colorant preferably used in the present invention include the following organic pigments or dyes and inorganic pigments.

  As the organic pigment or organic dye as the cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, or a basic dye lake compound can be used. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 66.

  Examples of the organic pigment or organic dye as the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  As the organic pigment or organic dye as the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

  As the black colorant, carbon black, a magnetic material, and a color toned to black using the yellow / magenta / cyan colorant are used.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner. The colorant is preferably used by adding 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

  Furthermore, the toner of the present invention may be a magnetic toner containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. Magnetic materials include iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, Examples include alloys of metals such as calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof. The magnetic material is more preferably a surface-modified magnetic material. When a magnetic toner is prepared by a polymerization method, it is preferable to apply a hydrophobic treatment with a surface modifier, which is a substance that does not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents. These magnetic materials have a number average particle diameter of 2 μm or less, preferably 0.1 μm or more and 0.5 μm or less. The amount contained in the toner particles is 20 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or binder resin, particularly preferably 40 parts by mass or more and 150 parts by mass with respect to 100 parts by mass of the binder resin. Less than mass part is good.

  The toner of the present invention can be used by mixing a charge control agent with toner particles as necessary. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system. As the charge control agent, known ones can be used, and in particular, a charge control agent that has a high frictional charging speed and can stably maintain a constant triboelectric charge amount is preferable. Examples of charge control agents include those that control the toner to be negatively charged, such as organometallic compounds and chelate compounds. Examples thereof include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Others include aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenols. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents. Examples of charge control agents include those that control the toner to be positively charged. Nigrosine modified products with nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Some onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid , Ferricyanides, ferrocyanides); metal salts of higher fatty acids; resin-based charge control agents. The toner of the present invention can contain these charge control agents alone or in combination of two or more. Among these charge control agents, a metal-containing salicylic acid-based compound is preferable from the viewpoint of charge rising characteristics and charge stability, and the metal is particularly preferably aluminum or zirconium. A particularly preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound. A preferable blending amount of the charge control agent is 0.01 parts by mass or more and 5 parts by mass or less, more preferably 0.05 parts by mass or more and 4.5 parts by mass or less with respect to 100 parts by mass of the binder resin.

  Furthermore, it is preferable to contain a charge control resin as necessary to supplement the charge holding ability. As the charge control resin, a polymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group in the side chain is preferably used. Among them, it is particularly preferable to use a polymer or copolymer of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group. Monomers having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group for producing a charge control resin are styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamide-2- There are methylpropane sulfonic acid, vinyl sulfonic acid, methacryl sulfonic acid and their alkyl esters.

  The polymer containing a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group may be a homopolymer of the above monomer, but is a copolymer of the above monomer with another monomer. It does not matter. As a monomer that forms a copolymer with the above monomer, there is a vinyl polymerizable monomer, and the monofunctional polymerizable monomer or the multifunctional polymerization exemplified in the description of the binder resin component above. Sex monomers can be used. The polymer having a sulfonic acid group or the like preferably contains 0.01% by mass or more and 5.00% by mass or less with respect to 100 parts by mass of the polymerizable monomer or binder resin. More preferably, they are 0.1 mass% or more and 3.00 mass% or less. When the polymer having a sulfonic acid group or the like is 0.01% by mass or more and 5.00% by mass or less, a sufficient charging stability effect of the toner particles is exhibited, and therefore, environmental characteristics and durability characteristics are excellent.

  When the toner particles are produced by a suspension polymerization method, it is preferable to add a polar resin during the polymerization reaction from the dispersion step to the polymerization step. In that case, the presence state of the polar resin can be controlled according to the balance of polarity exhibited by the polymerizable monomer composition serving as toner particles and the aqueous dispersion medium. That is, it is possible to form a thin shell of a polar resin on the surface of the toner particles, or to make the polar resin exist with an inclination from the toner particle surface toward the center. In addition, the strength of the shell portion of the core-shell structure can be freely controlled by adding the polar resin. Therefore, it is possible to optimize development durability and fixability of the toner.

  Polar resins include polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, or copolymers of nitrogen-containing monomers and styrene-unsaturated carboxylic acid esters; nitriles such as acrylonitrile Monomer; Halogen-containing monomer such as vinyl chloride; Unsaturated carboxylic acid such as acrylic acid and methacrylic acid; Unsaturated dibasic acid; Unsaturated dibasic acid anhydride; Polymer of nitro monomer or Styrene such as styrene monomer, styrene-acrylic acid copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid ester copolymer, styrene-maleic acid copolymer And copolymers with polyester copolymers; polyester resins; epoxy resins. Two or more of these polar resins may be used in combination.

  The polar resin has a weight average molecular weight Mw of 5,000 to 30,000 measured by gel permeation chromatography (GPC), and a ratio of the number average molecular weight to the weight average molecular weight (Mw / Mn) of 1.05 to What is 5.00 is preferable. More preferably, the weight average molecular weight Mw (A) is 8,000 to 20,000. The glass transition temperature Tg is preferably 60 to 100 ° C. Further, the acid value Av is preferably 5 to 30 mgKOH / g. The content of the polar resin is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polymerizable monomer or the binder resin. More preferably, it is 5 to 30 parts by mass.

  When the toner particles are produced by a polymerization method, the polymerization initiator used in the production of the toner particles is one having a half-life of 0.5 to 30 hours during the polymerization reaction, based on 100 parts by mass of the polymerizable monomer. It is preferably used in a proportion of 0.5 to 20 parts by mass, and the toner can have a desired strength and appropriate melting characteristics. As polymerization initiators, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), Azo or diazo polymerization initiators such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene Examples thereof include peroxide polymerization initiators such as hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, and t-butylperoxy 2-ethylhexanoate.

  When the toner particles are produced by a polymerization method, a crosslinking agent may be added, and a preferable addition amount is 0.001 to 15% by mass of the polymerizable monomer composition. As the crosslinking agent, a compound having two or more polymerizable double bonds is mainly used, and an aromatic-divinyl compound such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butane Carboxylic acid esters having two double bonds such as diol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and compounds having three or more vinyl groups; used alone or as a mixture It is done.

In the toner of the present invention, it is preferable to add inorganic fine powders such as silica, alumina and titania in order to improve charging stability, developability, fluidity and durability. As a main component of the inorganic fine powder to be added, silica is preferable, and the number average primary particle size of silica is preferably 4 nm or more and 80 nm or less. When the number average primary particle size is in the above range, the fluidity of the toner is improved and the storage stability of the toner is also improved. The number average primary particle size of the inorganic fine powder is measured as follows. The number average primary particle size is obtained by observing with a scanning electron microscope and measuring the particle size of 100 inorganic fine powders in the field of view to determine the average particle size. Silica and fine powders such as titanium oxide, alumina, or double oxides thereof can be used in combination. Among the inorganic fine powders used in combination with silica, titanium oxide is preferable. Examples of the silica of the inorganic fine powder include both dry silica produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside the silica fine powder and less production residue of Na ₂ O and SO ₃ ²⁻ is preferable. In addition, dry silica can also be used to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process.

  The inorganic fine powder is added for improving the fluidity of the toner and making the triboelectric charge uniform. Hydrophobic treatment of inorganic fine powder can provide functions such as adjustment of triboelectric charge amount of toner, improvement of environmental stability, improvement of characteristics under high humidity environment, etc. It is preferable to use inorganic fine powder. When the inorganic fine powder added to the toner absorbs moisture, the triboelectric charge amount as the toner decreases, and the developability and transferability tend to decrease.

  Examples of the treatment agent for the hydrophobic treatment of the inorganic fine powder include the following. Unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. These treatment agents may be used alone or in combination. Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the inorganic fine powder is hydrophobized with a silicone oil treatment at the same time or after the hydrophobic treatment with a coupling agent. Even in a high humidity environment, the triboelectric charge amount of the toner particles can be kept high, and the selective developability can be reduced.

  Next, a method for producing toner particles will be described. The toner particles used in the present invention can be produced by any of a pulverization method, a suspension polymerization method, and an emulsion aggregation method. Among them, the following method for producing toner particles in an aqueous dispersion medium is preferable from the viewpoint of excellent development stability even when a large amount of a wax component is added. Emulsion aggregation method in which an emulsion composed of essential toner components is agglomerated in an aqueous dispersion medium; after the essential toner components are dissolved in an organic solvent, granulation in the aqueous dispersion medium is followed by volatilization of the organic solvent. Particle method; Suspension polymerization method or emulsion polymerization method in which a polymerizable monomer in which essential toner components are dissolved is directly granulated in an aqueous dispersion medium and then polymerized; Then, seed polymerization is used to provide an outer layer on the toner; Microcapsule method represented by polycondensation and drying in liquid.

  Among these, the suspension polymerization method is particularly preferable. In the suspension polymerization method, a polymerizable monomer is uniformly dissolved or dispersed in a polymerizable monomer by dissolving or dispersing a wax and a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives). A meter composition is obtained. Thereafter, the polymerizable monomer composition is dispersed in an aqueous dispersion medium containing a dispersion stabilizer using an appropriate stirrer, and a polymerization reaction is performed to obtain toner particles having a desired particle size. It is. After the polymerization, the toner particles are filtered, washed and dried by a known method, and if necessary, a fluidity improver is mixed and adhered to the surface to obtain the toner of the present invention.

  As the dispersant used for preparing the aqueous dispersion medium, known inorganic and organic dispersants can be used. Specifically, examples of the inorganic dispersant include the following. Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina Is mentioned. Organic dispersants include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, and starch.

  Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.

  As the dispersant used in preparing the aqueous dispersion medium used in the toner of the present invention, an inorganic, poorly water-soluble dispersant is preferable, and a poorly water-soluble inorganic dispersant that is soluble in an acid is preferably used. Further, when preparing an aqueous dispersion medium using a hardly water-soluble inorganic dispersant, the amount of these dispersants used is 0.2 parts by mass or more, 2.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is preferable that it is below mass parts. Moreover, it is preferable to prepare an aqueous dispersion medium using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.

  When preparing an aqueous dispersion medium in which the above poorly water-soluble inorganic dispersant is dispersed, a commercially available dispersant may be used as it is. Further, in order to obtain dispersant particles having a fine uniform particle size, a water-based dispersion medium can be prepared by generating a poorly water-soluble inorganic dispersant as described above in a liquid medium such as water under high-speed stirring. Good. For example, when tricalcium phosphate is used as a dispersant, a preferred dispersant can be obtained by mixing aqueous sodium phosphate solution and aqueous calcium chloride solution at high speed to form fine particles of tricalcium phosphate. .

  The toner of the present invention can be used as a two-component developer in combination with a carrier, and conventionally known carriers can be used as a carrier in the two-component development method. Specifically, particles having an average particle diameter of 20 to 300 μm of metals such as surface oxidized or unoxidized iron, nickel, cobalt, manganese, chromium, rare earth and their alloys or oxides are used. A magnetic material-dispersed carrier in which a magnetic material is dispersed in a resin, a low specific gravity carrier in which a resin is embedded in porous iron oxide, and the like are also preferably used. Further, those obtained by attaching or coating a resin such as a styrene resin, an acrylic resin, a silicone resin, a fluorine resin, or a polyester resin on the surface of the carrier particles are preferably used.

  Below, the measuring method of a physical-property value is demonstrated.

[1] Wax gel permeation chromatography (GPC)
The molecular weight distribution of the wax is measured by gel permeation chromatography (GPC) as follows.

To o-dichlorobenzene for gel chromatography, special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added so that the concentration becomes 0.10 wt / vol%, and dissolved at room temperature. The wax and o-dichlorobenzene to which the above BHT is added are put into a sample bottle and heated on a hot plate set at 150 ° C. to dissolve the wax. Once the wax has melted, place it in a preheated filter unit and place it on the body. The sample that has passed through the filter unit is used as a GPC sample. The sample solution is adjusted so that the concentration is about 0.15% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Column: TSKgel GMHHR-H HT 2 series (manufactured by Tosoh Corporation)
Temperature: 135.0 ° C
Solvent: o-dichlorobenzene for gel chromatography (BHT added at 0.10 wt / vol%)
Flow rate: 1.0 ml / min
Injection volume: 0.4ml
In calculating the molecular weight of the wax, a standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

[2] Weight average particle diameter of toner (D4)
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precision particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

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

  Prior to measurement and analysis, the dedicated software is set as follows.

  In the screen for changing the standard measurement method (SOM) of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and the Kd value is “standard particles 10.0 μm” (manufactured by Beckman Coulter) Set the value obtained using. The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

  In the special software pulse to particle size conversion setting screen, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

  (1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.

  (2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water is placed in a water tank of an ultrasonic disperser, and about 2 ml of the contamination N is added to the water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the electrolyte solution liquid surface in a beaker may become the maximum.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

  Hereinafter, the present invention will be described with reference to specific examples. In addition, "part" described in an Example represents a mass part unless there is particular notice.

(Method for producing amide wax 10)
Using amide wax 1 as a raw material, using a wipe film evaporator, the temperature was maintained at 180 ° C. under a pressure of 2 Pa for 30 minutes, and then the temperature was raised stepwise to 195 ° C. to remove a 15% by mass light fraction. Subsequently, the pressure was raised to 1 Pa in steps, and the temperature was raised stepwise to 280 ° C. to obtain a distilled wax having a yield of 80% by mass from which 5% by mass of the distillation residue had been removed. From the fractionated distilled wax, a light fraction was removed using a molecular distillation apparatus under conditions of a temperature of 195 ° C. and a pressure of 0.2 Pa to obtain an amide wax 10 having a final yield of 70% by mass with respect to the raw material.

(Method for producing amide wax 11)
In the manufacturing method of the amide wax 10, the raw material wax was changed to the amide wax 2, and the treatment was performed in the same manner except that the distillation time was adjusted, whereby the amide wax 11 was obtained. The amide wax 11 was removed with 15% by weight of light fraction and 5% by weight of distillation residue with a wiped film evaporator, and then with 10% by weight of light fraction with a molecular distillation device. The final yield was 70% by weight. Obtained.

(Method for producing amide wax 12)
In the manufacturing method of the amide wax 10, the raw material wax was changed to the amide wax 3, and the treatment was performed in the same manner except that the distillation time was adjusted, whereby the amide wax 12 was obtained. The amide wax 12 was removed by removing 15% by weight of light fraction and 5% by weight of distillation residue with a wiped film evaporator, and then removed by 15% by weight of light fraction with a molecular distillation apparatus. The final yield was 65% by weight. Obtained.

(Method for producing amide wax 13)
In the manufacturing method of the amide wax 10, it processed by the same method except adjusting distillation time, and the amide wax 13 was obtained. The amide wax 13 was obtained by removing 5% by mass of light fraction and 5% by mass of distillation residue with a wiped film evaporator, then removing 10% by mass of light fraction with a molecular distillation device, and the final yield was 80% by mass. I got it.

(Method for producing amide wax 14)
In the manufacturing method of the amide wax 13, the same process was performed except not having performed the distillation process using the wiped film evaporator, and the amide wax 14 with a final yield of 90 mass% was obtained.

(Method for producing amide wax 15)
In the production method of the amide wax 12, the same treatment was performed except that the distillation step using the wiped film evaporator was not performed, and the amide wax 15 having a final yield of 80% by mass was obtained.

(Method for producing amide wax 16)
In the manufacturing method of the amide wax 15, it processed by the same method except adjusting distillation time, and the amide wax 16 with the final yield of 85 mass% was obtained.

(Method for producing amide wax 17)
The light fraction was removed using amide wax 4 as a raw material under the conditions of a temperature of 195 ° C. and a pressure of 0.2 Pa using a molecular distillation apparatus to obtain amide wax 17 having a final yield of 75% by mass with respect to the raw material.

(Method for producing amide wax 18)
In the manufacturing method of the amide wax 17, the same treatment was performed except that the amide wax 5 was used as a raw material, and an amide wax 18 having a final yield of 80% by mass with respect to the raw material was obtained.

(Method for producing amide wax 19)
In the method for producing the amide wax 17, the same treatment was performed except that the amide wax 6 was used as a raw material, and an amide wax 19 having a final yield of 90% by mass with respect to the raw material was obtained.

(Method for producing amide wax 20)
In the method for producing the amide wax 17, the same treatment was performed except that the amide wax 7 was used as a raw material, and an amide wax 20 having a final yield of 90% by mass with respect to the raw material was obtained.

(Method for producing amide wax 21)
In the manufacturing method of the amide wax 10, the raw material wax was changed to the amide wax 8, and the treatment was performed in the same manner except that the distillation time was adjusted, whereby the amide wax 21 was obtained. In addition, after removing 15% by weight of light fraction and 5% by weight of distillation residue with a wiped film evaporator, the amide wax 21 was removed with 10% by weight of light fraction with a molecular distillation device, and the final yield was 70% by weight. Obtained.

(Method for producing amide wax 22)
In the manufacturing method of the amide wax 18, it processed by the same method except adjusting distillation time, and the amide wax 22 of the final yield of 85 mass% was obtained.

(Method for producing amide wax 23)
In the manufacturing method of the amide wax 17, the same treatment was performed except that the amide wax 9 was used as a raw material, and an amide wax 23 having a final yield of 80% by mass with respect to the raw material was obtained.

  Table 1 shows the physical properties of the amide waxes 10-23.

<Example 1>
A suspension polymerization toner was produced by the following procedure. 9 parts of tricalcium phosphate is added to 1300 parts of ion-exchanged water heated to 60 ° C., and stirred at 10,000 r / min using a TK homomixer (manufactured by Special Machine Industries). Was prepared.

Moreover, the following material was melt | dissolved at 100 r / min with the propeller-type stirring apparatus, and the solution was prepared.
・ Styrene ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 70.0 parts ・ n-Butyl acrylate ・ ・ ・ ・ ・ ・30.0 parts FCA1001NS (Fujikura Kasei Co., Ltd.) 1.0 parts saturated polyester resin ...... 5.0 parts (acid value 10 mgKOH / g, peak molecular weight 15,000)
Next, in the above solution,
・ C. I. Pigment Blue 15: 3 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 6.5 parts ・ Charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 0 parts, amide wax 10 ... 20.0 parts, divinylbenzene ... ... 0.20 part is added, and then the mixture is heated to a temperature of 65 ° C and then adjusted to 10,000 r / min with a TK homomixer (made by Tokushu Kika Kogyo). Stir to dissolve and disperse.

Subsequently, the polymerizable monomer composition is charged into the aqueous medium, and as a polymerization initiator, perbutyl PV (10-hour half-life temperature 54.6 ° C. (manufactured by NOF Corporation)) 8.0 parts Was added and granulated by stirring at 10,000 r / min for 20 minutes at 70 ° C. using a TK homomixer.

  The mixture was transferred to a propeller type agitator and stirred at 120 r / min for 5 hours at 70 ° C., then heated to 80 ° C. and further reacted for 5 hours. After completion of the polymerization reaction, the slurry was cooled, washed with 10 times the amount of water as the slurry, filtered and dried, and then the particle diameter was adjusted by classification to obtain toner particles.

Hydrophobic silica fine powder (primary particle diameter: 7 nm, BET specific surface area) charged with negative polarity, treated with dimethyl silicone oil (20% by mass) as a fluidity improver for 100 parts of the toner particles. 130 m ^{2 /} g) 1.7 parts was mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) for 15 minutes at 3000 r / min, and toner No. having a weight average particle diameter (D4) of 6.5 μm was mixed. 1 was obtained. Toner No. 1 was evaluated by the following method. Toner No. Table 1 shows the physical properties of Table 1 and Table 2 shows the evaluation results.

  Toner No. 1 was subjected to a print test of 200,000 sheets using a modified machine of a commercially available laser beam printer LBP9500C (manufactured by Canon Inc.). The printer remodeling conditions were a plain paper mode process speed of 360 mm / sec and a fixing temperature control of 200 ° C. Furthermore, toner No. is added to all the yellow, magenta, cyan, and black stations. A cyan cartridge refilled with 1 was installed. As the durability evaluation chart, an original chart having a color printing rate of 5% (full color printing rate of 20%) was used. Each time the toner runs out, the cartridge was changed and the evaluation was continued.

[In-flight contamination assessment]
The above print test was conducted using a paper having a basis weight of 68 g / m ² in a plain paper mode under each environment of a normal temperature and normal humidity environment (23 ° C., 50% RH) and a low temperature low humidity environment (15 ° C., 10% RH). went. Thereafter, the contamination state around the fixing device was visually evaluated according to the following criteria.
A: Conspicuous contamination is hardly seen around the fixing device.
B: A slight amount of contamination is observed around the fixing device, but there is no problem.
C: Contamination spread is clearly observed in the fixing guide portion, but there is no practical problem.
D: Level at which a considerable amount of contamination is conspicuous around the fixing device and image loss occurs.

[Halftone image reproducibility]
The above print test was conducted using a paper having a basis weight of 68 g / m ² in a plain paper mode under each environment of a normal temperature and normal humidity environment (23 ° C., 50% RH) and a low temperature low humidity environment (15 ° C., 10% RH). went. At that time, a halftone image and a halftone image that is not subjected to dithering (an image that reproduces a halftone only by adjusting the amount of laser light without performing pseudo-halftone expression) were output every 1,000 sheets. With respect to the halftone image and the halftone image not subjected to dither processing, the presence or absence of vertical streaks on the image due to in-machine contamination on the transfer belt or the like was visually observed, and the worst image through the print test was evaluated according to the following criteria.
A: Both the halftone image and the halftone image not subjected to dithering are good without vertical stripes.
B: Vertical stripes are not seen in the halftone image, but there are portions that look slightly streaks in the halftone image that is not subjected to dithering.
C: A vertical stripe is slightly observed in the halftone image, and a clear vertical stripe is confirmed in the halftone image where the dither processing is not performed.
D: Vertical stripes are clearly confirmed in both the halftone image and the halftone image that is not subjected to dithering.

[Concentration stability]
The above print test was performed using a paper having a basis weight of 68 g / m ² in a plain paper mode in a normal temperature and humidity environment (23 ° C., 50% RH). At that time, an original image in which nine black solid patches of 20 mm square were arranged in every 1000 sheets in the development area was output. For the average density of 9 solid black patches, the density difference of the average density of the image output during the print test was compared with the average density of the initial image. Throughout the print test, the largest value of this density difference was taken as the maximum density difference. The image density was measured using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.).
A: The maximum density difference is less than 0.15.
B: The maximum density difference is 0.15 or more and less than 0.25.
C: The maximum density difference is 0.25 or more and less than 0.3.
D: The maximum density difference is 0.3 or more.

<Example 2>
A pulverized toner was produced by the following procedure. Styrene-butyl acrylate copolymer A (St / BA = 80/20, Tg) using 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane as a polymerization initiator in the suspension polymerization method. = 67 ° C, Mw = 820,000). Next, a styrene-butyl acrylate copolymer B (St / BA = 85/15, Tg = 61 ° C., Mw = 15,800) using di-t-butyl peroxide as a polymerization initiator by a solution polymerization method is prepared. did. Binder resin 1 was prepared by mixing 30 parts by mass of copolymer A in a solution with respect to 70 parts by mass of copolymer B.
-Binder resin 1100 parts-C.I. I. Pigment Blue 15: 3 6.0 parts, charge control agent Bontron E-88 (manufactured by Orient Chemical Co., Ltd.) 1.0 parts, amide wax 11 5.0 parts The above materials were premixed with a Henschel mixer and then set to 110 ° C. It knead | mixed with the twin-screw kneading extruder. The obtained kneaded product is cooled and coarsely pulverized with a cutter mill, and then finely pulverized using a pulverizer using a jet stream, and classified using a multi-division classifier utilizing the Coanda effect. Toner particles of 5 μm were obtained. A negatively charged hydrophobic silica fine powder (primary particle size: 7 nm, BET specific surface area: 130 m) treated with dimethyl silicone oil (20% by mass) as a fluidity improver on 100 parts by mass of the toner particles. ^{2 /} g) 1.7 parts was mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) for 15 minutes at 3000 r / min. 2 was obtained. The obtained toner No. The physical properties of 2 are shown in Table 1, and the results of evaluation in the same manner as in Example 1 are shown in Table 2.

<Example 3>
An emulsion aggregation toner was produced by the following procedure.

(Preparation of resin particle dispersion 1)
・ Styrene 90.0 parts ・ N-butyl acrylate 20.0 parts ・ Acrylic acid 3.0 parts ・ Dodecanethiol 6.0 parts ・ Carbon tetrabromide 1.0 part Surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) 1.5 parts and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.5 parts were dissolved in ion-exchanged water 140 parts. It was dispersed and emulsified in a flask containing an aqueous medium. While slowly mixing for 10 minutes, 10 parts of ion-exchanged water in which 1 part of ammonium persulfate was dissolved was added thereto, and after replacing with nitrogen, an oil bath was used until the contents reached 70 ° C. while stirring the flask. The emulsion polymerization was continued for 5 hours. Thus, a resin particle dispersion 1 was prepared by dispersing resin particles having an average particle size of 0.17 μm, a glass transition point of 57 ° C., and a weight average molecular weight (Mw) of 11,000.

(Preparation of resin particle dispersion 2)
-Styrene 75.0 parts-n-butyl acrylate 25.0 parts-Acrylic acid 2.0 parts Mixing and dissolving the above, a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) 5 parts and 3 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) dissolved in 140 parts of ion-exchanged water are dispersed in a flask, emulsified, and slowly mixed for 10 minutes. However, 10 parts of ion-exchanged water in which 0.8 part of ammonium persulfate was dissolved was added thereto, and after nitrogen substitution, the contents in the flask were heated with an oil bath until the temperature reached 70 ° C. while stirring. Emulsion polymerization is continued as it is for 5 hours to prepare a resin particle dispersion 2 in which resin particles having an average particle size of 0.1 μm, a glass transition point of 61 ° C., and a weight average molecular weight (Mw) of 550,000 are dispersed. Shi .

(Preparation of release agent particle dispersion)
Amido wax 3 50.0 parts Anionic surfactant 5.0 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-200.0 parts of ion-exchanged water was heated to 87 ° C and dispersed using a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge type homogenizer. A release agent particle dispersion liquid in which a release agent of 5 μm was dispersed was prepared.

(Preparation of Colorant Particle Dispersion 1)
・ C. I. Pigment Blue 15: 3 20.0 parts, anionic surfactant 2.0 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-78.0 parts or more of ion-exchanged water was mixed and dispersed using a sand grinder mill. The particle size distribution in this colorant particle dispersion 1 was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.). As a result, the average particle diameter of the colorant particles was 0.2 μm, and coarse particles exceeding 1 μm were not observed.

(Preparation of charge control particle dispersion)
20.0 parts of a metal compound of di-alkyl-salicylic acid (charge control agent, Bontron E-88, manufactured by Orient Chemical Industries)
・ Anionic surfactant 2.0 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-78.0 parts or more of ion-exchanged water was mixed and dispersed using a sand grinder mill. When the particle size distribution in this charge control particle dispersion was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the charge control particles contained was 0.2 μm, and 1 μm No larger coarse particles were observed.

(Mixed solution preparation)
-Resin particle dispersion 1 250.0 parts-Resin particle dispersion 2 110.0 parts-Colorant particle dispersion 1 50.0 parts-Release agent particle dispersion 80.0 parts , Put into a 1 liter separable flask equipped with a thermometer and stirred. The mixture was adjusted to pH = 5.2 using 1N potassium hydroxide.

(Agglomerated particle formation)
As a flocculant, 150 parts of a 10% sodium chloride aqueous solution was added dropwise to this mixed solution, and the flask was heated to 57 ° C. while stirring the inside of the flask. At this temperature, 3 parts of resin particle dispersion 2 and 10 parts of charge control agent particle dispersion were added. After maintaining at 50 ° C. for 1 hour, observation with an optical microscope confirmed that aggregated particles (A) having a weight average particle diameter of about 5.3 μm were formed.

(Fusion process)
Then, after adding 3 parts of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) here, the stainless steel flask was sealed and heated to 105 ° C. while stirring with a magnetic seal. And held for 1 hour. Then, after cooling, the reaction product was filtered, sufficiently washed with ion-exchanged water, and dried to obtain toner particles (2) having a weight average particle diameter (D4) of 6.0 μm. To 100 parts of the toner particles (2), a negatively charged hydrophobic silica fine powder (primary particle size: 7 nm, BET specific surface area: 130 m ² / g) treated with dimethyl silicone oil (20% by mass). ) 1.8 parts is charged into a Henschel mixer and mixed for 15 minutes at 3000 r / min. 3 was obtained. The obtained toner No. Table 1 shows the physical properties of No. 3 and Table 2 shows the results of evaluation in the same manner as in Example 1. As a result, good fixing characteristics and durability characteristics were obtained.

<Examples 4, 5, and 9>
In the same manner as in Toner Production Example 1 except that amide waxes 13, 14, and 18 are used instead of amide wax 10, suspension polymerization method toner No. 1 is used. 4, 5, 9 were obtained. Suspension polymerization toner no. Evaluations similar to the method described in Example 1 were performed for 4, 5, and 9. The evaluation results are shown in Table 2.

<Examples 8 and 10>
In the same manner as in Toner Production Example 2 except that amide waxes 17 and 19 are used instead of amide wax 11, pulverized toner no. 8 and 10 were obtained. Grinding method toner No. Evaluations similar to those described in Example 1 were performed for 8 and 10. The evaluation results are shown in Table 2.

[Examples 6 and 7]
In the same manner as in Toner Production Example 3 except that amide waxes 15 and 16 are used in place of amide wax 12, emulsion aggregation toner no. 6 and 7 were obtained. Emulsion aggregation toner No. Evaluations similar to the method described in Example 1 were performed for 6 and 7. The evaluation results are shown in Table 2.

[Comparative Examples 1, 2, 4]
In the same manner as in Toner Production Example 2 except that amide waxes 20, 21, and 23 were used instead of amide wax 11 and the amide wax content was changed as shown in Table 2, respectively, 11, 12, and 14 were obtained. Grinding method toner No. Evaluations similar to the method described in Example 1 were performed for 11, 12, and 14. The evaluation results are shown in Table 2.

[Comparative Example 3]
A suspension polymerization toner No. 1 was prepared in the same manner as in Toner Production Example 1 except that amide wax 22 was used instead of amide wax 10. 13 was obtained. Suspension polymerization toner no. 13 was evaluated in the same manner as in the method described in Example 1. The evaluation results are shown in Table 2.

Claims (3)

In a toner having toner particles containing a binder resin, an amide wax, and a colorant, the amide wax was heated at 200 ° C. for 10 minutes with a heat desorption device, and in the GC / MS analysis of the desorbed component, the carbon number of 16 The total amount (A) of volatile components detected after the hydrocarbon peak detection time is 2000 ppm or less (in terms of hexadecane), and the peak molecular weight of the amide wax measured by gel permeation chromatography is 3.5 × 10 ^2. The toner is 1.5 × 10 ³ or less.   In the GC / MS analysis of the desorbed component, the amide wax is heated at 200 ° C. for 10 minutes with a heat desorption apparatus, and the total amount (B) of volatile components detected after the detection time of the hydrocarbon having 30 carbon atoms, The relationship with the total amount (C) of volatile components detected after the detection time of hydrocarbons having 20 carbon atoms and before the detection time of hydrocarbons having 30 carbon atoms is (B) / (C) ≧ 8.0. The toner according to claim 1, wherein the toner is present.   In the GC / MS analysis of the desorbed component after heating the amide wax at 200 ° C. for 10 minutes with a heat desorption apparatus, the relationship between (D) and the above (A) is the amount of the volatile component detected as the maximum peak. The toner according to claim 1, wherein (D) / (A) ≧ 0.85.