JP5202002B2 - Non-magnetic toner - Google Patents

Description

  The present invention relates to toner particles used in image forming methods such as electrophotography, electrostatic recording, electrostatic printing, and toner jet.

  In recent years, it has become necessary to output color images at high speed in printers and copiers using electrophotography. To increase the process speed in image formation, the toner needs to be sufficiently charged in order to stably develop the electrostatic latent image. In order to sufficiently charge the toner, the triboelectric charging property of the resin component of the toner must be used. However, with this method alone, the toner charge amount cannot be sufficiently secured and the rise of the density is delayed, so that fog may occur on the image or the image density may not be sufficiently obtained.

  Therefore, in order to impart the necessary triboelectric chargeability to the toner, a dye, a pigment, or a charge control agent is added. Among the charge control agents used in the field of electrophotography, the negative charge control agents include metal complex salts of monoazo dyes, nitrohumic acid and its salts, salicylic acid, naphthoic acid, dicarboxylic acid such as Co, Cr and Fe. Also known are sulfonated copper phthalocyanine pigments, styrene oligomers introduced with nitro groups and halogens, chlorinated paraffins, melamine resins, metal complexes such as aromatic diols, resins containing acid components, and the like. As positively chargeable charge control agents, nigrosine dyes, azine dyes, triphenylmethane dyes and pigments, polymers having quaternary ammonium salts and quaternary ammonium salts in the side chain are known. Several proposals have been made regarding such charge control agents (Patent Document 1).

  However, in such a toner, a phenomenon called spent in which the charge control agent present on the toner surface adheres to the charge imparting material occurs. When used as a negatively chargeable toner, there is a problem that the charging ability of the charge-imparting material is reduced due to long-term printing durability, and toner fogging and scattering occur. In addition, when the toner is used as a positively chargeable toner, the charging ability of the charge imparting material is improved by long-term printing durability. However, since the charge amount of the toner becomes excessively high, developability such as image density is rather increased. There is a problem of lowering.

  Therefore, in order to obtain excellent image characteristics, a technique in which two kinds of charge control agents are used in combination with toner is known. For example, a toner containing positive and negative charge control agents, or a toner in which a charge control agent is contained in toner particles and the other is present on the particle surface, both charge control agents are present on the toner particle surface. An existing toner has been reported (Patent Document 2). However, when these charge control agents are used in combination, there are adverse effects such as it is difficult to balance the image density and fog, it is difficult to obtain a sufficient image density in a high humidity environment, and the dispersibility in the resin is deteriorated.

  Therefore, a technique of using a negatively chargeable resin (negative charge control resin) alone as a charge control agent has been reported, and the combined use of a charge control resin and a charge control agent has also been proposed (Patent Document 3).

  If the image forming process speed is increased, the fixing property cannot be secured unless it is melted with a small amount of heat. As another method for lowering the fixing temperature, it is effective to add a release agent having a low melting temperature to the toner. However, if the amount of the release agent added is too large, the amount of the release agent that exudes to the surface of the toner particles increases during durable printing. Further, the amount of toner remaining on the photoconductor increases and the cleaning performance deteriorates, and the toner adheres to the non-image area on the photoconductor and the image quality deteriorates. Eventually, the charging ability of the toner decreases due to the printing of a large number of sheets, and a sufficient image density cannot be obtained, so that the storage stability of the toner in the developing machine is deteriorated. Further, when the toner is easily melted at a low temperature, the toner may adhere to each member in the image forming process due to a rise in the temperature in the machine due to an increase in the speed of the printer / copier.

  Therefore, conventionally, it has been proposed to prevent the exudation of the release agent by forming the colored particles into a core-shell structure and including a release agent in the core layer to form a thick shell layer. However, this method solves the adverse effect of the release agent oozing out, and at the same time inhibits the effect of lowering the fixing temperature by the release agent. Furthermore, it can be improved by increasing the gel content of the binder resin in the core layer to harden the core layer and making it difficult to deteriorate the toner particle surface. However, the binder resin and release agent in the core layer are separated. There is a possibility that the effect of reducing the amount of exudation of the release agent may be reduced (Patent Document 4).

  As described above, in order to ensure the chargeability and fixing property of the toner, it is necessary to protect the toner surface layer with the resin and to increase the durability against the sliding of the toner while avoiding the separation of the binder resin and the release agent. There is. The conventional negative charge control resin cannot give a shell function, and the toner cannot be sufficiently durable against rubbing. Further, as described above, even if any toner is used, it has not been possible to sufficiently achieve both charging property and durability.

JP-A-8-160668 JP 2000-284543 A Japanese Patent Laid-Open No. 2002-341598 JP 2006-215411 A

  The problem to be solved by the present invention is to prevent contamination of various members and to secure sufficient fixing properties while further stabilizing the chargeability of the toner.

In order to achieve the above object, the first invention according to the present application is at least the following i) to v):
i) a polymerizable monomer;
ii) waxes;
iii) a colorant;
iv) A polymer obtained by polymerizing at least a polymerizable monomer having a functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, and a sulfonic acid ester group, and another vinyl polymerizable monomer. The copolymerization ratio C (A) of the polymerizable monomer having a functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, and a sulfonic acid ester group is 0.5 to 2.0% by mass. A polymer A;
v) A polymer obtained by polymerizing at least a polymerizable monomer having a functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, and a sulfonic acid ester group and another vinyl polymerizable monomer The copolymerization ratio C (B) of the polymerizable monomer having a functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, and a sulfonic acid ester group is 5.0 to 10.0% by mass. A polymer B;
A toner composition prepared by dispersing a monomer composition containing an aqueous medium in a water-based medium and polymerizing a polymerizable monomer contained in the monomer composition. Magnetic toner,
When the content of the polymer A with respect to 100 parts by mass of the polymerizable monomer of i) is M (A) (parts by mass) and the content of the polymer B is M (B) (parts by mass), A non-magnetic toner satisfying the following formula.
10.0 ≦ M (A) ≦ 30.0
0.5 ≦ M (B) ≦ 5.0
0.02 ≦ M (B) / M (A) ≦ 0.50

  The toner having the core-shell structure has a function mainly intended to protect the core portion by the shell layer. However, since the adhesion between the shell layer and the core portion is weak, if the toner is continuously stressed by continuous output or the like, the outer layer may be peeled off or scraped, and the toner surface composition may change suddenly at a certain point. is there.

  On the other hand, although the mechanism is not clear, conventional polymers intended for charge control can be obtained by using the polymers A and B containing the sulfonic acid group, sulfonic acid group and sulfonic acid ester group of the present invention. It has become possible to achieve both the chargeability of the shell and the function of shell formation. Specifically, in the toner of the present invention, two types of polymers having different copolymerization ratios derived from a polymerizable monomer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group are used in combination. It is essential to add at a specific ratio. Thereby, it is possible to obtain a toner that can cope with an increase in process speed.

  In the present invention, it is proposed that the development property, the reduction of contamination of members, the improvement of transferability, and the fixing property are satisfied at the same time.

  First, the improvement in developability is high toughness due to rubbing between the toner regulating member and the toner carrier, and there is little change in the charging characteristics of the toner even when images are continuously output, and high development efficiency is achieved. Is to get.

  Further, contamination of the toner regulating member and the photosensitive member due to toner destruction and fusion can be prevented. As a result, circumferential streaks due to foreign object pinching between the toner carrying members and toner scattering due to foreign object pinching between the toner carrying member and the toner end seal can be reduced.

  The next improvement in transferability is that even if images are output continuously, it is possible to maintain the same high transfer efficiency as in the initial stage, enabling uniform transfer to the transfer material, and uniformity within the page in halftone. It is that a thing with high property is obtained.

  The improvement in the fixing property is to enhance the function of appropriately forming the shell portion of the core-shell structure of the toner, and to prevent toner fixing unevenness during fixing.

  The appropriate range of the present invention will be described below.

The acid value AV (A) of the polymer A is
5.0 mgKOH / g ≦ AV (A) ≦ 30.0 mgKOH / g
It is preferable that When the acid value is 5.0 to 30.0 mgKOH / g, the outer layer formation of the toner becomes strong, and the toughness of the toner is improved. Reduce streaks in the circumferential direction on the agent carrier.

AV (B) is the acid value of the polymer B.
10.0 mgKOH / g ≦ AV (B) ≦ 40.0 mgKOH / g
It is preferable that When the acid value is 10.0 to 40.0 mgKOH / g, the functional separation of the shell portion and the core portion in the toner of the polymer A and the polymer B becomes clear, so that toner scattering is reduced and high transfer efficiency is achieved. Can be made.

Further, the ratio of the acid values of the polymers A to B is 1.0 ≦ AV (B) / AV (A) ≦ 5.0.
It is preferable that The reason for this is that when the acid value ratio does not fall within the above range, the granulation property of the toner is adversely affected and a sufficient particle size distribution may not be obtained.

  The peak molecular weight Mp in gel permeation chromatography (GPC) is preferably 15000 to 100,000 for the polymer A and 10,000 to 30,000 for the polymer B. When the peak molecular weight cannot be set within the above range, the dispersibility of the polymer A and the polymer B in the toner is extremely deteriorated.

In the present invention, the glass transition temperature (TgL) of the toner in the differential scanning calorimeter (modulation DSC) is preferably 40 to 60 ° C. The maximum peak temperature (P1) is preferably 70 to 90 ° C. The temperature difference between TgL and P1 is 15.0 ° C. ≦ P1−TgL ≦ 50.0 ° C.
It is preferable that

  When the Tg of the toner is less than 40 ° C., and when the melt viscosity at 100 ° C. is less than 2000, the bleeding property is increased and the toughness is also deteriorated. .

  When the Tg of the toner exceeds 60 ° C., and when the melt viscosity at 100 ° C. exceeds 25,000, the adhesion to the transfer paper is reduced, so that sufficient effects cannot be obtained with respect to low-temperature fixability and wrapping properties. In addition, it is difficult to obtain a fixed image with high glossiness.

  When the temperature difference between TgL and P1 is less than 15.0 ° C. or more than 50.0 ° C., the storage stability of the toner at a high temperature is deteriorated.

  The glass transition temperature TgA of the polymer A is preferably 80.0 ° C. ≦ TgA ≦ 120.0 ° C. The glass transition temperature TgB of the polymer B is preferably 65.0 ° C. ≦ TgB ≦ 95.0 ° C. When the glass transition temperatures of the polymers A and B are not within the above range, the toner shell portion is not sufficiently formed, and the desired chargeability cannot be obtained.

  The weight average particle diameter (D4) of the toner is preferably 4.0 to 9.0 μm. When D4 is less than 4.0 μm, the amount of fine particles becomes excessive, deteriorating the contamination of the member, and the developability is not satisfied. If D4 exceeds 9.0 μm, the dot reproducibility on the photoreceptor is inferior to that in the optimum range, and the developability and transferability of the present invention are not satisfied.

  The average circularity of the toner in the present invention is preferably 0.960 to 1.000. More preferably, it is desired to be 0.965 to 1.000. When the average circularity is less than 0.960, it becomes difficult to uniformly adhere to the toner surface of the inorganic fine powder in addition to the deterioration of the transferability due to the shape factor. , Developability deteriorates.

The total content S (A) of the functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group of the polymer A in the present invention is 2.0 × 10 ^{19 to} 8.0 ×. 10 ¹⁹ pieces / g, and the total content S (B) of the functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group of the polymer B is 15.0 × 10 ^19. It is preferably 35.0 × 10 ¹⁹ pieces / g. If the content of a functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group is not obtained within this range, the chargeability of the toner will not be stabilized.

  Below, the material used by this invention is demonstrated.

  The polymerizable monomer used in the present invention includes a vinyl polymerizable monomer, and a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p A styrenic polymerizable monomer such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n -Hexyl acrylate, 2-ethylhexyl acrylate Acrylic polymerizable monomers such as relate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Body; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n- Octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl Methacrylic polymerizable monomers such as tacrylate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl methyl ether; And vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone; and the like.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, 2,2′-bis (4-methacryloxy / polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, and the like.

  In the present invention, it is preferable to use a polymer of a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group, such as the polymers A and B, mainly for the purpose of charge control and stabilization of granulation in an aqueous medium.

  The polymerizable monomer having the sulfonic acid group, sulfonic acid group or sulfonic acid ester group for producing the polymer is styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamide. There are 2-methylpropane sulfonic acid, vinyl sulfonic acid, methacryl sulfonic acid and the like. The polymer of the sulfonic acid group, sulfonic acid group or sulfonic acid ester group used in the present invention may be a homopolymer of the monomer, but the polymerizable monomer and other polymerizable monomer may be used. It may be a copolymer with a monomer. As a monomer that forms a copolymer with the monomer, there is a vinyl polymerizable monomer, and the monofunctional polymerizable monomer or the polyfunctional polymerizable monomer may be used. I can do it.

In the toner of the present invention, the contents (parts by mass) of the polymer A and the polymer B with respect to 100 parts by mass of the polymerizable monomer constituting the binder resin are M (A) and M (B). When the following equation is satisfied.
10.0 ≦ M (A) ≦ 30.0
0.5 ≦ M (B) ≦ 5.0
0.020 ≦ M (B) / M (A) ≦ 0.50

  When the content M (A) of the polymer A is less than 10.0 parts by mass, the toner core-shell structure is not sufficiently formed, and the toner charge distribution is not uniform. On the other hand, when the amount exceeds 30.0 parts by mass, the layer thickness of the toner shell becomes too thick, and the speed of exudation of wax cannot be sufficiently obtained during fixing.

  And if content M (B) of the said polymer B is less than 0.5 mass part, charging property cannot fully be taken, but the transferability of this invention cannot be satisfied. When the amount exceeds 5.0 parts by mass, the mechanism is not clear, but the granulation property in the aqueous medium is disturbed, and the distribution of toner particles becomes broad. As a result, the toner becomes non-uniformly charged, and the developability and transferability of the present invention cannot be satisfied.

  In the polymer A, the copolymerization ratio (mass%) C (A) derived from a polymerizable monomer having a functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, and a sulfonic acid ester group is 0. If it is less than 5% by mass, the chargeability of the shell formed is inferior. On the other hand, if it exceeds 2.0% by mass, the charge amount of the toner may become excessive in a low temperature and low humidity environment.

  In the polymer B, a copolymerization ratio (mass%) C (B) derived from a polymerizable monomer having a functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, and a sulfonic acid ester group. Is less than 5.0% by mass, the charging property cannot be sufficiently obtained and the developing property cannot be satisfied. If it exceeds 10.0% by mass, the mechanism is not clear, but the granulation property in the aqueous medium is disturbed and the distribution of toner particles becomes broad, resulting in a non-uniformly charged toner. Cause contamination of parts.

  The toner of the present invention may contain a charge control agent in addition to the polymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group in order to stabilize charging characteristics. As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable. Specific compounds include, as negative charge control agents, metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, metal salts or metal complexes of azo dyes or azo pigments, boron compounds , Silicon compounds, calixarene and the like. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, a nigrosine compound, and an imidazole compound.

  The amount of these charge control agents used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. When added internally, it is preferably used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin. Further, when added externally, the amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.3 part by mass with respect to 100 parts by mass of the toner.

  The waxes used in the present invention include petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method, and polyolefin waxes typified by polyethylene. And derivatives thereof, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof, which include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hardened castor oil and derivatives thereof, plant waxes, animal waxes, silicone oils, etc. are also used. it can. Among these, ester wax and hydrocarbon wax are preferable from the viewpoint of excellent releasability. More preferably, a compound containing 50 to 95% by mass of a compound having the same total number of carbon atoms has high wax purity and easily develops the effects of the present invention from the viewpoint of developability.

  The wax preferably contains 1 to 40% by mass with respect to the binder resin. More preferably, it is 3 to 25% by mass. When the content of the wax is less than 1% by mass, the effect of adding the wax is not sufficient, and furthermore, the high temperature offset resistance is insufficient. On the other hand, if the amount exceeds 40% by mass, the exposure of the wax exceeding the required amount is likely to occur on the toner surface, and the function and effect of the present invention cannot be satisfied by maintaining long-term development characteristics and high transfer efficiency. In addition, when the particles are produced in an aqueous medium, it is an adverse effect on sharpening the particle size distribution. Uniformity such as individual shape and chargeability of the toner is easily lost.

  As the polymerization initiator used in the present invention, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. When the polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 10,000 and 100,000 is usually obtained. A toner having strength and melting characteristics can be obtained. Examples of polymerization initiators include 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, t-butylperoxy 2-ethylhexa Noate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxide polymerization such as peroxide and lauroyl peroxide Agents. Particularly preferred is a polymerization initiator that produces an ether compound upon decomposition during the polymerization reaction.

  In the present invention, in order to control the degree of polymerization of the polymerizable monomer, a known chain transfer agent, polymerization inhibitor or the like can be further added and used.

  As the crosslinking agent, a compound having two or more polymerizable double bonds is mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline; And divinyl compounds such as divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These can be used alone or as a mixture. A preferable addition amount is 0.001 to 15% by mass.

  As the colorant used in the invention, carbon black, a magnetic material, and a yellow / magenta / cyan colorant shown below are used as the black colorant, and colors adjusted to each color are used. Moreover, it is necessary to pay attention to the polymerization inhibitory property and water phase transferability of the colorant. The colorant is preferably subjected to surface modification (for example, a hydrophobic treatment without polymerization inhibition). In particular, since dyes and carbon black have many polymerization-inhibiting properties, care must be taken when using them.

  As the yellow colorant, compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 155, 168, 180, 185, 214, etc. are preferably used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19 is particularly preferable.

  As the cyan colorant used in the present invention, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are particularly preferably used.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant 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 added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin.

  Further, the toner of the present invention can be used as a magnetic toner containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. In the present invention, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel, or aluminum, cobalt, copper, lead, magnesium and tin of these metals. And alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

  The magnetic material used in the present invention is more preferably a surface-modified magnetic material. When used in a polymerization toner, the magnetic material is subjected to a hydrophobizing treatment with a surface modifier that is a substance that does not inhibit polymerization. Is preferred. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.

  These magnetic materials preferably have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount to be contained in the toner particles is 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

  Any appropriate stabilizer is added to the aqueous medium used in the present invention. For example, as an inorganic compound, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, Examples thereof include silica and alumina. As an organic compound, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt / polyacrylic acid and its salt / starch, and the like can be dispersed in an aqueous phase. This stabilizer is preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Further, 0.001 to 0.1 parts by mass of a surfactant may be used for fine dispersion of these stabilizers. This is to promote the intended action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate. , Potassium stearate, calcium oleate and the like.

  Among these dispersion stabilizers, when an inorganic compound is used, a commercially available one may be used as it is, but in order to obtain finer particles, the inorganic compound may be produced in an aqueous medium. For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high stirring.

  Further, in the toner of the present invention, it is necessary to add an inorganic fine powder for the purpose of improving the fluidity of the toner. Any inorganic fine powder can be used as long as it can be added to toner particles (colorant-containing resin particles) and the fluidity can be increased as compared with that before the addition.

  For example, fluorine resin powder such as fine vinylidene fluoride powder, polytetrafluoroethylene fine powder; fatty acid metal salt such as zinc stearate, calcium stearate, lead stearate; titanium oxide powder, aluminum oxide powder, zinc oxide powder Or a powder obtained by hydrophobizing the above metal oxide; and a silica fine powder such as a wet process silica or a dry process silica, or a process such as a silane coupling agent, a titanium coupling agent, or a silicone oil. A surface-treated silica fine powder that has been surface-treated with an agent is exemplified. The inorganic fine powder is preferably used in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the toner particles.

  A method for producing toner particles will be described below.

  As a method for producing toner particles in an aqueous medium, an emulsion aggregation method in which an emulsion composed of essential toner components is aggregated in an aqueous medium, an essential toner component is dissolved in an organic solvent, and then the aqueous toner medium is used. Suspension granulation method that volatilizes the organic solvent after granulation, suspension polymerization method and emulsion polymerization method that directly polymerize polymerizable monomer in which toner essential components are dissolved in aqueous medium, and then seed Examples thereof include a method of providing an outer layer on the toner using polymerization, a microcapsule method represented by interfacial polycondensation and drying in liquid.

  Among these, the suspension polymerization method is particularly preferable as the one that easily exhibits the effects of the present invention. In this suspension polymerization method, a monomer composition is prepared by uniformly dissolving or dispersing a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) in the polymerizable monomer. Then, the monomer composition is dispersed in a continuous layer (for example, an aqueous phase) containing a dispersion stabilizer by using an appropriate stirrer, and a polymerization reaction is performed to have a desired particle size. Toner particles are obtained. After the polymerization is completed, the toner of the present invention can be obtained by filtering, washing and drying by a known method, mixing inorganic fine powder and adhering it to the surface.

  When the toner is produced by this suspension polymerization method, since the individual toner particle shapes are substantially spherical, the charge amount distribution is relatively uniform and a toner having satisfactory development characteristics can be easily obtained. Further, it is easy to obtain a toner that maintains a high transferability with little dependence on external additives. Examples of the polymerizable monomer for producing the toner by the suspension polymerization method include the monofunctional polymerizable monomer and the polyfunctional polymerizable monomer.

  The physical property value measuring method of the present invention will be described below.

  The peak molecular weight of the THF solubles of the polymers A and B in the present invention is measured by the following measuring method.

(Preparation of calibration curve polystyrene and measurement sample)
Make 3 L of 30 mol of citric acid monohydrate in THF. A calibration curve sample, a standard product FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) and a measurement sample are prepared. Polystyrene for calibration curve: classified into STD1 to STD4 in the same manner as for normal toner measurement, and polystyrene for calibration curve (standard polystyrene resin (TSK standard polystyrene F-850, F-450, F-288, F-288 manufactured by Tosoh Corporation). , F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500) each) Dissolve 5 mg in 10 ml citric acid solution.
Standard: 20 mg of FCA1001NS is dissolved in 10 ml of citric acid solution.
Measurement sample: 20 mg of sample is dissolved in 10 ml of citric acid solution. The number of samples is limited to 4 in a series of measurements.

(Measurement condition)
Equipment: High-speed GPC “HLC8120 GPC” (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: THF
Flow rate: 1.0 ml / min (1.0 ml at the column side, 0.5 ml at the reference)
Oven temperature: 35.0 ° C
Sample injection volume: 0.10 ml

  The melt viscosity of the toner in the present invention is measured by the following method.

The melt viscosity in the present invention is obtained from the value of the viscosity of the toner by a flow tester heating method. As an apparatus, for example, a flow tester CFT-500D (manufactured by Shimadzu Corporation) is used, and measurement is performed under the following conditions.
Sample: About 1.1 g of toner is weighed, and molded with a pressure molding machine to prepare a sample.
・ Die hole diameter: 0.5mm
-Die length: 1.0mm
・ Cylinder pressure: 9.807 × 10 ⁵ (Pa)
Measurement mode: Temperature rising method Temperature rising rate: 4.0 ° C./min

  The viscosity of the toner at 50 ° C. to 200 ° C. is measured by the above method, and the viscosity at 100 ° C. is obtained.

  In the present invention, the TgL of the toner and the TgA and TgB of the polymers A and B are measured using the modulated mode under the following conditions and obtained from the peak position of the DSC curve at the first temperature increase. An aluminum pan is used as a measurement sample, and an empty pan is set for control and measured.

  The Tg of the present invention uses a value obtained by analyzing the obtained DSC curve by the midpoint method.

<Measurement conditions>
・ Equilibrium at 20 ° C. for 5 minutes ・ Modulation of 1.0 ° C./min is applied and the temperature is raised to 140 ° C. at 1 ° C./min.

  The acid values (mgKOH / g) of the polymers A and B in the present invention are determined according to the following method.

The acid value is obtained from the following calculation formula.
Acid value = [(sample end point−blank end point) × 1.009 × 56 × 1/10] / sample mass

(Sample preparation)
Weigh accurately 1.0 g of sample in a 200 ml beaker, dissolve in 120 ml of toluene while stirring with a stirrer, and add 30 ml of ethanol.

(apparatus)
As an apparatus, for example, an automatic potential difference correction apparatus AT-400WIN is used. The setting of the apparatus is intended for a sample dissolved in an organic solvent. The glass electrode and the comparative electrode to be used should be compatible with organic solvents. For example, product code # 100-H112 is used as the pH glass electrode. Cork type reference electrode uses product code # 100-R115. In addition, the tip of any electrode is never dried. Check if the internal liquid is filled up to the internal liquid replenishment port. As the internal solution, a 3.3 mol / KCL solution is used.

(procedure)
The adjusted sample is set in the autosampler of the apparatus, and the electrode is immersed in the sample solution.

  Next, a titrant (1/10 N KOH (ethanol solution)) is set on the sample solution, and 0.05 ml is added dropwise by automatic intermittent titration to calculate the acid value.

  The number of functional groups (pieces / g) selected from the group consisting of sulfonic acid groups, sulfonic acid groups, and sulfonic acid ester groups contained in the polymers A and B is the same as the amount of sulfur obtained by quantitative analysis. It was calculated as derived from sulfonic acid. Quantitative analysis was performed using a fluorescent X-ray analyzer (RIX3000) and preparing a calibration curve using a known sample whose sulfur content is known by elemental analysis.

  The circularity of the toner in the present invention is calculated by a flow type particle image analyzer.

  The measurement of the present invention uses a flow type particle image measuring apparatus.

  The measurement principle of the flow-type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) is to take a flowing particle as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is subjected to image processing at an image processing resolution of 512 × 512 (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted, Projected area, perimeter, etc. are measured.

  The image signal is A / D converted by the image processing unit, captured as image data, and image processing for determining the presence or absence of particles is performed on the stored image data. Next, contour enhancement processing is performed as preprocessing for accurately extracting the contour of the particle image. Then, the image data is binarized at an appropriate threshold level.

  When the image data is binarized at a certain appropriate threshold level, each particle image becomes a binarized image as shown in FIG. Next, it is determined whether each of the binarized particle images is an edge point (contour pixel representing a contour), and in which direction there is an edge point adjacent to the target edge point. Information, that is, chain code is generated.

  Next, the projected area S and the perimeter L of each particle image are obtained. Using the area S and the perimeter L, the equivalent circle diameter and the circularity are obtained. The circular equivalent diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity is a value obtained by dividing the circumference of the circle obtained from the circular diameter by the circumference of the projected particle image. Defined and calculated by the following formula 2.

  When the particle image is circular, the degree of circularity is 1, and the degree of unevenness on the outer periphery of the particle image increases, and the degree of circularity decreases.

  After calculating the circularity of each particle, the range of the circularity of 0.2 to 1.0 is divided into 800, and the average circularity is calculated using the center value of the dividing points and the number of measured particles.

  As a specific measurement method, 10 ml of ion-exchanged water from which impure solids and the like have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a dispersing means, an ultrasonic disperser UH-50 type (manufactured by SMT Co., Ltd.) having a φ5 mm titanium alloy chip as a vibrator is used and subjected to a dispersion treatment for 5 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not become 40 degree | times or more.

  The weight average particle diameter and toner particle diameter before and after heating and stirring in the present invention are measured with a Coulter counter.

  Measurement of particle size distribution of toner: As a measuring device, for example, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Co.) is used. As the electrolyte, first grade sodium chloride is used to prepare an approximately 1% NaCl aqueous solution. For example, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the above electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles are measured for each channel by using the above-described measuring apparatus using a 100 μm aperture as an aperture. The toner volume distribution and number distribution are calculated. A weight-average toner weight average particle diameter D4 (μm) obtained from the volume distribution of toner particles is obtained (the median value of each channel is a representative value for each channel).

  Channels are 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00 to 40.30 μm are used.

  The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way.

  First, the image forming method of the present invention will be described with reference to FIGS.

  The configuration of the image forming apparatus including the image forming method of this embodiment is shown in FIG. The image forming apparatus of this example is a laser beam printer using a transfer type electrophotographic process.

  FIG. 2 is a sectional view of a tandem type color LBP (color laser printer) as an example of an image forming apparatus used in the image forming method according to the present invention.

  In FIG. 2, reference numeral 101 (101a to 101d) denotes a drum-type electrophotographic photosensitive member (hereinafter referred to as a photosensitive drum) as a latent image carrier that rotates in a direction indicated by an arrow (counterclockwise) at a predetermined process speed. The photosensitive drums 101a, 101b, 101c, and 101d respectively share the yellow (Y) component, magenta (M) component, cyan (C) component, and black (Bk) component of the color image. These photosensitive drums 101a to 101d are rotationally driven by a drum motor (DC servo motor) (not shown), but independent driving sources may be provided for the respective photosensitive drums 101a to 101d. The rotational drive of the drum motor is controlled by a DSP (digital signal processor) (not shown), and other controls are performed by a CPU (not shown).

  The electrostatic adsorption conveyance belt 109a is stretched around a driving roller 109b, fixed rollers 109c and 109e, and a tension roller 109d. The electrostatic adsorption conveyance belt 109a is rotationally driven by the driving roller 109b in the direction of the arrow in the figure to adsorb and convey the recording medium S. To do.

  Hereinafter, yellow (Y) of the four colors will be described as an example.

  The photosensitive drum 101a is uniformly charged to a predetermined polarity and potential by the primary charging means 102a during its rotation. The photosensitive drum 101a is exposed to a light image by a laser beam exposure means (hereinafter referred to as a scanner) 103a, and an electrostatic latent image of image information is formed on the photosensitive drum 101a.

  Next, a toner image is formed on the photosensitive drum 101a by the developing unit 104a, and the electrostatic latent image is visualized. Similar steps are performed for the other three colors (magenta (B), cyan (C), and black (Bk)).

  Thus, the four color toner images are synchronized with the photosensitive drums 101a to 101d by the registration rollers 108c that stop and re-transport the recording medium S conveyed by the paper feed roller 108b at a predetermined timing. The toner images are sequentially transferred onto the recording medium S at the nip portion with the belt 109a. At the same time, the photosensitive drums 101a to 101d after the transfer of the toner image to the recording medium S are subjected to repeated image formation by removing residual deposits such as transfer residual toner by the cleaning means 106a, 106b, 106c and 106d. .

  The recording medium S on which the toner images are transferred from the four photosensitive drums 101a to 101d is separated from the surface of the electrostatic attraction / conveyance belt 109a by the driving roller 109b and sent to the fixing device 110, and the toner image is fixed by the fixing device 110. Then, the sheet is discharged to the discharge tray 113 by the discharge roller 110c.

  Next, a specific example of an image forming method using a non-magnetic one-component contact developing method applied as the present invention will be described with reference to an enlarged view of the developing portion (FIG. 1). In FIG. 1, the developing unit 13 is located in a developer container 23 containing a nonmagnetic toner 17 as a one-component developer, and an opening extending in the longitudinal direction in the developer container 23. A photosensitive drum) 10 and a toner carrier 14 disposed opposite to each other, and the electrostatic latent image on the latent image carrier 10 is developed and visualized. The latent image carrier contact charging member 11 is in contact with the latent image carrier 10. The bias of the latent image carrier contact charging member 11 is applied by a power source 12.

  The toner carrier 14 is horizontally provided with the substantially right half-periphery surface shown in the drawing through the opening into the developer container 23 and the left substantially half-periphery surface exposed outside the developer container 23. The surface exposed to the outside of the developer container 23 is in contact with the latent image carrier 10 located on the left side of the developing unit 13 as shown in FIG.

  The toner carrier 14 is rotationally driven in the direction of arrow B, the peripheral speed of the latent image carrier 10 is 50 to 170 mm / s, and the peripheral speed of the toner carrier 14 is 1 to 2 with respect to the peripheral speed of the latent image carrier 10. It is rotating at twice the peripheral speed.

  At a position above the toner carrier 14, a metal plate such as SUS, a rubber material such as urethane or silicone, a metal thin plate of SUS or phosphor bronze having spring elasticity, and a contact surface side to the toner carrier 14. A restricting member 16 made of a rubber material and the like is supported on the restricting member support metal plate 24 and is provided so that the vicinity of the free end side is in contact with the outer peripheral surface of the toner carrying member 14 by surface contact. The contact direction is a so-called counter direction in which the tip side with respect to the contact portion is located upstream of the rotation direction of the toner carrier 14. As an example of the regulating member 16, a plate-like urethane rubber having a thickness of 1.0 mm is bonded to the regulating member support sheet metal 24, and the contact pressure (linear pressure) with respect to the toner carrier 14 is appropriately set. is there. The contact pressure is preferably 20 to 300 N / m. The measurement of the contact pressure is converted from a value obtained by inserting three metal thin plates with known friction coefficients into the contact portion and pulling out the central one with only a spring. The regulating member 16 having a rubber material or the like bonded to the abutting surface is desirable in terms of adhesion to the toner, and can suppress the fusion and fixing of the toner to the regulating member in long-term use. Further, the restricting member 16 may be in contact with the toner carrier 14 by edge contact in which the tip is contacted. In the case of edge contact, it is more desirable in terms of toner layer regulation to set the contact angle of the regulating member with respect to the tangent of the toner carrying body at the contact with the toner carrying body to be 40 degrees or less.

  The toner supply roller 15 is in contact with the contact portion of the regulating member 16 with the surface of the toner carrier 14 on the upstream side in the rotation direction of the toner carrier 14 and is rotatably supported. The contact width of the toner supply roller 15 with respect to the toner carrier 14 is preferably 1 to 8 mm, and it is preferable that the toner carrier 14 has a relative speed at the contact portion.

  The charging roller 29 is not essential for the image forming method of the present invention, but is preferably installed. The charging roller 29 is an elastic body such as NBR or silicone rubber, and is attached to the suppression member 30. The contact load of the charging roller 29 on the toner carrier 14 by the suppressing member 30 is set to 0.49 to 4.9N. Due to the contact of the charging roller 29, the toner layer on the toner carrier 14 is finely filled and uniformly coated. The longitudinal positional relationship between the regulating member 16 and the charging roller 29 is preferably arranged so that the charging roller 29 can reliably cover the entire contact area of the regulating member 16 on the toner carrier 14.

  Further, for the driving of the charging roller 29, a driven or the same peripheral speed is indispensable between the charging roller 29 and the toner carrier 14, and if a peripheral speed difference occurs between the charging roller 29 and the toner carrier 14, the toner coat becomes uneven. This is not preferable because unevenness occurs on the image.

  The bias of the charging roller 29 is applied by a power source 27 between the toner carrier 14 and the latent image carrier 10 in a direct current (27 in FIG. 1), and the nonmagnetic toner 17 on the toner carrier 14 is charged by the charging roller. From 29, charge is applied by discharge.

  The bias of the charging roller 29 is a bias equal to or higher than the discharge start voltage having the same polarity as that of the nonmagnetic toner, and is set so that a potential difference of 1000 to 2000 V is generated with respect to the toner carrier 14.

  After being charged by the charging roller 29, the toner layer formed as a thin layer on the toner carrier 14 is uniformly conveyed to a developing unit that is a portion facing the latent image carrier 10.

  In this developing unit, the toner layer formed as a thin layer on the toner carrier 14 is transferred to the latent image by a DC bias applied between the toner carrier 14 and the latent image carrier 10 by the power source 27 shown in FIG. The electrostatic latent image on the carrier 10 is developed as a toner image.

  A method for producing toner particles will be described below. Incidentally, all parts and percentages in the examples and comparative examples are based on mass unless otherwise specified.

  Hereinafter, production examples of the polymers A to B will be described.

(Production Example 1 of Polymer A)
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts by mass of methanol as a solvent, 150 parts by mass of 2-butanone and 100 parts by mass of 2-propanol, As a monomer, 95.0 parts by mass of styrene, 2.0 parts by mass of methyl methacrylate, 2.0 parts by mass of methacrylic acid and 1.0 part by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and refluxed while stirring. Until heated. A solution obtained by diluting 1 part by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours to complete the process. In this way, Polymer 1A was produced. Peak molecular weight Mp = 23000, glass transition temperature Tg = 85 ° C., acid value = 8.0, Mw / Mn = 2.1. The total content S (A) of the functional group selected from the group consisting of sulfonic acid group, sulfonic acid group or sulfonic acid ester group of the polymer 1A was 3.2 × 10 ¹⁹ / g. .

(Production Example 2 of Polymer A)
Among the monomers in the production example of the polymer 1A, 2-acrylamido-2-methylpropanesulfonic acid is a sulfonic acid group, sulfonate group or R ¹ = Me, R ² = Ph, R ³ = Me A polymer 2A was produced in the same manner except that 1.0 part by mass of the monomer having a sulfonate group was added. Peak molecular weight Mp = 25000, glass transition temperature Tg = 84 ° C., acid value = 9.0, and Mw / Mn = 2.1. The total content S (A) of the functional groups selected from the group consisting of sulfonic acid groups, sulfonic acid groups, or sulfonic acid ester groups in the polymer 2A was 3.2 × 10 ¹⁹ / g. .

(Production Example 3 of Polymer A)
In the production example of the polymer 1A, as monomers, 93.0 parts by mass of styrene, 1.5 parts by mass of methyl methacrylate, 2.0 parts by mass of methacrylic acid, 3.0 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid A polymer 3A having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group was produced in the same manner except that was added. Peak molecular weight Mp = 20000, glass transition temperature Tg = 83 ° C., acid value = 15.0, Mw / Mn = 2.1. The total content S (A) of the functional group selected from the group consisting of sulfonic acid group, sulfonic acid group or sulfonic acid ester group in the polymer 3A was 9.6 × 10 ¹⁹ / g. .

(Production Example 4 of Polymer A)
In the production example of the polymer 1A, 94.0 parts by mass of styrene, 1.5 parts by mass of methyl methacrylate, 1.5 parts by mass of methacrylic acid, and 0.3 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid are used as monomers. Polymer 4A was produced in the same manner except that was added. Peak molecular weight Mp = 27000, glass transition temperature Tg = 86 ° C., acid value = 4.0, Mw / Mn = 2.1. The total content S (A) of functional groups selected from the group consisting of sulfonic acid groups, sulfonic acid groups or sulfonic acid ester groups in the polymer 4A was 0.96 × 10 ¹⁹ / g. .

(Production Example 5 of Polymer A)
In the production example of the polymer 1A, a solution obtained by diluting 5 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes and stirred for 5 hours. Was finished. Similarly, Polymer 5A was produced. Peak molecular weight Mp = 14000, glass transition temperature Tg = 84 ° C., acid value = 10.0, and Mw / Mn = 2.1. The total content S (A) of the functional group selected from the group consisting of sulfonic acid group, sulfonic acid group or sulfonic acid ester group in the polymer 5A was 9.6 × 10 ¹⁹ / g. .

(Production Example 6 of Polymer A)
In the production example of the polymer 1A, except that 79.0 parts by mass of styrene, 10 parts by mass of methyl methacrylate, 10 parts by mass of methacrylic acid, and 1.0 part by mass of 2-acrylamido-2-methylpropanesulfonic acid are added as monomers. In the same manner, a polymer 6A was produced. Peak molecular weight Mp = 15000, glass transition temperature Tg = 79 ° C., acid value = 31.0, and Mw / Mn = 2.1. In addition, the total content S (A) of the functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group in the polymer 6A was 3.2 × 10 ¹⁹ / g. .

(Production Example 7 of Polymer A)
In the production example of the polymer 1A, as monomers, 95.0 parts by mass of styrene, 2.0 parts by mass of methyl methacrylate, 2.0 parts by mass of methacrylic acid, 0.5 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid A polymer 7A having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group was produced in the same manner except that was added. Peak molecular weight Mp = 23000, glass transition temperature Tg = 88 ° C., acid value = 8.5, and Mw / Mn = 2.1. In addition, the total content S (A) of the functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group in the polymer 7A was 1.6 × 10 ¹⁹ / g. .

(Production Example 8 of Polymer A)
In the production example of the polymer 1A, as monomers, 94.0 parts by mass of styrene, 2.0 parts by mass of methyl methacrylate, 2.0 parts by mass of methacrylic acid, 2.0 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid A polymer 8A having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group was produced in the same manner except that was added. Peak molecular weight Mp = 21000, glass transition temperature Tg = 82 ° C., acid value = 12.0, and Mw / Mn = 1.9. The total content S (A) of the functional group selected from the group consisting of sulfonic acid group, sulfonic acid group or sulfonic acid ester group in the polymer 8A was 6.4 × 10 ¹⁹ / g. .

(Production Example 1 of Polymer B)
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts by mass of methanol as a solvent, 150 parts by mass of 2-butanone and 100 parts by mass of 2-propanol, 80 parts by mass of styrene, 13.5 parts by mass of 2-ethylhexyl acrylate, and 6.5 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added as monomers and heated to the reflux temperature while stirring.

A solution obtained by diluting 1 part by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts by mass of 2-butanone was added dropwise over 30 minutes, and stirring was continued for 5 hours to complete the process. In this way, Polymer 1B was produced. Peak molecular weight Mp = 26000, glass transition temperature Tg = 80 ° C., acid value = 16.0, and Mw / Mn = 2.1. The total content S (B) of the functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group in the polymer 1B was 20.8 × 10 ¹⁹ / g. .

(Production Example 2 of Polymer B)
In the production example of the polymer 1B, except that 83.0 parts by mass of styrene, 13.0 parts by mass of 2-ethylhexyl acrylate, and 4.0 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid are added as monomers. Thus, a polymer 2B was produced. Peak molecular weight Mp = 30000, glass transition temperature Tg = 83 ° C., acid value = 4.0, Mw / Mn = 2.1. The total content S (B) of the functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group in the polymer 2B was 12.8 × 10 ¹⁹ / g. .

(Production Example 3 of Polymer B)
In the production example of the polymer 1B, except that 70.0 parts by mass of styrene, 19.0 parts by mass of 2-ethylhexyl acrylate, and 11.0 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added as monomers. Thus, a polymer 3B was produced. Peak molecular weight Mp = 15000, glass transition temperature Tg = 84 ° C., acid value = 45.0, Mw / Mn = 2.1. The total content S (B) of functional groups selected from the group consisting of sulfonic acid groups, sulfonic acid groups, or sulfonic acid ester groups in the polymer 3B was 35.2 × 10 ¹⁹ / g. .

(Production Example 4 of Polymer B)
In the production example of the polymer 1B, a polymer 4B was produced in the same manner except that the addition amount of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was 5.0 parts by mass. Peak molecular weight Mp = 9000, glass transition temperature Tg = 75 ° C., acid value = 20.0, and Mw / Mn = 2.0. The total content S (B) of functional groups selected from the group consisting of sulfonic acid groups, sulfonic acid groups or sulfonic acid ester groups in the polymer 4B was 16.0 × 10 ¹⁹ / g. .

(Production Example 5 of Polymer B)
In the production example of the polymer 1B, except that 70.0 parts by mass of styrene, 23.0 parts by mass of 2-ethylhexyl acrylate, and 7.0 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid are added as monomers. Thus, polymer 5B was produced. Peak molecular weight Mp = 14000, glass transition temperature Tg = 63 ° C., acid value = 35.0, and Mw / Mn = 1.9. The total content S (B) of the functional groups selected from the group consisting of sulfonic acid groups, sulfonic acid groups, or sulfonic acid ester groups in the polymer 5B was 22.4 × 10 ¹⁹ / g. .

(Production Example 6 of Polymer B)
In the production example of the polymer 1B, heavy weight was similarly obtained except that 80 parts by mass of styrene, 15.0 parts by mass of 2-ethylhexyl acrylate, and 5.0 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added as monomers. Combined 6B was produced. Peak molecular weight Mp = 20000, glass transition temperature Tg = 83 ° C., acid value = 13.0, Mw / Mn = 1.9. The total content S (B) of functional groups selected from the group consisting of sulfonic acid groups, sulfonic acid groups or sulfonic acid ester groups in the polymer 6B was 16.0 × 10 ¹⁹ / g. .

(Production Example 7 of Polymer B)
In the production example of the polymer 1B, heavy weight was similarly obtained except that 75 parts by mass of styrene, 15.0 parts by mass of 2-ethylhexyl acrylate, and 10.0 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added as monomers. Combined 7B was produced. Peak molecular weight Mp = 18000, glass transition temperature Tg = 75 ° C., acid value = 38.0, and Mw / Mn = 1.9. The total content S (B) of the functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group in the polymer 7B was 32.0 × 10 ¹⁹ / g. .

  Examples of toner production will be described below.

(Toner Production Example 1)
A polymerized toner was produced according to the following procedure. To 1300 parts by mass of ion-exchanged water heated to 60 ° C., 9 parts by mass of tricalcium phosphate and 11 parts by mass of 10% hydrochloric acid are added, and 10,000 r using a TK type homomixer (manufactured by Special Machine Industries). The aqueous medium was prepared by stirring at / min.

Moreover, the following polymerizable monomer composition was obtained with a propeller type stirrer at 100 r / min.
Styrene ... 70 mass parts n-butyl acrylate ... ... 30 parts by weight polymer 1A ... 20 parts by weight Combined 1B ... 3 parts by mass

Next, in the above solution,
C. I. Pigment Blue 15: 3 ···················· 7 parts by mass Aluminum salicylate compound (Bontron E-88: manufactured by Orient Chemical Co.) 1 part by mass stearyl stearate (melting point) After adding 15 parts by mass, the mixture was heated to 60 ° C. with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) and then 9,000 r / min. In the aqueous medium, the polymerizable monomer composition is charged and stirred at 11000 r / min using a TK homomixer in a nitrogen atmosphere at 60 ° C. Granulated. In this, 5 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved.

  Thereafter, the mixture was transferred to a propeller type agitator and stirred at 100 r / min. After 7 hours, the temperature was raised to 80 ° C., and the reaction was further continued for 5 hours to produce toner particles. After the completion of the polymerization reaction, the slurry containing the particles was cooled, washed with an amount of water 10 times that of the slurry, filtered and dried, and then the particle diameter was adjusted by classification to obtain cyan toner particles.

Hydrophobic silica fine powder (primary particle diameter: 10 nm, BET specific surface area) treated with silicone oil as an inorganic fine powder and charged to the same polarity (negative polarity) as the toner particles with respect to 100 parts by mass of the cyan toner particles : 170 m ^{2 /} g) Cyan toner 1 was obtained by mixing 2.0 parts by mass with a Henschel mixer (Mitsui Miike) for 5 minutes. The physical properties of cyan toner 1 are shown in Tables 1 and 2.

(Toner Production Example 2)
Cyan toner 2 was obtained in the same manner as cyan toner 1 except that the amount of polymer 1A added was changed to 10.0 parts by mass in toner production example 1. The physical properties of Cyan Toner 2 are shown in Tables 1 and 2.

(Toner Production Example 3)
Cyan toner 3 was obtained in the same manner as cyan toner 1, except that the amount of polymer 1A added was changed to 30.0 parts by mass in toner production example 1. The physical properties of cyan toner 3 are shown in Tables 1 and 2.

(Toner Production Example 4)
Cyan toner 4 was obtained in the same manner as cyan toner 1, except that the amount of polymer 1B added was changed to 0.5 parts by mass in toner production example 1. The physical properties of cyan toner 4 are shown in Tables 1 and 2.

(Toner Production Example 5)
Cyan toner 5 was obtained in the same manner as cyan toner 1 except that the amount of polymer 1B added was changed to 5.0 parts by mass in toner production example 1. The physical properties of cyan toner 5 are shown in Tables 1 and 2.

(Toner Production Example 6)
Cyan toner 6 was obtained in the same manner as cyan toner 1 except that the polymer 1A was changed to 7A in toner production example 1. The physical properties of cyan toner 10 are shown in Tables 1 and 2.

(Toner Production Example 7)
A cyan toner 7 was obtained in the same manner as in the cyan toner 1 except that the polymer 1A was changed to 8A in the toner production example 1. The physical properties of cyan toner 7 are shown in Tables 1 and 2.

(Toner Production Example 8)
Cyan toner 8 was obtained in the same manner as cyan toner 1 except that the polymer 1B was switched to 6B in toner production example 1. The physical properties of cyan toner 8 are shown in Tables 1 and 2.

(Toner Production Example 9)
A cyan toner 9 was obtained in the same manner as the cyan toner 1 except that the polymer 1B was changed to 7B in the toner production example 1. The physical properties of cyan toner 9 are shown in Tables 1 and 2.

(Toner Production Example 10)
A cyan toner 10 was obtained in the same manner as the cyan toner 1 except that the polymer 1A was changed to 2A in the toner production example 1. The physical properties of cyan toner 10 are shown in Tables 1 and 2.

(Toner Production Example 11)
A cyan toner 11 was obtained in the same manner as in the cyan toner 1 except that the polymer 1A was changed to 5A in the toner production example 1. The physical properties of the cyan toner 11 are shown in Tables 1 and 2.

(Toner Production Example 12)
A cyan toner 12 was obtained in the same manner as the cyan toner 1 except that the polymer 1A was changed to 6A in the toner production example 1. The physical properties of the cyan toner 12 are shown in Tables 1 and 2.

(Toner Production Example 13)
A cyan toner 13 was obtained in the same manner as the cyan toner 1 except that the polymer 1B was changed to 4B in the toner production example 1. The physical properties of the cyan toner 13 are shown in Tables 1 and 2.

(Toner Production Example 14)
A cyan toner 14 was obtained in the same manner as in the cyan toner 1 except that the polymer 1B was changed to 5B in the toner production example 1. The physical properties of the cyan toner 14 are shown in Tables 1 and 2.

(Toner Production Example 15)
A cyan toner 15 was obtained in the same manner as in the cyan toner 1 except that the styrene was 79 parts by mass and the n-butyl acrylate was 21 parts by mass in Toner Production Example 1. The physical properties of the cyan toner 15 are shown in Tables 1 and 2.

(Toner Production Example 16)
27 parts by mass of tricalcium phosphate and 33 parts by mass of 10% hydrochloric acid are added to 1300 parts by mass of ion-exchanged water heated to 60 ° C. in Toner Production Example 1, and a TK homomixer (manufactured by Special Machine Industries) is used. The aqueous medium was prepared by stirring at 10,000 r / min. Otherwise, cyan toner 16 was obtained in the same manner as cyan toner 1. The physical properties of the cyan toner 16 are shown in Tables 1 and 2.

(Toner Production Example 17)
In the toner production example 1, granulation was performed in the same manner as cyan toner 1, reacted at 70 ° C. for 4 hours, stirred for 10 minutes at 10,000 r / min using a TK homomixer, and then heated to 80 ° C. Further, the reaction was carried out for 5 hours to produce toner particles. Except for the above, cyan toner 17 was obtained in the same manner as cyan toner 1. The physical properties of cyan toner 17 are shown in Tables 1 and 2.

(Toner Production Example 18)
A cyan toner 18 was obtained in the same manner as in the cyan toner 1 except that the polymer 1A was changed to 3A and the addition amount was 15 parts by mass in Toner Production Example 1. The physical properties of the cyan toner 18 are shown in Tables 1 and 2.

(Toner Production Example 19)
A cyan toner 19 was obtained in the same manner as the cyan toner 1 except that the polymer 1A was changed to 4A in the toner production example 1. The physical properties of the cyan toner 19 are shown in Tables 1 and 2.

(Toner Production Example 20)
A cyan toner 20 was obtained in the same manner as the cyan toner 1 except that the amount of the polymer 1A added was changed to 5 parts by mass in Toner Production Example 1. The physical properties of the cyan toner 20 are shown in Tables 1 and 2.

(Toner Production Example 21)
A cyan toner 21 was obtained in the same manner as the cyan toner 1 except that the amount of the polymer 1A added was changed to 35 parts by mass in Toner Production Example 1. The physical properties of cyan toner 21 are shown in Tables 1 and 2.

(Toner Production Example 22)
A cyan toner 22 was obtained in the same manner as the cyan toner 1 except that the amount of the polymer 1A added was changed to 0.2 parts by mass in Toner Production Example 1. The physical properties of the cyan toner 22 are shown in Tables 1 and 2.

(Toner Production Example 23)
A cyan toner 23 was obtained in the same manner as the cyan toner 1 except that the amount of the polymer 1B added was changed to 7.0 parts by mass in Toner Production Example 1. The physical properties of the cyan toner 23 are shown in Tables 1 and 2.

(Toner Production Example 24)
A cyan toner 24 was obtained in the same manner as in the cyan toner 1 except that the polymer 1B was switched to 2B in the toner production example 1. The physical properties of the cyan toner 24 are shown in Tables 1 and 2.

(Toner Production Example 25)
A cyan toner 25 was obtained in the same manner as the cyan toner 1 except that the polymer 1B was changed to 3B in the toner production example 1. The physical properties of the cyan toner 25 are shown in Tables 1 and 2.

(Toner Production Example 26)
A cyan toner 26 was obtained in the same manner as the cyan toner 26 except that the polymer 1A was changed to 3A and the polymer 1B was changed to 2B in the toner production example 1. The physical properties of the cyan toner 26 are shown in Tables 1 and 2.

(Toner Production Example 27)
Binder resin (styrene-acrylic resin glass transition point Tg 80 ° C.) .. 100 parts by mass C.I. I. Pigment Blue 15: 3 ······································································· 7 parts by mass Polymer 1B having a mass part sulfonic acid group, a sulfonate group or a sulfonic acid ester group 3 parts by mass stearyl wax stearate (melting point 62 ° C.) .... 5 mass parts The said mixture was melt-kneaded with the biaxial extruder heated at 125 degreeC, and the cooled kneaded material was coarsely ground with the hammer mill.

  The coarsely pulverized product was pulverized and classified using a turbo mill T-250 type manufactured by Turbo Kogyo Co., Ltd., which is a mechanical pulverizer, to obtain cyan toner particles.

Hydrophobic silica fine powder (primary particle diameter: 10 nm, BET specific surface area) treated with silicone oil as an inorganic fine powder and charged to the same polarity (negative polarity) as the toner particles with respect to 100 parts by mass of the cyan toner particles : 170 m ^{2 /} g) Cyan toner 27 was obtained by mixing 2.0 parts by mass with a Henschel mixer (Mitsui Miike) for 5 minutes. The physical properties of the cyan toner 27 are shown in Tables 1 and 2.

(Toner Production Example 28)
A cyan toner 28 was obtained in the same manner as in the cyan toner 1 except that the polymer 1B was not added in Toner Production Example 1. The physical properties of the cyan toner 28 are shown in Tables 1 and 2.

(Toner Production Example 29)
A cyan toner 29 was obtained in the same manner as in the cyan toner 1 except that the polymer 1A was not added in Toner Production Example 1. The physical properties of the cyan toner 29 are shown in Tables 1 and 2.

(Toner Production Example 30)
In Toner Production Example 1, C.I. I. Pigment Blue 15: 3 to C.I. I. A yellow toner 1 was obtained in the same manner as the cyan toner 1 except that the pigment yellow 180 was changed to 7 parts. The physical properties of yellow toner 1 are shown in Tables 1 and 2.

(Toner Production Example 31)
In Toner Production Example 1, C.I. I. Pigment Blue 15: 3 to C.I. I. A magenta toner 1 was obtained in the same manner as the cyan toner 1 except that the pigment red 122 was changed to 10 parts. The physical properties of magenta toner 1 are shown in Tables 1 and 2.

(Toner Production Example 32)
In Toner Production Example 1, C.I. I. Black toner 1 was obtained in the same manner as cyan toner 1 except that the amount of carbon black was changed to 8 parts from pigment blue 15: 3. The physical properties of the black toner 1 are shown in Tables 1 and 2.

(Toner Production Example 33)
In Toner Production Example 26, C.I. I. Pigment Blue 15: 3 to C.I. I. A yellow toner 2 was obtained in the same manner as the cyan toner 27 except that the pigment yellow 180 was changed to 7 parts. The physical properties of yellow toner 2 are shown in Tables 1 and 2.

(Toner Production Example 34)
In Toner Production Example 26, C.I. I. Pigment Blue 15: 3 to C.I. I. A magenta toner 2 was obtained in the same manner as the cyan toner 27 except that the pigment red 122 was changed to 10 parts. The physical properties of magenta toner 2 are shown in Tables 1 and 2.

(Toner Production Example 35)
In Toner Production Example 26, C.I. I. Black toner 2 was obtained in the same manner as cyan toner 27 except that the pigment black 15: 3 was changed to 8 parts of carbon black. The physical properties of the black toner 2 are shown in Tables 1 and 2.

[Examples 1 to 18, Comparative Examples 1 to 13]
The toner particles described in Tables 1 and 2 were subjected to image evaluation using the combinations described in Table 3.

  The evaluation method and evaluation criteria of the present invention will be described below.

  In the image forming apparatus of the contact city component development system shown in FIG. 2, 200 g of the toners described in Examples and Comparative Examples were filled in the developer shown in FIG. In addition, when evaluating monocolor with cyan toner, the LBP remodeling machine switched to monochrome output and evaluated the image. Evaluation was performed by inserting magenta, yellow, and black cartridges in which the toner remaining amount detection mechanism was disabled. Thereafter, density detection correction is performed, and continuous output is performed using a chart with a printing ratio of 1%. When the total number of output sheets was 10,000 sheets (manufactured by Xerox Co., Ltd., LETTER size, 75 g paper), images were evaluated in each environment. Specifically, it was examined in a high temperature and high humidity environment (30 ° C., 80 RH%), a normal temperature and normal humidity environment (20 ° C., 60 RH%), and a low temperature low humidity environment (10 ° C., 20% RH). The evaluation results are shown in Table 4.

(1) Evaluation of developability (a) Image density reduction rate 10 solid whole area images (toner applied amount 0.55 mg / cm ² ) are output, and the image density reduction rates of the first and tenth images are measured.
Density reduction rate = (first image density−tenth image density) / (first image density) × 100

The image evaluation conforms to the following judgments A, B, C, and D.
A: The concentration reduction rate is less than 5%, and there is no problem in practical use.
B: Concentration reduction rate of 5% or more and less than 10%, a level that is not problematic in actual use.
C: A concentration reduction rate of 10% or more and less than 15%, which is a low possibility of causing a problem in actual use.
D: Concentration reduction rate of 15% or more, which is highly likely to cause a problem in actual use.

(B) Halftone uniformity When confirming halftone uniformity, half-tone image (toner applied amount 0.20 mg / cm ² ) was forcibly turned off during development and developed. The dot reproducibility on the photosensitive drum was confirmed. Evaluation was performed while visually observing an image magnified 100 times with an optical microscope. The criteria are shown below.
A: The dot reproducibility is good and there is no problem in actual use.
B: Although there is some disturbance in dot reproducibility, there is no problem in practical use.
C: A level in which the dot reproducibility is slightly disturbed but is not likely to cause a problem in actual use.
D: A level at which the dot reproducibility is largely disturbed and is likely to cause a problem in use.

(2) Evaluation of Member Adhesion (a) Drum Fusion Evaluate the stain on the white part on the image due to contamination of the photoreceptor. On the output image, the stain on the image in an arbitrary 2 × 2 cm square was visually evaluated.
A: There are no spots.
B: There are 1 to 4 spots.
C: There are 5 to 9 spots.
D: There are 10 or more spots. There are practical problems.

(B) Contamination of toner carrier When confirming circumferential streaks and toner scattering, after outputting one solid whole image (toner loading amount of 0.55 mg / cm ² ), the developer container is disassembled and the toner carrier The surface and end of the body were visually observed. The criteria are shown below.
A: The surface and edges of the toner carrier have no circumferential streak due to toner destruction or fusing, and the surface of the toner carrier is not at all scratched.
B: The surface and edges of the toner carrier have slight streaks in the circumferential direction due to toner destruction and fusion, and scraping of the toner carrier surface, which is a level at which there is no problem in practical use.
C: The surface and edges of the toner carrier have some circumferential streaks due to toner destruction and fusion, and the surface of the toner carrier is scraped slightly, and 1 to 10 circumferential streaks can be seen at the edges. A level that is unlikely to cause a problem in actual use.
D: Toner is fused in the circumferential direction on the surface of the toner carrying member, and the end of the carrying member is shaved and the toner leaks. Highly likely to cause problems in actual use.

(C) Contamination of regulating member When confirming circumferential streaks and toner scattering, after outputting one halftone whole area image (toner loading amount 0.20 mg / cm ² ), the developing container is disassembled and the regulating member is disassembled. Was performed visually. It was visually evaluated whether or not fine vertical stripes occurred in any 2 × 2 cm square on the halftone image. The criteria are shown below.
A: There is no fused toner material on the regulating member, and there are no streaks on the image.
B: Although there are some toner fusion products on the regulating member, there are no streaks on the image. There are 1 to 4 streaks.
C: There is a toner fusion product on the regulating member, and there are 1 to less than 10 streaks on the image, but the level that is not likely to cause a problem in actual use.
D: There is a toner melt on the regulating member, and there are 10 or more streaks on the image, which is problematic in practical use.

(3) Transferability Evaluation (a) Transfer Uniformity When measuring transfer efficiency, a half-tone whole image (toner loading amount 0.20 mg / cm ² ) and a solid whole image (toner loading amount 0.55 mg / cm). ² ) One sheet was output and evaluated. The criteria are shown below.
A: The uniformity within one page is excellent for both halftone and solid, and there is no problem in practical use.
B: Although a slightly inferior uniformity in one page is recognized in a halftone image, there is no problem in practical use.
C: Although both halftone and solid are slightly inferior in uniformity within the page, the level is less likely to cause a problem in actual use.
D: Since the uniformity in one page is inferior in both halftone and solid, it is highly likely to cause a problem in actual use.

(4) Fixability Evaluation (a) Fixing Uniformity The machine and the toner-filled cartridge are allowed to stand for 24 hours in a low-temperature and low-humidity environment (15 ° C., 10% RH) for 24 hours. One sheet having a width of 200 μm and an interval of 100 μm was output, and the printed image was used for evaluation of fixability. The fixing property was evaluated by rubbing the image with silver paper for 5 reciprocations with a load of 100 g, and peeling of the image was evaluated by the average of the reduction rate (%) of the reflection density.

For the evaluation, bond paper having a surface smoothness of 10 [sec] or less was used. The evaluation criteria are shown below.
A: Density reduction rate is less than 5%. There is no problem in actual use.
B: Level at which the concentration decrease rate is 5% or more and less than 15%, and there is no problem in practical use.
C: Concentration reduction rate of 15% or more, a level that is unlikely to cause a problem in actual use.
D: A fixing defect has occurred in the evaluation image before rubbing with Sylbon paper

It is an enlarged view of the developing unit of the electrophotographic apparatus. 1 is a cross-sectional view of an electrophotographic apparatus using an image forming method of the present invention. It is a figure which shows an example of the binarized image of a toner particle.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Photosensitive drum 11 Charging roller 13 Developing unit 14 Toner carrier 15 Toner supply roller 16 Control member 17 Toner 23 Developer container 25 Stirring blade 29 Charging roller

Claims (8)

At least the following i) to v)
i) a polymerizable monomer;
ii) waxes;
iii) a colorant;
iv) A polymer obtained by polymerizing at least a polymerizable monomer having a functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, and a sulfonic acid ester group, and another vinyl polymerizable monomer. The copolymerization ratio C (A) of the polymerizable monomer having a functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, and a sulfonic acid ester group is 0.5 to 2.0% by mass. A polymer A;
v) A polymer obtained by polymerizing at least a polymerizable monomer having a functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, and a sulfonic acid ester group, and another vinyl polymerizable monomer. The copolymerization ratio C (B) of the polymerizable monomer having a functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, and a sulfonic acid ester group is 5.0 to 10.0% by mass. A polymer B;
A toner composition prepared by dispersing a monomer composition containing an aqueous medium in a water-based medium and polymerizing a polymerizable monomer contained in the monomer composition. Magnetic toner,
When the content of the polymer A with respect to 100 parts by mass of the polymerizable monomer of i) is M (A) (parts by mass) and the content of the polymer B is M (B) (parts by mass), A nonmagnetic toner characterized by satisfying the following formula:
10.0 ≦ M (A) ≦ 30.0
0.5 ≦ M (B) ≦ 5.0
0.02 ≦ M (B) / M (A) ≦ 0.50 The polymers A and B are the following i) to iii) as copolymerization components:
The nonmagnetic toner according to claim 1, comprising i) styrene ii) 2-acrylamido-2-methylpropanesulfonic acid derivative iii) acrylic acid or methacrylic acid derivative. The polymer A is represented by the following formula (1) as a partial structure derived from a polymerizable monomer having a functional group selected from the group consisting of the sulfonic acid group, sulfonic acid group, and sulfonic acid ester group. The nonmagnetic toner according to claim 1, which has a structure .

(In the formula, R ¹ , R ² and R ³ are any combination of the following.
i) R ¹ is a hydrogen atom, R ² is a 2-methylpropylene group, and R ³ is a hydrogen atom.
ii) R ¹ is a methyl group, R ² is a phenyl group, and R ³ is a methyl group. ) The AV (A) and AV (B) satisfy the following formula, where the acid value of the polymer A is AV (A) and the acid value of the polymer B is AV (B). The nonmagnetic toner according to any one of 3.
5.0 mgKOH / g ≦ AV (A) ≦ 30.0 mgKOH / g
10.0 mgKOH / g ≦ AV (B) ≦ 40.0 mgKOH / g
1.0 ≦ AV (B) / AV (A) ≦ 5.0 The total content S (A) of the functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group in the polymer A is 2.0 × 10 ^{19 to} 8.0 × 10 ^19. Pieces / g,
The total content S (B) of the functional group selected from the group consisting of a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group in the polymer B is 15.0 × 10 ^{19 to} 35.0 × 10 ^19. The nonmagnetic toner according to claim 1, wherein the number of toner particles / g.   6. The nonmagnetic toner according to claim 1, wherein the polymer A has a peak molecular weight of 15,000 to 100,000, and the polymer B has a peak molecular weight of 10,000 to 30,000. The glass transition temperature of the polymer A is TgA, and the glass transition temperature of the polymer B is TgB, and TgA and TgB satisfy the following formulas. Non-magnetic toner.
80.0 ° C ≦ TgA ≦ 120.0 ° C
65.0 ° C ≦ TgB ≦ 95.0 ° C The temperature difference between the glass transition temperature (TgL) existing at 40 to 60 ° C. and the maximum peak temperature (P1) at 70 to 90 ° C. in the differential scanning calorimeter (modulation DSC) of the nonmagnetic toner is expressed by the following formula. Meet,
15.0 ° C ≦ P1-TgL ≦ 50.0 ° C
The nonmagnetic toner according to any one of claims 1 to 7, wherein the toner has a melt viscosity of 2000 to 25000 Pa · s at 100 ° C.

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