JP2023153685A - Toner, image forming apparatus, image forming method, and method for manufacturing printed material - Google Patents

Abstract

To provide a toner that can achieve crushability, low temperature fixability, heat resistance, and durability at high level.SOLUTION: A toner contains at least an amorphous polyester resin, a crystalline polyester resin, wax, and an aromatic petroleum resin. The wax has an SP value of 8.0 or more and 8.5 or less. The wax has a melting point of 80°C or more and 100°C or less. The mass ratio of the crystalline polyester resin to the aromatic petroleum resin is 1.0 or more and 1.2 or less.SELECTED DRAWING: Figure 1

Description

The present invention relates to a toner, an image forming apparatus, an image forming method, and a method for manufacturing printed matter.

In recent years, pulverized toners are required to have excellent pulverization properties due to environmental considerations. In order to improve the crushability, it is necessary to improve not only the manufacturing process but also the materials.
In addition to conventional energy saving, improving low-temperature fixing properties is important for the purpose of suppressing particulate volatile components, and in particular it is necessary to ensure heat-resistant storage and durability in actual machines.
As described above, it is necessary for pulverized toner technology to achieve a high level of pulverizability, low-temperature fixability, heat-resistant storage stability, and durability.

For example, Patent Documents 1, 2, and 4 claim that both pulverizability and low-temperature fixability are achieved by using a low molecular weight thermoplastic resin and controlling the thermophysical properties of the binder resin.
Further, Patent Document 3 states that by using a hydrogenated petroleum resin, both low-temperature fixability and heat-resistant storage stability are achieved.
Further, Patent Document 5 states that a core-shell toner achieves both low-temperature fixability and heat-resistant storage stability.
As another document related to pulverized toner, Patent Document 6 states that a styrene resin having certain physical properties is used to improve low-temperature fixability and heat-resistant storage stability.

An object of the present invention is to provide a toner that can achieve high levels of grindability, low-temperature fixability, heat resistance, and durability.

The above problem is solved by the following configuration 1).
1) A toner containing at least an amorphous polyester resin, a crystalline polyester resin, a wax, and an aromatic petroleum resin,
The SP value of the wax is 8.0 or more and 8.5 or less,
A toner characterized in that the melting point of the wax is 80° C. or more and 100° C. or less, and the ratio of the crystalline polyester resin to the aromatic petroleum resin is 1.0 or more and 1.2 or less in terms of mass ratio.

According to the present invention, it is possible to provide a toner that can achieve high levels of grindability, low-temperature fixability, heat resistance, and durability.

1 is a diagram for explaining an embodiment of an image forming apparatus of the present invention. FIG. 3 is a diagram for explaining another embodiment of the image forming apparatus of the present invention. FIG. 3 is a diagram for explaining another embodiment of the image forming apparatus of the present invention. FIG. 3 is a diagram for explaining an image forming unit.

The present invention will be explained in detail below.
(toner composition)
The toner of the present invention contains at least an amorphous polyester resin, a crystalline polyester resin, a wax, and an aromatic petroleum resin. By containing these materials and satisfying the composition and physical properties described below, it is possible to provide a toner that can achieve high levels of grindability, low-temperature fixability, heat resistance, and durability.

(Amorphous polyester resin)
The amorphous polyester resin used in the toner of the present invention is not particularly limited, and any known amorphous polyester resin can be used. In particular, it is preferable to contain at least bisphenol A and ethylene glycol as diol components. By containing bisphenol A as a diol component, it is possible to ensure good heat resistance as a toner. Furthermore, by containing ethylene glycol as a diol component, good dispersibility with waxes having a low SP value can be maintained. As a result, the durability of the toner can be improved.

The proportion of bisphenol A and ethylene glycol in the diol component of the amorphous polyester resin is preferably 70 to 100% by mass. Further, the ratio (mol %) of bisphenol A and ethylene glycol is preferably 50:50 to 90:10 as the former:the latter.

In addition to bisphenol A and ethylene glycol, monomers constituting the amorphous polyester include the following.
Examples of dihydric alcohol components include 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, or diols obtained by polymerizing bisphenol A with cyclic ethers such as ethylene oxide and propylene oxide. .

As a means for crosslinking the polyester resin, it is also possible to use a trihydric or higher alcohol in combination. Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexantetrol, 1,4-sorbitan, pentaerythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , etc.

Examples of the acid component forming the amorphous polyester include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, or their anhydrides, and alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid. or anhydrides thereof, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride Examples include unsaturated dibasic acid anhydrides such as

In addition, as trivalent or higher polyvalent carboxylic acid components, trimetic acid, pyrometic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra(methylene (carboxy)methane, 1,2,7,8-octane tetracarboxylic acid, Empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

The acid value of the amorphous polyester is preferably 0.1 mgKOH/g to 100 mgKOH/g, more preferably 0.1 mgKOH/g to 70 mgKOH/g, and 0.1 mgKOH/g to 50 mgKOH/g. Most preferably, it is g.

In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.

The content of the amorphous polyester resin in the toner is preferably 60% by mass or more and 90% by mass or less.

(Crystalline polyester resin)
The toner of the present invention contains a crystalline polyester resin. Due to the effect of the crystalline polyester resin, good low-temperature fixability can be ensured.
The melting point of the crystalline polyester resin is preferably 100°C or more and 120°C or less. In crystalline polyester, there is a portion that is not crystallized, and the glass transition temperature thereof increases depending on the melting point. Further, the closer the glass transition temperature of the non-crystallized portion to the glass transition temperature of the amorphous polyester resin, the higher the compatibility and the higher the low-temperature fixability. For the above reasons, it is preferable that the melting point of the crystalline polyester resin is 100°C or higher. However, if the melting point of the crystalline polyester resin is too high, melting due to the amount of heat during fixing will be insufficient, resulting in poor low-temperature fixability. For the above reasons, the melting point of the crystalline polyester resin is preferably 120°C or lower.

The crystalline polyester resin includes (I) a polyvalent carboxylic acid composed of a linear unsaturated aliphatic dicarboxylic acid or a reactive derivative thereof (acid anhydride, lower alkyl ester having 1 to 4 carbon atoms, acid halide, etc.); It can be produced by subjecting an acid component and (II) a polyhydric alcohol component consisting of a linear aliphatic diol to a polycondensation reaction using a conventional method. In this case, a small amount of other polycarboxylic acid can be added to the polycarboxylic acid component, if necessary. In this case, the polyvalent carboxylic acids include (i) unsaturated aliphatic divalent carboxylic acids having branched chains, (ii) saturated aliphatic carboxylic acids such as saturated aliphatic divalent carboxylic acids and saturated aliphatic trivalent carboxylic acids. In addition to polyvalent carboxylic acids, (iii) aromatic polyvalent carboxylic acids such as aromatic divalent carboxylic acids and aromatic trivalent carboxylic acids are included. The amount of these polyhydric carboxylic acids added is usually 30 mol % or less, preferably 10 mol % or less, based on the total carboxylic acids, and is added as appropriate within the range where the resulting polyester has crystallinity.

Specific examples of polyhydric carboxylic acids that can be added as necessary include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. divalent carboxylic acids; trimetic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, Examples include polyvalent carboxylic acids of trivalent or higher valence, such as 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, and 1,2,7,8-octanetetracarboxylic acid. can.

In addition to a small amount of aliphatic branched dihydric alcohol and cyclic dihydric alcohol, a trivalent or higher polyhydric alcohol can be added to the polyhydric alcohol component, if necessary. The amount added is 30 mol % or less, preferably 10 mol % or less, based on the total alcohol, and is added as appropriate within the range where the resulting polyester has crystallinity. Examples of polyhydric alcohols that may be added as necessary include 1,4-bis(hydroxymethyl)cyclohexane, polyethylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, and glycerin.

The crystalline polyester resin preferably has a sharp molecular weight distribution from the viewpoint of low-temperature fixability, and preferably has a relatively low molecular weight. The molecular weight of the crystalline polyester resin is as follows: in the molecular weight distribution of the o-dichlorobenzene soluble portion determined by GPC, the weight average molecular weight (Mw) is 5,500 to 6,500, the number average molecular weight (Mn) is 1,300 to 1,500, and It is preferable that the Mw/Mn ratio is 2 to 5.
The molecular weight distribution of the crystalline polyester resin is based on a molecular weight distribution diagram in which the horizontal axis is logM (M is molecular weight) and the vertical axis is mass %.

In the case of the crystalline polyester resin used in the present invention, it is preferable to have a molecular weight peak in the range of 3.5 to 4.0 (mass%) in this molecular weight distribution diagram, and the half width of the peak is 1.5. It is preferable that it is below.

The content of the crystalline polyester resin in the toner is preferably 5.0% by mass or less. By setting the content to 5.0% by mass or less, it is possible to suppress adhesion to the photoreceptor due to recrystallization after toner formation, and it is possible to suppress the occurrence of image fading.

More preferably, the content of the crystalline polyester resin in the toner is 2.5% by mass or more and 5.0% by mass or less.

(wax)
The toner of the present invention contains wax. In particular, it is preferable that the SP value is 8.0 or more and 8.5 or less and the melting point is 80°C or more and 100°C or less.
By having a wax SP value of 8.0 or more, it is possible to maintain good dispersion of the aromatic petroleum resin described below, and it is possible to achieve both high levels of crushability and low-temperature fixability without causing fixation inhibition. Become. Further, by having a wax SP value of 8.5 or less, compatibility with aromatic petroleum resins can be prevented. As a result, it is possible to achieve a state in which a certain amount of aromatic petroleum resin is dispersed within the toner, and it is possible to ensure good crushability even when a certain amount of crystalline polyester is used. become.

By having a wax melting point of 80°C or higher, it is possible to make the thermal properties similar to those of aromatic petroleum resins and crystalline polyesters. As a result, these materials can be plasticized during heating, and good low-temperature fixability can be ensured. Further, since the melting point of the wax is 100° C. or lower, it is possible to prevent poor mold release properties due to insufficient melting of the wax during heating, and it is also possible to ensure good low-temperature fixing properties.

Any known type of wax can be used as long as the SP value and melting point can be maintained within the above-mentioned levels. Examples include Fischer-Tropsch wax and microcrystalline wax, with Fischer-Tropsch wax being particularly preferred. Fischer-Tropsch wax has a high melting point and a sharp molecular weight distribution, so it has excellent heat resistance and durability.

The amount of wax added in the toner is preferably 2.5% by mass or more and 6.5% by mass or less, particularly preferably 3.5% by mass or more and 5.5% by mass or less. By controlling the amount of wax added to 3.5% by mass or more and 5.5% by mass or less, deterioration in durability due to excessive wax can be suppressed while ensuring mold releasability.

Note that the melting point of wax can be measured by the following method.
The glass transition temperature and melting point were measured using a thermal analysis workstation TA-60WS and a differential scanning calorimeter DSC-60 (manufactured by Shimadzu Corporation) under the conditions shown below.
Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50ml/min)
Temperature raising/lowering conditions: As follows Starting temperature: 20°C
Temperature increase rate: 10℃/min
End temperature: 150℃
Holding time: None Cooling rate: 10℃/min
End temperature: 20℃
Holding time: None Heating rate: 10℃/min
(The endothermic peak observed during this temperature raising process was adopted as the melting point.)
End temperature: 150℃

(Aromatic petroleum resin)
The toner of the present invention contains an aromatic petroleum resin. By containing the aromatic petroleum resin, it is possible to improve the crushability and improve heat resistance while maintaining low-temperature fixability.
The aromatic petroleum resin is a resin synthesized using C9 petroleum fractions such as styrene, vinyltoluene, and indene as raw materials. In particular, styrene copolymers of styrene or α-methylstyrene are preferred.
The weight average molecular weight (Mw) of the aromatic petroleum resin is preferably 2000 or more and 3500 or less. By having a weight average molecular weight of 2000 or more, durability in actual equipment can be ensured. Further, by having a weight average molecular weight of 3500 or less, good pulverizability can be ensured.

The styrenic copolymer is not particularly limited, but includes, for example, polymers of styrene and its substituted products such as polystyrene, polyp-styrene, and polyvinyltoluene, styrene-α-methylstyrene copolymer, and styrene-p-chloro. Styrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-meth Methyl acrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl Styrenic copolymers such as methyl ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, and styrene-maleic acid ester copolymers. Examples include polymers. Among these, it is particularly preferable to contain a styrene-α-methylstyrene copolymer.

The glass transition temperature (Tg) of the styrenic copolymer is preferably 60°C or higher, more preferably 65 to 85°C. When the Tg of the styrenic copolymer is 60°C or higher, heat-resistant storage stability is improved.

Note that Tg is measured using a differential scanning calorimeter (Q-200, manufactured by TA Instruments). Specifically, after putting about 5.0 mg of the target sample into an aluminum sample container, the sample container was placed on a holder unit, set in an electric furnace, and then heated at a heating rate of 10°C/min under a nitrogen atmosphere. The temperature is raised from -80°C to 150°C, and the glass transition temperature (Tg) of the target sample is determined from the obtained DSC curve using an analysis program in the differential scanning calorimeter.

In the toner of the present invention, the ratio of the crystalline polyester to the aromatic petroleum resin is preferably 1.0 or more and 1.2 or less in terms of mass ratio. The aromatic petroleum resin used in the present invention is dispersed in the toner to improve the crushability, but since it has a glass transition temperature above a certain level, it acts in the direction of inhibiting the low-temperature fixability. On the other hand, although crystalline polyester resin improves low-temperature fixing properties, the crystallized portion acts in a direction that inhibits crushability. That is, the aromatic petroleum resin and the crystalline polyester resin used in the present invention have contradictory effects in terms of crushability and low-temperature fixability. In order to properly bring out the effects of both materials, it is important that the proportions of both materials in the toner be approximately the same. Generally, since crystalline polyester has a property of being partially compatible with amorphous polyester, the proportion of the crystallized portion is slightly smaller than the amount added in the toner. As a result of considering and investigating the above, by setting the ratio of crystalline polyester to aromatic petroleum resin in the range of 1.0 or more and 1.2 or less, it becomes possible to achieve both high levels of crushability and low-temperature fixability.

In the toner of the present invention, the content of aromatic petroleum resin is preferably 3.0% by mass or more. By setting the content to 3.0% by mass or more, it is possible to maintain grindability above a certain level and improve wax dispersibility, thereby improving durability.

More preferably, the content of the aromatic petroleum resin in the toner is 3.5% by mass or more and 5.0% by mass or less.

(colorant)
The toner of the present invention can contain a colorant.
As colorants, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow ( GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Iso Indolinone Yellow, Red Red, Red Lead, Lead Vermilion, Cadmium Red, Cadmium Mercuri Red, Antimony Vermilion, Permanent Red 4R, Para Red, Phise Red, Parachlororthonitroaniline Red, Lysol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carn Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belcampus Rubin B, Brilliant Scarlet G, Lysole Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red , pyrazolone red, polyazole red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, Indanthrene blue (RS, BC), indigo, ultramarine, navy blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, Examples include emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litobone, and mixtures thereof. The content of the colorant is preferably 1 to 15% by weight, more preferably 3 to 10% by weight based on the toner.

The coloring agent used in the present invention can also be used as a masterbatch composited with a resin. As the binder resin to be kneaded together with the masterbatch, the same binder resin as described above can be used. Further, the binder resin may be used alone or in combination of two or more.

The masterbatch can be obtained by mixing and kneading a masterbatch-preparing resin and a colorant under high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, there is also the so-called flushing method, in which an aqueous paste of a colorant containing water is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin, and the water and organic solvent components are removed. Since the wet cake can be used as it is, there is no need to dry it and it is suitable for use. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used. The amount of the masterbatch used is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the binder resin.

Further, the resin for masterbatch preparation has an acid value of 30 mgKOH/g or less and an amine value of 1 to 100, and is preferably used with a colorant dispersed therein. 10 to 50, and it is more preferable to use the colorant dispersed therein. When the acid value is 30 mgKOH/g or less, the charging property under high humidity becomes appropriate and the pigment dispersibility becomes sufficient. Further, when the amine value is 1 or more and when the amine value is 100 or less, the pigment dispersibility becomes sufficient. Note that the acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237.

Further, a dispersant can be used to improve the dispersibility of the pigment. In terms of pigment dispersibility, the dispersant preferably has high compatibility with the binder resin, and specific commercially available products include "Ajisper PB821", "Ajisper PB822" (manufactured by Ajinomoto Fine Techno), " Examples include "Disperbyk-2001" (manufactured by BYK Chemie) and "EFKA-4010" (manufactured by EFKA).
The mass average molecular weight of the dispersant is preferably 500 to 100,000 as the molecular weight of the maximum value of the main peak in terms of styrene equivalent mass in gel permeation chromatography, and from the viewpoint of pigment dispersibility, 3,000 to 100. ,000 is more preferable. In particular, it is preferably 5,000 to 50,000, most preferably 5,000 to 30,000. When the molecular weight is 500 or more, the polarity becomes appropriate and the dispersibility of the colorant improves. When the molecular weight is 100,000 or less, the affinity with the solvent becomes appropriate and the dispersibility of the colorant improves. The dispersant is preferably blended into the toner in a proportion of 0.1 to 10% by mass based on the colorant. When the blending ratio is 0.1% by mass or more, pigment dispersibility becomes sufficient, and when the blending ratio is 10% by mass or less, deterioration in charging property under high humidity can be prevented.

(Charge control agent)
The toner of the present invention may contain a charge control agent if necessary. All known charge control agents can be used. However, for color toners, white or light-colored toners are preferred. In the case of colored charge control agents, the content of the toner needs to be reduced because the color is mixed into the toner and the toner becomes dull.

Examples of charge control agents include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified quaternary ammonium salts), etc. ), alkylamides, phosphorus alone or compounds, tungsten alone or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.

Specifically, Bontron 03 is a nigrosine-based dye, Bontron P-51 is a quaternary ammonium salt, Bontron S-34 is a metal-containing azo dye, E-82 is an oxynaphthoic acid-based metal complex, and E- is a salicylic acid-based metal complex. 84, phenolic condensate E-89 (manufactured by Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complexes TP-302 and TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymeric compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

In the present invention, the amount of charge control agent used is determined by the toner manufacturing method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method. Although not limited to, it is preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the binder resin. Preferably, the amount is in the range of 0.2 to 5 parts by mass. When the blending ratio is 10 parts by mass or less, the chargeability of the toner becomes appropriate, the effect of the main charge control agent can be improved, the electrostatic attraction force with the developing roller becomes appropriate, and the fluidity of the developer is reduced. It is possible to prevent a decrease in image density. These charge control agents and mold release agents can be melt-kneaded together with the masterbatch and resin.

(external additive)
In addition, in order to improve the fluidity, storage stability, developability, transferability, and durability of the toner, inorganic fine particles such as oxide fine particles, hydrophobic silica fine powder, and polymeric fine particles are added to the toner base particles as external additives. Fine resin particles may be added and mixed. This effect is achieved by covering the wax, which reduces transferability and durability, with these external additives and by covering the toner surface with fine particles, thereby reducing the contact area. The surfaces of these inorganic fine particles are preferably subjected to hydrophobizing treatment, and hydrophobized metal oxide fine particles such as silica and titanium oxide are preferably used. By increasing the amount of hydrophobized titanium oxide externally added than the amount of hydrophobized silica, a toner with excellent charging stability against humidity, improved toner transfer rate, and good filming resistance. It can be done.

The primary particle diameter of the inorganic fine particles and the resin fine particles is preferably 5 nm to 2 μm. The proportion of inorganic fine particles used varies depending on the type, but is used in the range of 0.01 to 5% by mass based on the toner particles. Specific examples of inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, Examples include diatomaceous earth, chromium oxide, cerium oxide, pengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. These can be used alone or in combination of two or more. Examples of polymeric resin particles include polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylic ester and acrylic ester copolymers, silicone, benzoguanamine, and polycondensation resins such as nylon. , polymer particles made of thermosetting resin.

In the toner of the present invention, when a glycerin fatty acid ester or a polyglycerin fatty acid ester is used in combination with the ketone wax as a release agent, it is preferable to use silica and titanium oxide in combination. Silica and titanium oxide have strong negative chargeability, and can change positively chargeable particles to negative chargeability without an external additive.

Representative examples of the hydrophobizing agent include the following. Dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allyl phenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, Chlormethyldimethylchlorosilane, chlormethyltrichlorosilane, p-chlorophenyltrichlorosilane, 3-chloropropyltrichlorosilane, 3-chloropropyltrimethoxysilane, vinyltriethoxysilane, vinylmethoxysilane, vinyl-tris(β-methoxyethoxy) ) Silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinyldichlorosilane, dimethylvinylchlorosilane, octyl-trichlorosilane, decyl-trichlorosilane, nonyl-trichlorosilane, (4-t-propylphenyl) -Trichlorosilane, (4-t-butylphenyl)-trichlorosilane, dipentyl-dichlorosilane, dihexyl-dichlorosilane, dioctyl-dichlorosilane, dinonyl-dichlorosilane, didecyl-dichlorosilane, didodecyl-dichlorosilane, dihexadecyl-dichlorosilane, (4-t-butyl phenyl)-octyl-dichlorosilane, dioctyl-dichlorosilane, didecenyl-dichlorosilane, dinonenyl-dichlorosilane, di-2-ethylhexyl-dichlorosilane, di-3,3-dimethylpentyl-dichlorosilane, trihexyl-chlorosilane, trioctyl-chlorosilane, tridecyl-chlorosilane, Dioctyl-methyl-chlorosilane, octyl-dimethyl-chlorosilane, (4-t-propylphenyl)-diethyl-chlorosilane, octyltrimethoxysilane, hexamethyldisilazane, hexaethyldisilazane, diethyltetramethyldisilazane, hexaphenyldisilazane , hexatolyldisilazane, and the like. In addition, titanate coupling agents and aluminum coupling agents can also be used.

A general powder mixer is used to mix the above external additives, but it is preferably equipped with a jacket or the like so that the internal temperature can be adjusted. For example, a V-type mixer, rocking mixer, Loedige mixer, Nauta mixer, Henschel mixer, etc. are preferably used.

By including the above-mentioned inorganic fine particles and resin fine particles in the toner (internal addition), the effect is less than when added externally, but the effect of improving transferability and durability can be obtained, and the crushability of the toner can be improved. Can be done. Further, by using external addition and internal addition in combination, it is possible to suppress the externally added fine particles from being embedded, thereby stably obtaining excellent transferability and improving durability.

(Other ingredients)
Further, the toner of the present invention may contain other components as appropriate depending on the purpose. Examples of other components include fluidity improvers, cleaning performance improvers, magnetic materials, metal soaps, and the like.

The fluidity improver is one that can be surface-treated to increase hydrophobicity and prevent deterioration of fluidity and charging characteristics even under high humidity, such as silane coupling agents, silylation agents, Examples include a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.

The cleaning property improver is added to the toner in order to remove developer remaining on the electrostatic latent image carrier or intermediate transfer member after transfer, and includes, for example, fatty acid such as zinc stearate, calcium stearate, and stearic acid. Examples include metal salts, polymethyl methacrylate fine particles, polymer fine particles produced by soap-free emulsion polymerization such as polystyrene fine particles, and the like. The polymer fine particles preferably have a relatively narrow particle size distribution, and preferably have a weight average particle size of 0.01 to 1 μm.

The magnetic material is not particularly limited and can be appropriately selected from known materials depending on the purpose, such as iron powder, magnetite, ferrite, and the like. Among these, white ones are preferred in terms of color tone.

(Toner manufacturing method)
The method for producing the toner in the present invention is not particularly limited, and includes a melt-kneading pulverization method, a polymerization method, a polyaddition reaction method using an isocyanate group-containing prepolymer, a method of dissolving in a solvent, removing the solvent, and pulverizing. In addition to this, it can also be manufactured by a melt spray method.
For example, melt-kneading methods, polymerization methods in which a monomer composition containing a specific crystalline polymer and a polymerizable monomer is directly polymerized in an aqueous phase (suspension polymerization method/emulsion polymerization method), specific A polyaddition reaction method in which a composition containing a crystalline polymer and an isocyanate group-containing prepolymer is directly extended/crosslinked with an amine in an aqueous phase, a method in which the composition is dissolved in a solvent, the solvent is removed, and the composition is pulverized can also be employed. As mentioned above, in the present invention, a binder resin whose main component is a polyester resin is preferably used.

In the melt-kneading and pulverizing method, devices for melt-kneading the toner include a batch-type two-roll machine, a Banbury mixer, and a continuous twin-screw extruder, such as a KTK-type twin-screw extruder manufactured by Kobe Steel, Ltd., and a Toshiba Machine Co., Ltd. TEM twin-screw extruder, KCK twin-screw extruder, Ikegai Tekko Co., Ltd. PCM twin-screw extruder, Kurimoto Iron Works KEX twin-screw extruder, and continuous single-screw kneading machine, such as Bussu. A molding machine, a kneader, etc. are preferably used.

In the above polymerization method and the polyaddition reaction method using an isocyanate group-containing prepolymer, it is essential to forcibly emulsify (form droplets) by applying mechanical energy in the aqueous phase. Examples of means for applying such mechanical energy include strong stirring such as a homomixer, ultrasonic waves, and Manton-Gorlin, or means for applying ultrasonic vibration energy.

For pulverization, it is possible to coarsely pulverize using a hammer mill, rotoplex, etc., and then use a pulverizer using a jet stream or a mechanical pulverizer, resulting in an average particle size of 3 to 15 μm. It is desirable to do so. Furthermore, the particle size of the pulverized product is adjusted to 5 to 20 μm using a wind classifier or the like.

The softening temperature (T _1/2 : temperature at which half of the sample flows out under elevated temperature and predetermined load) determined by a flow tester of the toner is preferably 115 to 140°C. From the viewpoint of toner storage stability, the glass transition temperature (Tg) is preferably 55 to 70°C, more preferably 57 to 70°C. When the Tg is 55° C. or higher, toner deterioration in a high-temperature atmosphere can be prevented, and offset can also be prevented from occurring during fixing. Furthermore, when Tg is 70° C. or less, fixing performance is improved.

The external additive is added to the toner matrix by mixing and stirring the toner matrix and the external additive using a mixer, thereby causing the external additive to be crushed and coated on the toner surface. At this time, it is important from the viewpoint of durability that external additives such as inorganic fine particles and resin fine particles are uniformly and firmly adhered to the toner base.

(Developer)
The developer using the toner of the present invention may be either a one-component developer or a two-component developer. For example, a two-component developer includes the toner of the present invention and a carrier.
The carrier is not particularly limited and can be appropriately selected depending on the purpose, but preferably has a core material and a resin layer covering the core material.
The material of the core material is not particularly limited and can be selected as appropriate depending on the purpose. Mn--Mg) type materials are preferable, and from the viewpoint of ensuring image density, highly magnetized materials such as iron powder (100 emu/g or more) and magnetite (75 emu/g or more and 120 emu/g or less) are preferable. In addition, copper-zinc (Cu-Zn) type materials (30 emu/g or more and 80 emu/g or less) etc. are effective in reducing the contact of the toner with the photoconductor in which the toner is in a standing state, which is advantageous for achieving high image quality. Weakly magnetized materials are preferred. These may be used alone or in combination of two or more.
The volume average particle size of the core material is preferably 25 μm or more and 200 μm or less.

The material for the resin layer is not particularly limited and can be selected as appropriate depending on the purpose, for example, amino resin, polyvinyl resin, polystyrene resin, halogenated olefin resin, polyester resin, polycarbonate resin. , polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride Polymers, fluoro terpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride, and non-fluorinated monomers, silicone resins, and the like can be mentioned. These may be used alone or in combination of two or more.

The mixing ratio of toner and carrier in the two-component developer is preferably 2.0% by mass or more and 12.0% by mass or less, more preferably 2.5% by mass or more and 10.0% by mass or less, as a mass ratio of toner to carrier. .

(toner storage unit)
The toner storage unit in the present invention refers to a unit that has the function of storing toner and stores toner therein. Here, examples of the toner storage unit include a toner storage container, a developing device, a process cartridge, and the like.
The toner storage container refers to a container that stores toner.
A developing device has means for storing and developing toner.
A process cartridge is a cartridge that integrates at least an image carrier and a developing means, stores toner, and is removably attached to an image forming apparatus. The process cartridge may further include at least one selected from charging means, exposure means, and cleaning means.
The toner storage unit according to the present invention stores the toner according to the present invention.
By attaching the toner storage unit of the present invention to an image forming apparatus and forming an image, the image is formed using the toner of the present invention, and thus an excellent image with excellent low-temperature fixability and heat-resistant storage stability can be obtained. It will be done.

(process cartridge)
A process cartridge according to the present invention includes an electrostatic latent image carrier that carries an electrostatic latent image, and a visible image is formed by developing the electrostatic latent image carried on the electrostatic latent image carrier using toner. The image forming apparatus includes at least a developing means for carrying out the image forming process, and further includes other means such as a charging means, an exposure means, a developing means, a transfer means, a cleaning means, and a static eliminating means, which are appropriately selected as necessary.
The developing means includes a developer container that stores the toner or developer of the present invention, and a developer carrier that supports and transports the toner or developer contained in the developer container. , and may further include a layer thickness regulating member for regulating the thickness of the supported toner layer.
The process cartridge according to the present invention can be removably installed in various electrophotographic apparatuses, facsimile machines, and printers, and is preferably removably installed in an image forming apparatus of the invention described later.

(Image forming method and image forming device)
The image forming apparatus of the present invention includes: an electrostatic latent image carrier; an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier; a developing device that develops the electrostatic latent image using toner to form a toner image; a transfer device that transfers the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium; It includes a fixing means for fixing the toner image transferred to the surface of the recording medium, and further includes other means such as a static elimination means, a cleaning means, a recycling means, a control means, etc., as necessary.
The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and an electrostatic latent image formed on the electrostatic latent image carrier. a developing step of developing with toner to form a toner image; a transfer step of transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium; The fixing process includes a fixing process of fixing the toner image, and further includes other processes such as a static elimination process, a cleaning process, a recycling process, and a control process, as required.
In the image forming apparatus and image forming method of the present invention, the toner of the present invention, for example, a pulverized toner, is used as the toner.

Further, the method for manufacturing printed matter of the present invention is characterized in that a toner image using the toner of the present invention is formed on a recording medium using the image forming apparatus of the present invention.

(Electrostatic latent image forming process and electrostatic latent image forming means)
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier (hereinafter sometimes referred to as "electrophotographic photoreceptor" or "photoreceptor") is not particularly limited in its material, shape, structure, size, etc., and may be selected from among known ones. Although it can be selected as appropriate, the shape is preferably a drum shape, and the material includes, for example, an inorganic photoreceptor such as amorphous silicon or selenium, or an organic photoreceptor (OPC) such as polysilane or phthalopolymethine. can be mentioned. Among these, organic photoreceptors (OPCs) are preferable because higher definition images can be obtained.
Formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then imagewise exposing it to light, and may be performed by an electrostatic latent image forming means. Can be done.
The electrostatic latent image forming means includes, for example, a charging means (charger) that uniformly charges the surface of the electrostatic latent image carrier, and an exposure device that imagewise exposes the surface of the electrostatic latent image carrier. means (exposure device).
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and can be appropriately selected depending on the purpose, for example, a contact charger that is known per se and equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc. , corotron, scorotron, and other non-contact chargers that utilize corona discharge.
The charger is preferably one that is disposed in contact with or in a non-contact state with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying DC and AC voltages in a superimposed manner.
Further, the charger is a charging roller disposed close to the electrostatic latent image carrier through a gap tape in a non-contact manner, and the electrostatic latent image is transferred by superimposing direct current and alternating current voltages to the charging roller. One that charges the body surface is preferable.
The exposure can be performed, for example, by imagewise exposing the surface of the electrostatic latent image carrier using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger in the form of an image to be formed, and may be selected as appropriate depending on the purpose. Examples of exposure devices include copying optical systems, rod lens array systems, laser optical systems, liquid crystal shutter optical systems, and the like.
In the present invention, a back-light method may be adopted in which imagewise exposure is performed from the back side of the electrostatic latent image carrier.

(Developing process and developing means)
The developing step is a step of developing the electrostatic latent image using the toner to form a visible image.
Formation of the visible image can be performed, for example, by developing the electrostatic latent image using the toner, and can be performed by the developing means.
The developing means preferably includes at least a developing device that accommodates the toner and can apply the toner to the electrostatic latent image in a contact or non-contact manner, and the developing device includes a container containing toner. etc. are more preferable.
The developing device may be a single-color developing device or a multi-color developing device, and includes, for example, a stirrer that frictionally stirs the toner to charge it and a rotatable magnetic roller. Preferred examples include:

(Transfer process and transfer means)
The transfer step is a step of transferring the visible image to a recording medium, using an intermediate transfer body, and after first transferring the visible image onto the intermediate transfer body, transferring the visible image onto the recording medium. It is preferable to use two or more color toners, preferably full-color toners, and to transfer a visible image onto an intermediate transfer body to form a composite transfer image. A more preferred embodiment includes a second transfer step of transferring the transferred image onto a recording medium.
The transfer means (the first transfer means, the second transfer means) transfers the visible image formed on the electrostatic latent image carrier (photoreceptor) to the recording medium by peeling and charging it. It is preferable to have at least a container. The number of the transfer means may be one, or two or more.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
Note that the recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

(Fixing process and fixing means)
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the visible image is transferred to the recording medium for each color developer, or may be performed for each color developer. However, this may be done simultaneously in a laminated state.
The fixing device is not particularly limited and can be appropriately selected depending on the purpose, but known heating and pressing means are suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt, and the like.

The static elimination step is a process of applying a static elimination bias to the electrostatic latent image carrier to eliminate static electricity, and can be suitably performed by a static elimination means.
The static eliminating means is not particularly limited as long as it can apply a static eliminating bias to the electrostatic latent image carrier, and can be appropriately selected from known static eliminators, such as a static eliminating lamp, etc. Preferred examples include:

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier, and can be suitably carried out by a cleaning means.
The cleaning means is not particularly limited as long as it can remove the toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners, such as a magnetic brush cleaner. Preferred examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step in which the toner removed in the cleaning step is recycled by the developing means, and can be suitably carried out by a recycling means. The recycling means is not particularly limited, and includes known conveyance means and the like.

The control step is a step of controlling each of the steps, and each step can be suitably performed by a control means.
The control means is not particularly limited as long as it can control the movement of each of the means, and can be appropriately selected depending on the purpose, and examples thereof include equipment such as a sequencer and a computer.

FIG. 1 is a schematic explanatory diagram showing an example of an image forming apparatus of the present invention.
The image forming apparatus 100A includes a photosensitive drum 10, a charging roller 20, an exposure device, a developing device 40, an intermediate transfer belt 50, a cleaning device 60 having a cleaning blade, and a static elimination lamp 70.
The intermediate transfer belt 50 is an endless belt stretched between three rollers 51 disposed inside, and can move in the direction of the arrow in FIG. Some of the three rollers 51 also function as transfer bias rollers capable of applying a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is arranged near the intermediate transfer belt 50. Further, a transfer roller 80 to which a transfer bias (secondary transfer bias) for transferring the toner image onto the transfer paper 95 can be applied is arranged facing the intermediate transfer belt 50 .
Further, a corona charging device 58 for applying an electric charge to the toner image transferred to the intermediate transfer belt 50 is installed around the intermediate transfer belt 50 in a direction opposite to the photoreceptor drum 10 with respect to the rotational direction of the intermediate transfer belt 50. It is arranged between the contact portion of the intermediate transfer belt 50 and the contact portion between the intermediate transfer belt 50 and the transfer paper 95 .

The developing device 40 includes a developing belt 41, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C, which are provided around the developing belt 41. Note that the developing unit 45 for each color includes a developer storage section 42, a developer supply roller 43, and a developing roller (developer carrier) 44. Further, the developing belt 41 is an endless belt stretched between a plurality of belt rollers, and can move in the direction of the arrow in FIG. Further, a portion of the developing belt 41 is in contact with the photosensitive drum 10.

Next, a method of forming an image using the image forming apparatus 100A will be described. First, the surface of the photoreceptor drum 10 is uniformly charged using the charging roller 20, and then the photoreceptor drum 10 is exposed to exposure light L using an exposure device (not shown) to form an electrostatic latent image. form. Next, the electrostatic latent image formed on the photoreceptor drum 10 is developed with toner supplied from the developing device 40 to form a toner image. Furthermore, after the toner image formed on the photosensitive drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, the toner image is transferred by the transfer bias applied from the transfer roller 80. , are transferred onto the transfer paper 95 (secondary transfer). On the other hand, after the toner remaining on the surface of the photosensitive drum 10, on which the toner image has been transferred to the intermediate transfer belt 50, is removed by the cleaning device 60, the charge is removed by the charge removal lamp 70.

FIG. 2 shows a second example of the image forming apparatus used in the present invention. In the image forming apparatus 100B, a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C are arranged directly opposite to each other around the photoreceptor drum 10 without providing a developing belt 41. Other than that, it has the same configuration as the image forming apparatus 100A.

FIG. 3 shows a third example of the image forming apparatus used in the present invention. The image forming apparatus 100C is a tandem color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

The intermediate transfer belt 50 provided in the center of the copying apparatus main body 150 is an endless belt stretched around three rollers 14, 15, and 16, and can move in the direction of the arrow in FIG. . A cleaning device 17 having a cleaning blade for removing toner remaining on the intermediate transfer belt 50 on which the toner image has been transferred to the recording paper is arranged near the roller 15. Yellow, cyan, magenta, and black image forming units 120Y, 120C, 120M, and 120K are juxtaposed along the conveying direction and facing the intermediate transfer belt 50 stretched by rollers 14 and 15.

Further, an exposure device 21 is arranged near the image forming unit 120. Furthermore, a secondary transfer belt 24 is arranged on the side of the intermediate transfer belt 50 opposite to the side on which the image forming unit 120 is arranged. The secondary transfer belt 24 is an endless belt stretched between a pair of rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer belt 50 are transported between the rollers 16 and 23. can be contacted.

Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 includes a fixing belt 26, which is an endless belt stretched between a pair of rollers, and a pressure roller 27 placed under pressure against the fixing belt 26. is located. Note that a sheet reversing device 28 is arranged near the secondary transfer belt 24 and the fixing device 25 for reversing the recording paper when forming images on both sides of the recording paper.

Next, a method for forming a full-color image using the image forming apparatus 100C will be described. First, set a color original on the document table 130 of the automatic document feeder (ADF) 400, or open the automatic document feeder 400 and set the color original on the contact glass 32 of the scanner 300. Close the device 400.
When the start switch is pressed, if the original is set on the automatic document feeder 400, the original is transported and moved onto the contact glass 32; on the other hand, if the original is set on the contact glass 32, Immediately, the scanner 300 is driven, and the first traveling body 33 equipped with a light source and the second traveling body 34 equipped with a mirror travel. At this time, the reflected light from the document surface of the light irradiated from the first traveling body 33 is reflected by the second traveling body 34, and then received by the reading sensor 36 via the imaging lens 35, so that the original is The image information is read and black, yellow, magenta, and cyan image information is obtained.

The image information of each color is transmitted to each image forming means 18 in the image forming unit 120 of each color, and a toner image of each color is formed. As shown in FIG. 4, each color image forming unit 120 includes a photoreceptor drum 10, a charging roller 160 that uniformly charges the photoreceptor drum 10, and a charge roller 160 that charges the photoreceptor drum 10 uniformly based on the image information of each color. an exposure device that exposes with exposure light L to form an electrostatic latent image of each color; a developing device 61 that develops the electrostatic latent image with a developer of each color to form a toner image of each color; It includes a transfer roller 62 for transferring onto the transfer belt 50, a cleaning device 63 having a cleaning blade, and a discharge lamp 64.
The toner images of each color formed by the image forming units 120 of each color are sequentially transferred (primary transfer) onto an intermediate transfer belt 50 that moves while being stretched across rollers 14, 15, and 16, and are superimposed to form a composite toner image. It is formed.

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and the recording paper is fed out one by one by the separation roller 145. The paper is separated and sent to a paper feed path 146, conveyed by transport rollers 147, guided to a paper feed path 148 in the copying apparatus main body 150, and stopped against registration rollers 49. Alternatively, the recording paper on the manual feed tray 54 is fed out by rotating the paper feed roller, separated one by one by the separation roller 52, guided to the manual paper feed path 53, and stopped against the registration roller 49.
The registration roller 49 is generally used while being grounded, but may be used with a bias applied to remove paper dust from the recording paper.

Next, by rotating the registration roller 49 in synchronization with the composite toner image formed on the intermediate transfer belt 50, the recording paper is sent between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is formed on the intermediate transfer belt 50. Transfer the toner image onto recording paper (secondary transfer). Note that the toner remaining on the intermediate transfer belt 50 to which the composite toner image has been transferred is removed by the cleaning device 17.
The recording paper onto which the composite toner image has been transferred is conveyed by a secondary transfer belt 24, and then the composite toner image is fixed by a fixing device 25. Next, the conveyance path of the recording paper is switched by a switching claw 55, and the recording paper is discharged onto a paper discharge tray 57 by a discharge roller 56. Alternatively, the conveyance path of the recording paper is switched by the switching claw 55, the sheet is reversed by the sheet reversing device 28, an image is similarly formed on the back side, and then the recording paper is discharged onto the paper discharge tray 57 by the discharge roller 56. .

According to the image forming apparatus and image forming method of the present invention, since the toner of the present invention is used that can achieve high levels of pulverizability, low-temperature fixability, heat resistance, and durability, high-quality images can be provided for a long period of time. can do.

Aspects of the present invention are, for example, as follows.
<1> A toner containing at least an amorphous polyester resin, a crystalline polyester resin, a wax, and an aromatic petroleum resin,
The SP value of the wax is 8.0 or more and 8.5 or less,
A toner characterized in that the melting point of the wax is 80° C. or more and 100° C. or less, and the ratio of the crystalline polyester resin to the aromatic petroleum resin is 1.0 or more and 1.2 or less in terms of mass ratio.
<2> The toner according to <1>, wherein the content of the crystalline polyester resin in the toner is 5.0% by mass or less.
<3> The toner according to <1> or <2>, wherein the content of the aromatic petroleum resin in the toner is 3.0% by mass or more.
<4> The toner according to any one of <1> to <3>, wherein the aromatic petroleum resin is a copolymer of styrene or α-methylstyrene.
<5> The toner according to any one of <1> to <4>, wherein the crystalline polyester has a melting point of 100°C or more and 120°C or less.
<6> The toner according to any one of <1> to <5>, wherein the aromatic petroleum resin has a weight average molecular weight (Mw) of 2000-3500.
<7> The toner according to any one of <1> to <6>, wherein the wax is Fischer-Tropsch wax.
<8> The toner according to any one of <1> to <7>, wherein the amorphous polyester resin contains at least bisphenol A and ethylene glycol as diol components.
<9> A toner storage unit containing the toner according to any one of <1> to <8>.
<10> Electrostatic latent image carrier;
an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
a developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a toner image;
a transfer means for transferring the toner image formed on the electrostatic latent image carrier to the surface of a recording medium;
a fixing means for fixing the toner image transferred to the surface of the recording medium,
An image forming apparatus characterized in that the toner is the toner according to any one of <1> to <8>.
<11> An electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier;
a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a toner image;
a transfer step of transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
a fixing step of fixing the toner image transferred to the surface of the recording medium,
An image forming method, wherein the toner is the toner according to any one of <1> to <8>.
<12> A method for producing a printed matter, comprising forming a toner image using the toner according to any one of <1> to <8> on a recording medium using the image forming apparatus according to <10>.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. However, "parts" means "parts by mass" unless otherwise specified.

<Manufacturing example>
(Production of amorphous polyester resin 1)
The monomer species shown in Table 1 below and tetrabutoxy titanate as a condensation catalyst were placed in a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and while distilling off the water produced under a nitrogen stream, 230 The reaction was carried out at ℃ for 6 hours. Next, a reaction was carried out for 1 hour under reduced pressure of 5 mmHg to 20 mmHg to obtain amorphous polyester resin 1 used in Examples. In Table 1, "25 mol%" for bisphenol A (2,2) ethylene oxide indicates the proportion in the alcohol component when the acid component is 50 mol% and the alcohol component is 50 mol%.

(Production of amorphous polyester resin 2)
Amorphous polyester resin 2 was obtained in the same manner as in the production of amorphous polyester resin 1, except that the types of monomers used were changed as shown in Table 2 below.

(Production of crystalline polyester 1)
Fumaric acid and 1,6-hexanediol were charged in a 5L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple so that the OH/COOH ratio was 0.9, and titanium tetraisopropoxide was added. (500 ppm based on the resin component) at 180°C for 10 hours, then heated to 200°C and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to achieve a melting point of 103°C. Crystalline polyester 1 was obtained.

(Production of crystalline polyester 2)
Fumaric acid and 1,6-hexanediol were charged in a 5L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple so that the OH/COOH was 0.93, and titanium tetraisopropoxide was added. (500 ppm based on the resin component) at 180°C for 10 hours, then heated to 200°C and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to achieve a melting point of 117°C. Crystalline polyester 2 was obtained.

(Production of crystalline polyester 3)
Fumaric acid and 1,6-hexanediol were charged into a 5L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple so that the OH/COOH ratio was 0.85, and titanium tetraisopropoxide was added. (500 ppm based on the resin component) at 180°C for 10 hours, then heated to 200°C and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to achieve a melting point of 97°C. Crystalline polyester 3 was obtained.

(Production of crystalline polyester 4)
Fumaric acid and 1,6-hexanediol were charged in a 5L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple so that the OH/COOH ratio was 0.96, and titanium tetraisopropoxide was added. (500 ppm based on the resin component) at 180°C for 10 hours, then heated to 200°C and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to achieve a melting point of 123°C. Crystalline polyester 4 was obtained.

<Example/Comparative example>
(Example 1):
-Creation of toner base particle 1-
Amorphous polyester resin 1: 86.4 parts Crystalline polyester resin 1: 4.8 parts Aromatic petroleum resin: FTR-2140 (Styrenic copolymer manufactured by Mitsui Chemicals, Ltd.) 4.8 parts Wax: Wax 1 4 parts Carbon black (Mitsubishi Kaseisha #44): 10 copies

According to the above recipe, toner raw materials were premixed using a Henschel mixer (FM20B, manufactured by Mitsui Miike Kakoki Co., Ltd.), and then mixed at a temperature of 120°C with a twin-screw kneader (PCM-30, manufactured by Ikegai Tekko Co., Ltd.). Melted and kneaded. The obtained kneaded material was rolled to a thickness of 2.7 mm using rollers, cooled to room temperature using a belt cooler, and coarsely ground to 200 μm to 300 μm using a hammer mill. Next, after finely pulverizing using a supersonic jet pulverizer Labojet (manufactured by Nippon Pneumatic Industries Co., Ltd.), the weight average particle size was reduced to 5.5 mm using an air classifier (manufactured by Nippon Pneumatic Industries Co., Ltd., MDS-I). The toner base particles 1 of Example 1 were obtained by classifying the toner base particles 1 of Example 1 by appropriately adjusting the louver opening so that the particle size was 8±0.2 μm.

(Examples 2 to 14) and (Comparative Examples 1 to 6)
-Creation of toner base particles 2 to 20-
Examples 2 to 14 were prepared using the same procedure except that the type and number of amorphous polyester resin, the type and number of crystalline polyester resin, the type and number of aromatic petroleum resin, and the type of wax used were changed as shown in Table 3. , toner base particles 2 to 20 of Comparative Examples 1 to 6 were obtained.

The manufacturer, composition, and physical properties of the aromatic petroleum resin used are as follows.

Further, the type, SP value, and melting point of the wax used are as follows.

(Preparation of toner developer)
To 100 parts by mass of the above toner base particles, 1 part by mass of HDK-2000 (Clariant Co., Ltd.) as metal oxide fine particles was stirred and mixed with a Henschel mixer to prepare an externally added toner. 5% by mass of this externally-added toner and 95% by mass of the coated ferrite carrier were uniformly mixed at 48 rpm for 5 minutes using a Turbler mixer (manufactured by Willie Bacchofen (WAB)) to create a toner developer. did. Using this toner developer, crushability, low-temperature fixability, heat-resistant storage stability, and durability were evaluated by the following evaluation methods.

(Evaluation of crushability)
In the toner base particle manufacturing process, the weight average particle diameter was measured after finely pulverizing using a supersonic jet pulverizer Labojet (manufactured by Nippon Pneumatic Industries Co., Ltd.), and the pulverizability was judged based on the following evaluation criteria. .
- Evaluation criteria for crushability -
◎: Less than 5.3 μm ○: 5.3 μm or more and less than 5.5 μm ×: 5.5 μm or more It can be judged that the ◎ and ○ evaluations are practically sufficient results.

(Evaluation of low temperature fixability)
The above [toner developer] was put into a copying machine (RICOH MPC 6003) manufactured by Ricoh Co., Ltd., and an image was output. A solid image with an adhesion amount of 0.4 mg/cm ² was output on paper (Type 6200 manufactured by Ricoh Co., Ltd.) through exposure, development, and transfer steps. The linear speed of fixing was 256 mm/sec. The fixing temperature was sequentially output in 5°C increments, and the lower limit temperature at which cold offset does not occur (lower limit fixing temperature: low temperature fixability) was measured. The NIP width of the fixing device was 11 mm.
-Evaluation criteria for low temperature fixability-
◎: Less than 120°C 〇: 120°C or more and less than 130°C ×: 130°C or more It can be judged that the ◎ and ○ evaluations are practically sufficient results.

(Evaluation of heat-resistant storage stability)
The toner base particles were stored at 50° C. for 24 hours, and the penetration was measured according to JIS K2235 (25° C.). Penetrometer VR-5610 (Shimadzu Corporation) was used as the penetration measurement device.
-Evaluation criteria for heat-resistant storage stability-
◎: 4.0 mm or more ○: 0.5 mm or more and less than 4.0 mm ×: less than 0.5 mm ◎ and ○ evaluations can be judged to be practically sufficient results.

(durability)
100,000 copies of a test chart with an image area of 6% were made using a low-temperature fixing Ricoh copying machine imajio MF-6550, and the degree of decrease in the amount of charge of the developer was evaluated.
◎: Excellent durability with very little decrease in charge amount ○: Excellent durability compared to conventional toner with little decrease in charge amount ×: Low durability equivalent to or lower than conventional toners ◎ and 〇 ratings are practical It can be concluded that the results are satisfactory.

The evaluation results for each toner are shown in Table 6.

From the results in Table 6, it was found that the toners of each example were able to achieve high levels of grindability, low-temperature fixability, heat resistance, and durability.

10 Electrostatic latent image carrier (photosensitive drum)
14 Roller 15 Roller 16 Roller 17 Cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 1st running body 34 2nd running body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer storage section 42Y Developer storage section 42M Developer storage section 42C Developer storage section 43K Developer supply roller 43Y Developer supply Roller 43M Developer supply roller 43C Developer supply roller 44K Developing roller 44Y Developing roller 44M Developing roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer belt 51 Roller 52 Separation Roller 53 Manual feed path 54 Manual tray 55 Switching claw 56 Ejection roller 57 Ejection tray 58 Corona charging device 60 Cleaning device 61 Developing device 62 Transfer roller 63 Photoreceptor cleaning device 64 Static elimination lamp 70 Static eliminator lamp 80 Transfer roller 90 Cleaning device 95 Transfer Paper 100A, 100B, 100C Image forming apparatus 120 Image forming unit 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Conveyance roller 148 Paper feed path 150 Copying device main body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Patent No. 5152372 Patent No. 4535017 Patent No. 3525216 JP2007-264222A Japanese Patent Application Publication No. 2014-056143 Japanese Patent Application Publication No. 2021-144186

Claims (12)

A toner containing at least an amorphous polyester resin, a crystalline polyester resin, a wax, and an aromatic petroleum resin,
The SP value of the wax is 8.0 or more and 8.5 or less,
A toner characterized in that the melting point of the wax is 80° C. or more and 100° C. or less, and the ratio of the crystalline polyester resin to the aromatic petroleum resin is 1.0 or more and 1.2 or less in terms of mass ratio. The toner according to claim 1, wherein the content of the crystalline polyester resin in the toner is 5.0% by mass or less. The toner according to claim 1, wherein the content of the aromatic petroleum resin in the toner is 3.0% by mass or more. 2. The toner according to claim 1, wherein the aromatic petroleum resin is a copolymer of styrene or α-methylstyrene. The toner according to claim 1, wherein the crystalline polyester has a melting point of 100°C or more and 120°C or less. The toner according to claim 1, wherein the aromatic petroleum resin has a weight average molecular weight (Mw) of 2000-3500. The toner according to claim 1, wherein the wax is Fischer-Tropsch wax. The toner according to claim 1, wherein the amorphous polyester resin contains at least bisphenol A and ethylene glycol as diol components. A toner storage unit containing the toner according to any one of claims 1 to 8. an electrostatic latent image carrier;
an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
a developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a toner image;
a transfer means for transferring the toner image formed on the electrostatic latent image carrier to the surface of a recording medium;
a fixing means for fixing the toner image transferred to the surface of the recording medium,
An image forming apparatus characterized in that the toner is the toner according to any one of claims 1 to 8. an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier;
a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a toner image;
a transfer step of transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
a fixing step of fixing the toner image transferred to the surface of the recording medium,
An image forming method, wherein the toner is the toner according to any one of claims 1 to 8. A method for producing printed matter, comprising forming a toner image using the toner according to any one of claims 1 to 8 on a recording medium using the image forming apparatus according to claim 10.