Resin, resin composition, printed image, electrostatic charge image developing toner, and method for producing electrostatic charge image developing toner

Abstract

The invention relates to a resin, a resin composition, a printed image, a toner for developing an electrostatic charge image, and a method for producing the toner for developing the electrostatic charge image. The resin contains a structural unit represented by general formula (1). # imgabs0 # (In general formula (1), R1 represents a hydrogen atom or a methyl group. And R2 represents a hydrogen atom or an alkyl group having 1-4 carbon atoms. And R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1-4 carbon atoms. )

Description

Technical Field

[0001] The present invention relates to a resin, a resin composition, a printed image, a toner for electrostatic charge image development, and a method for producing the toner for electrostatic charge image development. In particular, it relates to a biomass-derived resin having excellent thermal and electrical properties, etc. Background Art

[0002] The production of industrially useful chemicals from non-edible biomass is one of the technologies contributing to the realization of a low-carbon society. So far, the biomass-derived chemicals that have been industrialized have been centered on aliphatic raw materials, and the production of aromatic raw materials that can impart polymer thermal stability, rigidity, and other functions has not been achieved.

[0003] As one of the aromatic materials that can be highly productively derived from cellulose as non-edible biomass, phenyl lactic acids can be cited. At present, it is possible to consider using them as polyester materials through polycondensation, but they have not yet reached practical use. If phenyl lactic acids can be derivatized into (meth)acrylates and used as monomer raw materials for addition polymerization, not only polycondensation but also the target uses of the resulting resins can be significantly expanded, and it is possible to expect the substitution of aromatic polymer raw materials from petroleum and the development of new functional materials. It is considered that through these developments, the creation of a low-carbon society can be greatly advanced.

[0004] Specifically, it is considered that the realization of a low-carbon society can be made a reality by producing a polymer material using phenyl lactic acids as described below.

[0005] (1) From low-molecular-weight phenyl lactic acids generated from glucose, find materials that have a high possibility of being effectively used as chemical raw materials.

[0006] (2) Derivatize the above phenyl lactic acids into aromatic monomers useful in industry.

[0007] (3) Produce a polymer material having desired properties from the above aromatic monomers.

[0008] As a use of a resin material, a toner for digital printing can be cited. As a main raw material of a conventional toner, styrene of a petroleum-based material can be cited. Styrene, as a hard segment with a relatively high glass transition temperature, accounts for a lot of the resin for toner. As a biomass monomer considered to be able to be used as this hard segment, biomass methyl methacrylate can be cited. By using raw materials derived from biomass, it is possible to contribute to the realization of a decarbonized society that does not use petroleum resources. On the other hand, it is difficult to satisfy both the thermal and electrical properties required for the resin material for toner. In the case of a toner, it is fixed on paper as a medium through heat, pressure, etc. and output as an image. However, the electric power consumed as heat during fixing accounts for 70% of the total electric power consumption of the toner image forming apparatus. Therefore, in order to reduce the power consumption during toner image formation, reducing the power consumption during thermal fixing of the toner has become a major ongoing issue.

[0009] In the past, for the issue of reducing such power consumption, the development of resin materials that can be melted with low energy has been studied (for example, refer to Japanese Patent Laid-Open No. 2007-279714, Japanese Patent Laid-Open No. 2008-287229, Japanese Patent Laid-Open No. 2010-15159). Specifically, the reduction of the glass transition temperature of the resin and the reduction of the melting viscosity of the toner by controlling the molecular weight distribution of the resin have been studied.

[0010] Regarding the glass transition temperature of the resin, in, for example, a styrene-acrylic resin, it can be adjusted by the ratio of the monomers. Specifically, it can be adjusted by the ratio of monomers such as styrene that become hard segments (high glass transition temperature components) and n-butyl acrylate that become soft segments (low glass transition temperature components).

[0011] However, regarding increasing the ratio of the soft segment in the resin, for example, when used as a toner, low-temperature fixing of the toner can be achieved. On the other hand, there is a problem that the fixing separability of the toner deteriorates. In addition, regarding n-butyl acrylate, which is generally used as a monomer that becomes a soft segment, the dielectric loss tangent (tanδ), which is an index of charge leakage, is high. Therefore, when using n-butyl acrylate, there is also a problem of reducing the charge retention of the toner. Regarding the low charge retention, problems such as internal contamination caused by toner scattering and occurrence of image defects are obvious due to the low charge amount of the toner.

[0012] In addition, there is a need for a resin that can reduce the viscosity with low energy and has low charge leakage, and a biomass-derived resin that can easily reduce the viscosity at low temperatures and has excellent charge retention. Summary of the Invention

[0013] The present invention has been completed in view of the above problems and situations. The present invention provides a resin derived from biomass having excellent thermal and electrical properties, a resin composition using the resin, a printed image, a toner for electrostatic charge image development, and a method for manufacturing the toner for electrostatic charge image development.

[0014] In order to achieve at least one of the above objects, the resin contains a structural unit represented by the following general formula (1).

[0015]

[0016] In the above general formula (1), R1 represents a hydrogen atom or a methyl group. R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Advantages and features provided by one or more embodiments of the present invention will be more fully understood from the detailed description and the drawings given below. The drawings are given only by way of illustration and thus are not intended as a definition of the limitations of the present invention:

[0018] Figure 1 A diagram showing a device used for measuring the charge amount in the examples.

[0019] Description of Reference Numerals

[0020] 31 Conductive sleeve

[0021] 32 Magnetic roller

[0022] 33 Bias power supply

[0023] 34 Cylindrical electrode DETAILED DESCRIPTION OF THE EMBODIMENTS

[0024] Hereinafter, one or more embodiments of the present invention will be described with reference to the drawings. However, the scope of the present invention is not limited to the disclosed embodiments.

[0025] The resin according to the present embodiment is characterized in that it has a structural unit represented by the above general formula (1). This feature is a common or corresponding technical feature in the following respective embodiments.

[0026] As the resin according to the present embodiment, it is preferable that R2 in the above general formula (1) is a methyl group, and R3 and R4 are hydrogen atoms. Thereby, the thermal and electrical properties become better. In addition, the stereoregularity of the lactic acid moiety can be any one of D-form, L-form, and a mixture of D-form and L-form.

[0027] As the resin according to this embodiment, a copolymer of a first polymerizable monomer having a structure represented by the following general formula (2) and a second polymerizable monomer copolymerizable with the first polymerizable monomer is preferable. Thereby, the effects of the present application can be more effectively exhibited.

[0028]

[0029] As for the resin according to this embodiment, the content rate of the structural unit derived from the first polymerizable monomer is preferably in the range of 10 to 40% by mass with respect to all the structural units (100% by mass) constituting the resin. Thereby, the thermal characteristics and electrical characteristics become better.

[0030] As an embodiment of the resin according to this embodiment, it is preferable that the second polymerizable monomer contains at least one monomer selected from styrenes, acrylic acid, methacrylic acid, acrylates, and methacrylates. Thereby, it becomes easy to adjust the glass transition temperature of the resin.

[0031] As an embodiment of the resin according to this embodiment, it is preferable that the second polymerizable monomer contains at least one monomer selected from styrene, acrylic acid, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, n-butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate. Thereby, it becomes easy to adjust the glass transition temperature of the resin.

[0032] The resin composition according to this embodiment contains a resin having a structural unit represented by the above general formula (1).

[0033] The printed image according to this embodiment contains a resin having a structural unit represented by the above general formula (1).

[0034] The toner for developing a static charge image according to this embodiment contains a resin having a structural unit represented by the above general formula (1).

[0035] The method for manufacturing a toner for developing a static charge image according to this embodiment includes: preparing a resin containing a structural unit represented by the above general formula (1), preparing a toner binder particle dispersion liquid, and aggregating toner binder particles in the toner binder particle dispersion liquid to thermally bond the particles to each other. Thereby, a resin derived from biomass having excellent thermal characteristics and electrical characteristics can be manufactured.

[0036] Regarding the method for manufacturing a toner for developing a static charge image according to this embodiment, the step of preparing a resin containing a structural unit represented by the above general formula (1) may include: a step of polymerizing a first polymerizable monomer having a structure represented by the above general formula (2).

[0037] Hereinafter, the present invention, its constituent elements, and the forms and modes for implementing the present invention will be described. It should be noted that in this application, "~" is used to mean including the values described before and after it as the lower limit value and the upper limit value.

[0038] [1. Resin having a structural unit represented by the general formula (1)]

[0039] The resin according to this embodiment has a structural unit represented by the following general formula (1).

[0040]

[0041] In the above general formula (1), R1 represents a hydrogen atom or a methyl group. R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.

[0042] As specific examples of R2, for example, a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a tert-butyl group can be cited.

[0043] As specific examples of R3 and R4, for example, a hydrogen atom, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, and a tert-butoxy group can be cited.

[0044] From the viewpoints of reducing hydrogen bonding property, moderately suppressing the interaction between molecular chains, and easily reducing the viscosity at a lower temperature, it is preferable that R2 is an alkyl group having 1 to 4 carbon atoms. Further, from the viewpoints of improving the polarity of the resin by reducing the influence of the lower polar alkyl group in addition to reducing the viscosity and easily reducing the charge leakage property, R2 is more preferably a methyl group. Similarly, from the viewpoints of thermal properties and electrical properties, it is preferable that R3 and R4 are hydrogen atoms.

[0045] The resin having a structural unit represented by the general formula (1) can be synthesized by polymerizing a first polymerizable monomer having a structure represented by the following general formula (2).

[0046]

[0047] In the above general formula (2), R1 represents a hydrogen atom or a methyl group. R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.

[0048] R2, R3, and R4 in the general formula (2) are synonymous with R2, R3, and R4 in the general formula (1), respectively.

[0049] The first polymerizable monomer can be used alone or in combination of two or more.

[0050] As specific examples of the first polymerizable monomer, the following exemplified compounds M1 to M7 can be cited. It should be noted that the first polymerizable monomer is not limited to these.

[0051]

[0052] The first polymerizable monomer can be synthesized, for example, by the following synthesis scheme.

[0053] Synthesis of phenyl lactate esters

[0054] In a four-necked flask, 275 mmol of phenyl lactic acid was dissolved in 405 ml of dry THF. After adding 560 mmol of triethylamine, 280 mmol of (meth)acryloyl chloride was added dropwise at 0 °C over 30 minutes. After the addition was completed, the reaction solution was stirred at room temperature for 1 hour, and then poured into deionized water to terminate the reaction. The mixture was extracted three times with ethyl acetate, the organic layer was washed with water, and dried over MgSO4. The solvent was distilled off, and the obtained compound was purified by silica gel chromatography using a hexane / ethyl acetate solvent.

[0055]

[0056] The resin according to this embodiment may be a polymer obtained only from the first polymerizable monomer having a structure represented by the general formula (2). However, from the viewpoint of more effectively exerting the effects of the present application, the above resin is preferably a copolymer of the first polymerizable monomer having a structure represented by the general formula (2) and other polymerizable monomers copolymerizable with the first polymerizable monomer (also referred to as the "second polymerizable monomer").

[0057] Examples of the second polymerizable monomer include

[0058] styrenes such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-acetoxystyrene, m-acetoxystyrene, p-acetoxystyrene;

[0059] acrylic esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate;

[0060] Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and other methacrylates;

[0061] Acrylic acid, methacrylic acid, etc.

[0062] Among these, monomers preferably include at least one selected from styrenes, acrylic acid, methacrylic acid, acrylates and methacrylates. In addition, it is preferred to select one or more from styrene, acrylic acid, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate. Furthermore, at least one of styrene and n-butyl acrylate is more preferred. By using such polymerizable monomers, it becomes easier to adjust the glass transition temperature of the resin.

[0063] As the second polymerizable monomer, a polymerizable monomer having an ionic dissociable group can be used. The polymerizable monomer having an ionic dissociable group has groups such as a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. Specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, etc. can be cited. Among these, acrylic acid or methacrylic acid is preferred.

[0064] The second polymerizable monomer can be used alone or in combination of two or more.

[0065] Regarding the resin according to this embodiment, the content rate of the structural unit derived from the first polymerizable monomer is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 40% by mass, and further preferably in the range of 15 to 35% by mass, relative to all the structural units (100% by mass) constituting the resin. If the content rate of the structural unit derived from the first polymerizable monomer is increased, the chargeability is likely to be improved. In addition, if the content rate of the structural unit derived from the first polymerizable monomer is 10 to 40% by mass, large-sized structural units are appropriately introduced, whereby it is easy to lower the melt viscosity, and in the case of being used for a toner, the low-temperature fixability is likely to be improved. In addition, if the content rate of the structural unit derived from the first polymerizable monomer is 15 to 35% by mass, it is even easier to lower the melt viscosity, and in the case of being used for a toner, the low-temperature fixability is likely to be further improved.

[0066] In the resin according to this embodiment, there is no particular limitation on the content rate of the structural unit derived from the second polymerizable monomer, and it can be appropriately adjusted according to the type of the structural unit.

[0067] For example, when the second polymerizable monomer contains styrene-based monomers, the content of the styrene-based monomers is preferably in the range of 20 to 80% by mass, more preferably in the range of 30 to 70% by mass, based on all the structural units (100% by mass) constituting the resin.

[0068] When the second polymerizable monomer contains acrylate or methacrylate, the content of the acrylate or methacrylate is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 40% by mass, based on all the structural units (100% by mass) constituting the resin.

[0069] When the second polymerizable monomer contains polymerizable monomers having an ionic dissociable group such as acrylic acid or methacrylic acid, the content of the polymerizable monomer having an ionic dissociable group is preferably in the range of 2 to 8% by mass, based on all the structural units (100% by mass) constituting the resin.

[0070] There is no particular limitation on the method for synthesizing the resin according to this embodiment using the first polymerizable monomer and, optionally, the second polymerizable monomer. However, from the viewpoint of easy polymerization, a method of radically polymerizing the monomers using a known oil-soluble or water-soluble radical polymerization initiator is preferred.

[0071] Specific examples of the oil-soluble polymerization initiator used in radical polymerization include azo-based or diazo-based polymerization initiators and peroxide-based polymerization initiators shown below. As needed, known chain transfer agents such as n-octyl mercaptan and n-octyl 3-mercaptopropionate can be used.

[0072] Examples of the polymerization initiator include

[0073] azo-based or diazo-based polymerization initiators such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile;

[0074] peroxide-based polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis-(4,4-tert-butylperoxycyclohexyl)propane, and tris-(tert-butylperoxy)triazine.

[0075] In addition, when synthesizing the above resin by emulsion polymerization, a water-soluble radical polymerization initiator can be used.

[0076] Examples of the water-soluble radical polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, and hydrogen peroxide.

[0077] The polymerization temperature varies depending on the type of monomer and polymerization initiator used, and is preferably in the range of 50 to 100 °C, more preferably in the range of 55 to 90 °C.

[0078] The polymerization time varies depending on the type of monomer and polymerization initiator used, and is preferably, for example, 1 to 12 hours.

[0079] Regarding the resin according to this embodiment, the peak molecular weight obtained from the molecular weight distribution in terms of polystyrene conversion measured by gel permeation chromatography (GPC) is preferably in the range of 3,500 to 35,000. More preferably, it is in the range of 10,000 to 30,000. If the peak molecular weight is in such a range, the melt viscosity during heating can be in an appropriate range, and the processability of the molten resin can be easily improved. For example, when used as a toner binder, the melt viscosity of the resin during fixing becomes appropriate, and good fixability and fixing separation properties can be achieved concurrently.

[0080] The above peak molecular weight is the molecular weight corresponding to the elution time at the peak in the molecular weight distribution. In the case where there are multiple peaks in the molecular weight distribution, the molecular weight corresponding to the elution time at the peak with the largest peak area ratio is defined as the peak molecular weight.

[0081] Regarding the peak molecular weight of the resin, the following method can be used for measurement. Specifically, the apparatus “HLC-8220” (manufactured by Tosoh Corporation) and the column “TSKguardcolumn + TSKgel SuperHZM-M3 connected in series” (manufactured by Tosoh Corporation) are used. Then, while maintaining the column temperature at 40 °C, tetrahydrofuran (THF) is allowed to flow as a carrier solvent at a flow rate of 0.2 ml / min. The measurement sample is dissolved in tetrahydrofuran under the dissolution conditions of being treated with an ultrasonic disperser for 5 minutes at room temperature (25 °C) so that the concentration becomes 1 mg / ml. The measurement sample dissolved in THF is filtered through a membrane filter with a pore size of 0.2 μm to obtain a sample solution. 10 μL of this sample solution is injected into the apparatus together with the above carrier solvent, and using a refractive index detector (RI detector), the molecular weight distribution of the sample is measured from the calibration curve made from multiple standard polystyrene samples. From this molecular weight distribution, the peak molecular weight is determined.

[0082] [2. Resin Composition]

[0083] The resin composition according to this embodiment contains a resin having a structural unit represented by the above general formula (1). The "resin composition" refers to a composition containing two or more components including the above resin.

[0084] Examples of the resin composition include a resin dispersion, a resin solution, a mixed resin, and the like.

[0085] Examples of components other than the resin having a structural unit represented by the above general formula (1) contained in the resin composition according to this embodiment include a resin not containing a structural unit represented by the above general formula (1), a solvent, a dispersant, an antioxidant, a colorant, an antifoaming agent, a surfactant, and the like.

[0086] The resin composition according to this embodiment can be used for resin molded articles and the like. Regarding the resin molded article according to this embodiment, it is formed using the above resin composition, and thus is easily molded with low energy and has low charge leakage.

[0087] Regarding the melt flow rate (MFR) of the resin composition according to this embodiment at 120 °C and a load of 2.16 kg, from the viewpoint of obtaining a thermoplastic resin composition with good moldability, it is preferably 0.01 to 200 g / 10 minutes, more preferably 0.01 to 60 g / 10 minutes. If the MFR of the resin composition is within the above range, it is easy to mold the resin composition with low energy. It should be noted that the MFR can be measured at 120 °C in accordance with JIS K 7210 (ISO1133).

[0088] The dielectric loss tangent of the components of the resin composition according to this embodiment measured at 100 kHz at 25 °C is preferably 0.001 to 0.01. If the dielectric loss tangent of the resin composition is within the above range, the charge leakage is easily reduced. Regarding the dielectric loss tangent of the resin composition, it is obtained by S-parameter methods such as the capacitance method (volumetric method), the free space S-parameter method, the corrugated circular waveguide S-parameter method, the balanced disk resonator method, the Fabry-Perot open resonator method, the split cylinder cavity resonator method, the split post dielectric resonator method, the cylindrical cavity resonator perturbation method, the cutoff cylindrical waveguide method, etc. From the viewpoint of the ease of measurement values, in this application, the value obtained by the capacitance method is used.

[0089] Regarding the resin molded article according to this embodiment, it is obtained by melting and molding the above resin composition in various molding machines. As the molding method, it can be appropriately selected according to the shape and use of the molded article. For example, injection molding, extrusion molding, compression molding, blow molding, calendering molding, inflation molding, etc. can be cited. In addition, for sheet-like or film-like molded articles obtained by extrusion molding, calendering molding, etc., secondary molding such as vacuum molding and pressure molding can be performed.

[0090] There is no particular limitation on the use of the resin molded article according to this embodiment. For example, components (electrical and electronic components, electrical equipment components, exterior components, interior components, etc.) in the fields of home appliances and automobiles, various packaging materials, household goods, office supplies, pipes, agricultural materials, etc. can be cited.

[0091] [3. Toner for Developing Electrostatic Charge Images]

[0092] The toner for developing electrostatic charge images (hereinafter also simply referred to as "toner") according to this embodiment contains a resin having a structural unit represented by the above general formula (1).

[0093] In this application, the so-called "toner" refers to an aggregate of toner particles. "Toner particles" can be composed of toner mother particles and external additives. "Toner mother particles" can be composed of a toner binder, a release agent, a colorant, a charge control agent, etc.

[0094] <Toner Binder>

[0095] Regarding the toner according to this embodiment, a resin containing a structural unit represented by the above general formula (1) is contained as a toner binder constituting the toner mother particles.

[0096] The toner binder may contain other resins in addition to the above resin. As other resins, resins generally used as toner binders constituting toner mother particles can be used without limitation.

[0097] Specifically, for example, acrylic resins not containing a structural unit represented by the above general formula (1), methacrylic resins not containing a structural unit represented by the above general formula (1), polyester resins, silicone resins, polyolefin resins, polyamide resins, or epoxy resins, etc. can be cited. These other resins can be used alone or in combination of two or more.

[0098] The polyester resin is a resin obtained by a polycondensation reaction of a carboxylic acid having two or more carboxyl groups (polycarboxylic acid component) and an alcohol having two or more hydroxyl groups (polyol component). The polyester resin can be amorphous or crystalline.

[0099] As the number of functional groups of the polycarboxylic acid component and the polyol component, it is preferably 2 to 3 for each, and particularly preferably 2 for each. Therefore, as a particularly preferred form, the case where the number of functional groups is 2 for each (i.e., the dicarboxylic acid component and the diol component) will be described.

[0100] As the dicarboxylic acid component, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid (dodecanedioic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid and other saturated aliphatic dicarboxylic acids; methylene succinic acid, fumaric acid, maleic acid, 3-hexenedioic acid, 3-octenedioic acid, dodecenyl succinic acid and other unsaturated aliphatic dicarboxylic acids; phthalic acid, terephthalic acid, isophthalic acid, tert-butylisophthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-phenylenediacetic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, anthracenedicarboxylic acid and other unsaturated aromatic dicarboxylic acids, etc. In addition, their lower alkyl esters and acid anhydrides can also be used. The dicarboxylic acid component can be used alone or in combination of two or more.

[0101] In addition, polycarboxylic acids having 3 or more functional groups such as trimellitic acid and pyromellitic acid, acid anhydrides of the above carboxylic acid compounds, or alkyl esters having 1 to 3 carbon atoms can also be used.

[0102] As the diol component, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol, neopentyl glycol and other saturated aliphatic diols; 2-butene-1,4-diol, 3-butene-1,4-diol, 2-butyne-1,4-diol, 3-butyne-1,4-diol, 9-octadecene-7,12-diol and other unsaturated aliphatic diols; bisphenols such as bisphenol A and bisphenol F, and alkylene oxide adducts of bisphenols such as their ethylene oxide adducts and propylene oxide adducts and other aromatic diols. In addition, their derivatives can also be used. The diol component can be used alone or in combination of two or more.

[0103] There is no particular limitation on the method for producing the polyester resin. The polyester resin can be produced by polycondensation (esterification) of a polycarboxylic acid component and a polyol component using a known esterification catalyst.

[0104] As catalysts that can be used in the production of polyester resins, the following can be cited:

[0105] Alkali metal compounds such as sodium and lithium;

[0106] Compounds containing Group 2 elements such as magnesium and calcium;

[0107] Compounds of metals such as aluminum, zinc, manganese, antimony, titanium, tin, zirconium, and germanium;

[0108] Phosphorous acid compounds; phosphoric acid compounds; and amine compounds, etc. Specifically, as tin compounds, dibutyltin oxide (dibutyltin dioxide), tin octoate, ditin octoate, and their salts, etc. can be cited.

[0109] As titanium compounds, tetra-n-butyl titanate (Ti(O-n-Bu)4), tetraisopropyl titanate, tetramethyl titanate, tetra-stearyl titanate, etc. alkoxytitaniums; acylates of titanium such as polyhydroxystearic acid titanate; titanium chelates such as tetraacetylacetonato titanium, titanium lactate, and triethanolamine titanium, etc. As germanium compounds, germanium dioxide, etc. can be cited. As aluminum compounds, polyaluminum hydroxide, alkoxyaluminum, tributyl aluminate, etc. can be cited. These can be used alone or in combination of two or more.

[0110] There is no particular limitation on the polymerization temperature, and it is preferably in the range of 70 to 250 °C. In addition, there is no particular limitation on the polymerization time, and it is preferably in the range of 0.5 to 10 hours. During polymerization, the reaction system can be depressurized as needed.

[0111] The above polyester resin can be a mixed polyester resin having a graft copolymer structure in which a polyester polymer chain segment and a styrene·acrylic polymer chain segment are grafted.

[0112] Regarding the content of the resin containing the structural unit represented by the above general formula (1) in the toner binder, when the total mass of the toner binder is set to 100% by mass, it is preferably in the range of 5 to 100% by mass, more preferably in the range of 5 to 50% by mass, and further preferably in the range of 10 to 40% by mass.

[0113] <Release agent>

[0114] The toner according to this embodiment preferably contains a release agent in the toner base particles. This release agent is preferably a fatty acid ester.

[0115] Examples of the fatty acid ester include, for example, behenyl behenate, stearyl stearate, stearyl behenate, behenyl stearate, butyl stearate, propyl oleate, hexadecyl palmitate, methyl lignocerate, glycerol monostearate (glyceryl stearate), diglycerol distearate (distearyl diglycerol), pentaerythritol tetrabehenate, diethylene glycol monostearate, dipropylene glycol distearate, sorbitan monostearate, cholesteryl stearate, trimethylolpropane tribehenate, pentaerythritol diacetate dibehenate, glyceryl tribehenate, tristearyl trimellitate, distearyl maleate, methyl melissate, etc. These fatty acid esters may be used alone or in combination of two or more.

[0116] The fatty acid ester may be a commercially available product or a synthetic product.

[0117] From the viewpoint of the interaction with the resin according to the present embodiment, the fatty acid ester preferably contains a fatty acid ester having 16 to 24 carbon atoms. Examples of such fatty acids include stearic acid, arachidic acid, behenic acid, lignoceric acid, etc.

[0118] More preferred release agents are at least one of behenyl behenate (behenyl behenate, the fatty acid ester having 22 carbon atoms), pentaerythritol tetrabehenate (pentaerythritol tetrabehenate, the fatty acid ester having 22 carbon atoms), ethylene glycol distearate (ethylene glycol distearate, the fatty acid ester having 18 carbon atoms), methyl lignocerate (the fatty acid ester having 24 carbon atoms), and hexadecyl palmitate (the fatty acid ester having 16 carbon atoms). In particular, behenyl behenate (behenyl behenate), pentaerythritol tetrabehenate, or ethylene glycol distearate is preferred.

[0119] The release agent may be a wax other than the fatty acid ester. Examples of the wax other than the fatty acid ester include polyolefin waxes such as low molecular weight polyethylene and low molecular weight polypropylene, branched chain hydrocarbon waxes such as microcrystalline wax, paraffin wax, long chain hydrocarbon waxes such as sasol wax, dialkyl ketone waxes such as distearyl ketone, and fatty acid amide waxes such as ethylene diamine behenamide and tristearyl trimellitate amide.

[0120] Regarding the content ratio of the release agent, from the viewpoint of the balance between fixing property and offset resistance, the total mass of the resin containing the structural unit represented by the above general formula (1) is set to 100% by mass, preferably in the range of 1 to 25% by mass. More preferably, it is in the range of 5 to 20% by mass.

[0121] <Colorant>

[0122] Regarding the toner according to this embodiment, the toner mother particles may contain a colorant. As the colorant, generally known dyes and pigments can be used.

[0123] As the colorant for obtaining a black toner, carbon black, magnetic materials, iron-titanium composite oxide black, etc. can be mentioned. As the above carbon black, channel black, furnace black, acetylene black, pyrolytic carbon black, lamp black, etc. can be mentioned. In addition, as the magnetic material, ferrite, magnetite, etc. can be mentioned.

[0124] As the colorant for obtaining a yellow toner, dyes such as C.I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, etc.; pigments such as C.I. Pigment Yellow 14, 17, 74, 93, 94, 138, 155, 180, 185, etc. can be mentioned.

[0125] As the colorant for obtaining a magenta toner, dyes such as C.I. Solvent Red 1, 49, 52, 58, 63, 111, 122, etc.; pigments such as C.I. Pigment Red 5, 48:1, 53:1, 57:1, 122, 139, 144, 149, 166, 177, 178, 222, etc. can be mentioned.

[0126] As the colorant for obtaining a cyan toner, dyes such as C.I. Solvent Blue 25, 36, 60, 70, 93, 95, etc.; pigments such as C.I. Pigment Blue 1, 7, 15, 60, 62, 66, 76, etc. can be mentioned.

[0127] Regarding the colorant for obtaining toners of each color, for each color, one kind or a combination of two or more kinds can be used.

[0128] Regarding the content ratio of the colorant, the total mass of the toner mother particles is set to 100% by mass, preferably in the range of 0.5 to 20% by mass, more preferably in the range of 2 to 10% by mass.

[0129] <Charge control agent>

[0130] The toner mother particles of the toner according to this embodiment may contain a charge control agent.

[0131] As for the charge control agent used, there is no particular limitation as long as it is a substance that can be positively or negatively charged by triboelectrification and is colorless. Therefore, as the above charge control agent, various known positively charged charge control agents and negatively charged charge control agents can be used.

[0132] Specifically, as the positively charged charge control agent, for example, nigrosine-based dyes such as "Nigrosine Base EX" (manufactured by Orient Chemical Industries, Ltd.), quaternary ammonium salts such as "Quaternary Ammonium Salt P-51" (manufactured by Orient Chemical Industries, Ltd.), "Copy Charge PX VP435" (manufactured by Hoechst Japan Ltd.), etc., alkoxylated amines, alkylamides, molybdate chelate pigments, and imidazole compounds such as "PLZ1001" (manufactured by Shikoku Chemicals Corporation), etc. can be cited.

[0133] In addition, as the negatively charged charge control agent, for example, metal complexes such as "Bontron (registered trademark) S-22", "Bontron (registered trademark) S-34", "Bontron (registered trademark) E-81", "Bontron (registered trademark) E-84" (the above are manufactured by Orient Chemical Industries, Ltd.), "Spiro Black TRH" (manufactured by Hodogaya Chemical Co., Ltd.), etc., thioindigo-based pigments, quaternary ammonium salts such as "Copy Charge NX VP434" (manufactured by Hoechst Japan Ltd.), calixarene compounds such as "Bontron (registered trademark) E-89" (manufactured by Orient Chemical Industries, Ltd.), boron compounds such as "LR147" (manufactured by Nippon Carlit Co., Ltd.), and fluorine compounds such as magnesium fluoride and carbon fluoride can be cited.

[0134] As the metal complex used as the negatively charged charge control agent, in addition to those shown above, substances having various structures such as hydroxycarboxylic acid metal complexes, dicarboxylic acid metal complexes, amino acid metal complexes, diketone metal complexes, diamine metal complexes, benzene-benzene derivative skeleton metal complexes containing an azo group, and benzene-naphthalene derivative skeleton metal complexes containing an azo group can also be used.

[0135] By configuring the toner base particles to contain a charge control agent in this way, the chargeability of the toner is improved.

[0136] Regarding the content ratio of the charge control agent, assuming the total mass of the toner base particles is 100% by mass, it is preferably in the range of 0.01 to 30% by mass, and more preferably in the range of 0.1 to 10% by mass.

[0137] <Morphology of Toner Base Particles>

[0138] There is no particular limitation on the morphology of the toner mother particles. For example, it can exhibit so-called single-layer structures, core-shell structures, multi-layer structures of three or more layers, domain-matrix structures, etc. It should be noted that the above single-layer structure refers to a homogeneous structure that is not of the core-shell type.

[0139] <External Additives>

[0140] In the above toner mother particles, external additives such as fluidizing agents and cleaning aids, which are so-called post-treatment agents, can be added to form the toner according to this embodiment. By adding such external additives, the fluidity, chargeability, cleanability, etc. of the toner can be improved.

[0141] Examples of external additives include inorganic oxide particles such as silica particles, alumina particles, and titanium oxide particles, inorganic stearic acid compound particles such as aluminum stearate particles and zinc stearate particles, and inorganic titanate compound particles such as strontium titanate particles and zinc titanate particles. These can be used alone or in combination of two or more.

[0142] Regarding these inorganic particles, in order to improve heat-resistant storage stability and environmental stability, surface treatment can be carried out with silane coupling agents, titanium coupling agents, higher fatty acids, silicone oils, etc.

[0143] Regarding the addition amount of the external additive, it is preferably in the range of 0.05 to 5 parts by mass, more preferably in the range of 0.1 to 3 parts by mass, relative to 100 parts by mass of the toner mother particles.

[0144] <Median Diameter of Toner Particles>

[0145] The volume-based median diameter (D50) of the toner particles is preferably in the range of 4 to 10 μm, more preferably in the range of 5 to 9 μm. By having the volume-based median diameter (D50) within the above range, the transfer efficiency is improved, the halftone image quality is improved, and the image quality of thin lines, dots, etc. is improved.

[0146] In this embodiment, regarding the volume-based median diameter (D50) of the toner particles, it is measured and calculated using a measuring device that connects a computer system (manufactured by Beckman Coulter, Inc.) equipped with the data processing software "Software V3.51" to a "Coulter Counter 3" (manufactured by Beckman Coulter, Inc.).

[0147] Specifically, 0.02 g of the measurement sample (toner) is added to 20 mL of the surfactant solution to make them compatible. Regarding the above surfactant solution, for the purpose of dispersing the toner particles, for example, it is a surfactant solution obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water.

[0148] Then, ultrasonic dispersion is carried out for 1 minute to prepare a toner dispersion liquid. The toner dispersion liquid is injected into a beaker with "ISOTON II" (manufactured by Beckman Coulter, Inc.) in a sample holder using a pipette until the indicated concentration of the measuring device becomes 8%.

[0149] Here, by forming this concentration range, reproducible measurement values can be obtained. In the measuring device, the number of measured particles is set to 25,000, the pore diameter is set to 50 μm, and the frequency values obtained by dividing the range of 1 to 30 μm as the measurement range into 256 parts are calculated. Then, the particle diameter at 50% starting from the larger volume integral ratio is set as the volume-based median diameter (D50).

[0150] [4. Method for manufacturing toner]

[0151] The method for manufacturing the toner is not particularly limited. For example, the toner can be manufactured by the following emulsion aggregation method. In addition, the resin, release agent, colorant, etc. according to the present embodiment can be melt-kneaded and then pulverized and classified to manufacture the toner.

[0152] As the emulsion aggregation method, the methods described in Japanese Patent Laid-Open No. 5-265252, Japanese Patent Laid-Open No. 6-329947, Japanese Patent Laid-Open No. 9-15904, etc. can be adopted. Furthermore, it can be a manufacturing method using suspension polymerization described in Japanese Patent Laid-Open No. 2010-191043. Among them, from the viewpoints of easy control of particle diameter and shape and reduction of energy cost during production, a manufacturing method using the emulsion aggregation method is preferred.

[0153] Regarding the manufacturing method using such an emulsion aggregation method, it preferably includes the following steps.

[0154] (1A) Toner binder particle dispersion liquid preparation step for preparing a dispersion liquid of toner binder particles

[0155] (1B) Colorant particle dispersion liquid preparation step for preparing a dispersion liquid of colorant particles

[0156] (1C) Release agent particle dispersion liquid preparation step for preparing a dispersion liquid of release agent particles

[0157] (2) Association step of adding a coagulant and performing salting out in an aqueous medium in the presence of toner binder particles, colorant particles, and release agent particles, and simultaneously performing aggregation and thermal bonding (fusion) to form associated particles

[0158] (3) Aging step of forming toner mother particles by controlling the shape of the associated particles

[0159] (4) A filtration and cleaning process of filtering and separating toner mother particles from an aqueous medium and removing surfactants, etc. from the toner mother particles

[0160] (5) A drying process of drying the toner mother particles that have been subjected to cleaning treatment

[0161] (6) An external additive addition process of adding external additives to the dried toner mother particles

[0162] Hereinafter, the processes of (1A) to (1C) will be described.

[0163] (1A) Toner binder particle dispersion preparation process

[0164] In this process, resin particles are formed by conventionally well-known emulsion polymerization, etc., and the resin particles are aggregated and thermally bonded to form toner binder particles. As an example, the polymerizable monomers (the above-mentioned first polymerizable monomer, second polymerizable monomer) constituting the toner binder are put into an aqueous medium, dispersed therein, and these polymerizable monomers are polymerized by a polymerization initiator. Thus, a dispersion of toner binder particles is prepared.

[0165] In addition, as a method for obtaining a dispersion of toner binder particles, in addition to the method of polymerizing polymerizable monomers by a polymerization initiator in the above-mentioned aqueous medium, there are the following methods. For example, there is a method of performing a dispersion treatment in an aqueous medium without using a solvent. Or, a method can be cited in which a polymer is dissolved in an organic solvent such as ethyl acetate to form a solution, the solution is emulsified and dispersed in an aqueous medium using a disperser, and then a desolvation treatment is performed.

[0166] At this time, a release agent may be contained in the toner binder in advance as needed. In addition, for dispersion, it is also preferable to polymerize it in the presence of a suitable conventionally well-known surfactant. As the above-mentioned conventionally well-known surfactant, for example, anionic surfactants such as polyoxyethylene (2) sodium lauryl ether, sodium lauryl sulfate, and sodium dodecylbenzenesulfonate can be cited.

[0167] The volume-based median diameter of the toner binder particles in the dispersion is preferably in the range of 50 to 300 nm. This median diameter can be measured by the dynamic light scattering method using "Microtrac UPA-150" (manufactured by Nikkiso Co., Ltd.).

[0168] (1B) Colorant particle dispersion preparation process

[0169] The process for preparing the coloring agent particle dispersion is a process for preparing a dispersion of coloring agent particles by dispersing the coloring agent in a water-based medium in the form of fine particles. For the dispersion of the coloring agent, mechanical energy can be utilized. The volume-based median diameter of the coloring agent particles in the dispersion is preferably in the range of 10 to 300 nm, more preferably in the range of 50 to 200 nm.

[0170] Regarding the volume-based median diameter of the coloring agent particles in the dispersion, similarly to the above, it can be measured by the dynamic light scattering method using "Microtrac UPA-150" (manufactured by Nikkiso Co., Ltd.).

[0171] (1C) Process for preparing the release agent particle dispersion

[0172] The process for preparing the release agent particle dispersion is a process for preparing a dispersion of release agent particles by dispersing the release agent in a water-based medium in the form of fine particles. The dispersion of the release agent can be carried out using mechanical energy. The volume-based median diameter of the release agent particles in the dispersion is preferably in the range of 100 to 1000 nm, more preferably in the range of 200 to 700 nm. The volume-based median diameter of the release agent particles in the dispersion can be measured by, for example, a laser diffraction particle size distribution analyzer LA-750 (manufactured by Horiba, Ltd.).

[0173] (Water-based medium)

[0174] Examples of the water-based medium used in the processes (1A) to (1C) include water, or a water-based medium having water as the main component (50 mass% or more) and containing optional components such as water-soluble solvents such as alcohols and diols, surfactants, and dispersants. The water-based medium is preferably a product obtained by mixing water and a surfactant.

[0175] Examples of the above water-soluble solvents include methanol, ethanol, isopropyl alcohol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Among these, alcohols such as methanol, ethanol, isopropyl alcohol, and butanol, which are organic solvents that do not dissolve polymers, are preferred.

[0176] As surfactants, for example, cationic surfactants, anionic surfactants, nonionic surfactants, etc. can be cited. As cationic surfactants, for example, dodecylammonium chloride, dodecylammonium bromide, dodecyltrimethylammonium bromide, dodecylpyridinium chloride, dodecylpyridinium bromide, cetyltrimethylammonium bromide, etc. can be cited. As anionic surfactants, for example, fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, etc. can be cited. In addition, as nonionic surfactants, for example, polyoxyethylene dodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monocapryloyl sucrose, etc. can be cited.

[0177] Such surfactants can be used alone or in combination of two or more. Among the surfactants, anionic surfactants are preferably used, and sodium dodecylbenzenesulfonate and sodium dodecyl sulfate are more preferably used.

[0178] Regarding the addition amount of the surfactant, relative to 100 parts by mass of the aqueous medium, it is preferably in the range of 0.01 to 10 parts by mass, and more preferably in the range of 0.04 to 2 parts by mass.

[0179] For the processes from the (2) association process to the (6) external additive addition process, they can be carried out according to various conventionally well-known methods.

[0180] It should be noted that there is no particular limitation on the coagulant used in the (2) association process, and a coagulant selected from metal salts is preferably used.

[0181] As metal salts for the coagulant, for example, monovalent metal salts such as salts of alkali metals such as sodium, potassium, and lithium can be cited; divalent metal salts such as calcium, magnesium, manganese, and copper; trivalent metal salts such as iron and aluminum, etc.

[0182] As specific metal salts, sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, polyaluminum chloride, etc. can be cited. Among these, from the consideration of being able to carry out coagulation with a smaller amount, divalent or trivalent metal salts are particularly preferably used. These can be used alone or in combination of two or more.

[0183] There is no particular limitation on the usage amount of the above-mentioned coagulant. From the viewpoint of controlling the particle size of the toner, it is preferably 2% to 30% by mass relative to the solid content of the toner binder.

[0184] [5. Developer]

[0185] Regarding the toner according to this embodiment, it can be used as a one-component developer alone or as a two-component developer by mixing with carrier particles.

[0186] When used as a one-component developer, the toner can be a magnetic toner containing a magnetic material or a non-magnetic toner without a magnetic material. As the above magnetic material, for example, magnetite, γ-hematite, or various ferrites can be used.

[0187] As the carrier particles constituting the two-component developer, magnetic particles made of known materials such as metals like iron, steel, nickel, cobalt, ferrites, magnetite, and alloys of these metals with metals such as aluminum and lead can be used.

[0188] As the carrier particles, coated carrier particles obtained by coating the surface of magnetic particles with a coating agent such as resin and so-called resin-dispersed carrier particles in which magnetic powder is dispersed in a binder resin are preferably used.

[0189] The resin for coating is not particularly limited. For example, olefin resin, styrene resin, styrene-acrylic resin, silicone resin, polyester resin, or fluororesin can be used.

[0190] The resin used to form the resin-dispersed carrier particles is not particularly limited, and known resins can be used. As such resins, for example, acrylic resin, styrene-acrylic resin, polyester resin, fluororesin, phenolic resin, etc. can be used.

[0191] The volume-based median diameter of the carrier particles is preferably in the range of 20 to 100 μm, more preferably in the range of 25 to 60 μm.

[0192] The volume-based median diameter of the carrier particles can typically be measured by a laser diffraction particle size distribution measuring device equipped with a wet disperser. As the above laser diffraction particle size distribution measuring device, "HELOS" (manufactured by SYMPATEC) can be cited.

[0193] Regarding the mixing amount of the toner particles relative to the carrier particles, when the total mass of the toner particles and the carrier particles is set to 100% by mass, it is preferably in the range of 2 to 10% by mass.

[0194] [6. Image Forming Method Using Toner]

[0195] The toner according to this embodiment can be suitably used in an image forming method including a fixing step using a thermal pressure fixing method capable of heating while applying pressure. In particular, the fixing temperature in the fixing step can be suitably used in an image forming method for fixing at a relatively low temperature. Regarding the above fixing temperature, it is a temperature within the range of 115 to 140°C, preferably 115 to 130°C, of the surface temperature of the heating member in the fixing nip portion.

[0196] The toner according to this embodiment can also be suitably applied to an image forming method for high-speed fixing with a fixing line speed in the range of 200 to 600 mm / second.

[0197] In an image forming method including a fixing step using a thermal pressure fixing method, for example, first, a static charge image formed on a photoreceptor is developed with a toner to obtain a toner image. The toner image is transferred from the photoreceptor to an image support. Then, the toner image transferred on the image support is fixed to the image support by a fixing process using a thermal pressure fixing method. Thereby, a printed matter on which a visible image is formed is obtained.

[0198] In addition, the toner according to this embodiment can be used in a monochromatic image forming method and a full-color image forming method. In a full-color image forming method, it can be applied to a 4-cycle image forming method composed of 4 color developing devices each related to yellow, magenta, cyan, and black and 1 photoreceptor. In addition, an image forming unit having a color developing device and a photoreceptor related to each color can also be applied to a tandem image forming method mounted by color respectively. The toner according to this embodiment can be applied in any of the above image forming methods.

[0199] [7. Ink]

[0200] Regarding the resin of this embodiment having a structural unit represented by the above general formula (1), it can also be included in the ink. Regarding the ink, in addition to the resin according to this embodiment, a colorant, a solvent, other resins, various additives, etc. can also be included.

[0201] The ink containing the resin according to this embodiment can form an image excellent in light resistance and adhesion to a medium.

[0202] Since the resin according to this embodiment has an aromatic ring, it has a high ultraviolet absorption ability. Therefore, in an image formed using the ink containing this resin, the colorant is not easily affected by ultraviolet rays because the resin absorbs ultraviolet rays. By such an action, the light resistance of the image formed using the ink containing the resin according to this embodiment becomes good.

[0203] In addition, since the resin involved in this embodiment has polar groups, the adhesiveness to media such as paper becomes good for the image formed by the ink containing the resin involved in this embodiment.

[0204] As an example of the ink application method in image formation using ink, spraying method, mangle method (pad method or dipping method), coating method, inkjet method, etc. can be cited. In the case of forming a high-precision image, the inkjet method is preferred.

[0205] [8. Printed Image]

[0206] The printed image according to this embodiment is characterized by containing a resin having a structural unit represented by the above general formula (1).

[0207] This printed image can be formed using the above toner and ink.

[0208] For this printed image, by containing a resin having a structural unit represented by the above general formula (1), the light resistance and the adhesiveness to the medium are excellent.

[0209] Examples

[0210] Hereinafter, examples are given to specifically illustrate the present invention, but the present invention is not limited to these. It should be noted that in the following examples, unless otherwise specified, the operations are carried out at room temperature (25 °C). In addition, unless otherwise specified, "%" and "parts" respectively mean "mass %" and "mass parts".

[0211] [Polymerizable Monomer]

[0212] As the first polymerizable monomer having a structural unit represented by the general formula (2), the above-exemplified compounds M1 to M7 are used.

[0213] In addition, as a comparative compound, M8 having the following structure is used.

[0214]

[0215] Regarding R1, R2, R3, and R4 in the general formula (2) among M1 to 8, they are as shown in the following table.

[0216]

Table 1

[0217] <![CDATA[R1]]> <![CDATA[R2]]> <![CDATA[R3]]> <![CDATA[R4]]> M1 Me Me H H M2 H Me H H M3 H H H H M4 Me n-Bu H H M5 H Me OMe OMe M6 H Me H O-t-Bu M7 H Me O-t-Bu H M8 Et n-Hex O-n-Hex O-n-Hex

[0218] The abbreviations described in Table 1 respectively represent the following atoms or substituents.

[0219] H: Hydrogen atom

[0220] Me: Methyl

[0221] Et: Ethyl

[0222] n-Bu: n-Butyl

[0223] n-Hex: n-Hexyl

[0224] OMe: Methoxy

[0225] O-t-Bu: tert-Butoxy

[0226] O-n-Hex: n-Hexyloxy

[0227] In addition, the following compounds were used as the second polymerizable monomer.

[0228] St: Styrene

[0229] MMA: Methyl methacrylate

[0230] nBA: n-Butyl acrylate

[0231] iBA: Isobutyl acrylate

[0232] 2EHA: 2-Ethylhexyl acrylate

[0233] MAA: Methacrylic acid

[0234] AA: Acrylic acid

[0235] [Synthesis of Resin]

[0236] Prepare a surfactant solution by dissolving 8 g of sodium dodecyl sulfate in 3 L of ion-exchanged water. In a 5-L stainless steel kettle (SUS kettle) equipped with a stirring device, a temperature sensor, a condenser, and a nitrogen introduction device, load the above surfactant solution. Then, while stirring at a stirring speed of 230 rpm under a nitrogen stream, heat up to a liquid temperature of 80 °C.

[0237] In this surfactant solution, add an initiator solution prepared by dissolving 10 g of potassium persulfate in 200 g of ion-exchanged water, and keep the temperature at 80 °C. Then, prepare a mixed solution in which polymerizable monomers are added at the addition ratios shown in Table 2 below so that the solid content concentration of the resulting resin particle dispersion becomes 20% by mass, and dropwise add it to the above surfactant solution over 100 minutes. Polymerize the polymerizable monomers by heating and stirring this system at 80 °C for 2 hours.

[0238] The addition amounts of the polymerizable monomers described in Table 2 represent the respective addition amounts when the total addition amount of the first and second polymerizable monomers is set to 100% by mass.

[0239] Thus, resin particle dispersions 1 to 14 with a solid component concentration of 20% by mass were prepared respectively. The resins contained in resin particle dispersions 1 to 14 were designated as resins 1 to 14 respectively.

[0240] The peak molecular weights of resins 1 to 14 are shown in Table 2. The peak molecular weight was measured as follows. Using the apparatus “HLC-8220” (manufactured by Tosoh Corporation) and the column “TSKguardcolumn+TSKgelSuperHZM-M3 connection” (manufactured by Tosoh Corporation). While maintaining the column temperature at 40°C, tetrahydrofuran (THF) was made to flow at a flow rate of 0.2 ml / min as the carrier solvent. Next, the measurement sample was dissolved in tetrahydrofuran at a concentration of 1 mg / ml under the dissolution conditions of being treated with an ultrasonic disperser at room temperature (25°C) for 5 minutes. Next, it was treated with a membrane filter with a pore size of 0.2 μm to obtain a sample solution, and 10 μL of this sample solution was injected into the apparatus together with the above-mentioned carrier solvent. Then, a refractive index detector (RI detector) was used to detect the molecular weight distribution of the measurement sample. From this molecular weight distribution, the peak molecular weight was obtained.

[0241] The volume-based median diameters of the resin particles in resin particle dispersions 1 to 14 were all 128 nm. This median diameter was measured by the dynamic light scattering method using “Microtrac UPA-150” (manufactured by Nikkiso Co., Ltd.).

[0242] [Preparation of toner]

[0243] Using resin particle dispersions 1 to 14 as toner binder particle dispersions, toner was prepared as follows.

[0244] <Preparation of colorant dispersion>

[0245] Colorant: Carbon black (Mogul (registered trademark) L manufactured by Cabot Corporation)

[0246] 10 parts by mass

[0247] Anionic surfactant (20% aqueous solution of sodium dodecylbenzenesulfonate)

[0248] 1.5 parts by mass

[0249] 90 parts by mass of ion-exchanged water

[0250] The above components were mixed and dispersed using an SC mill to obtain a colorant dispersion.

[0251] The volume-based median diameter of the colorant particles in the colorant dispersion was 154 nm. This median diameter was measured by the dynamic light scattering method using “Microtrac UPA-150” (manufactured by Nikkiso Co., Ltd.).

[0252] <Preparation of mold release agent dispersion liquid>

[0253] 100 parts by mass of behenyl behenate

[0254] 5 parts by mass of sodium lauryl sulfate

[0255] 240 parts by mass of ion-exchanged water The above components were dispersed in a round stainless steel flask using a homogenizer "ULTRA-TURRAX (registered trademark) T50" (manufactured by IKA Corporation) for 10 minutes. Then, dispersion treatment was performed using a pressure discharge type homogenizer to obtain a mold release agent dispersion liquid.

[0256] The median diameter of the mold release agent particles in the mold release agent dispersion liquid based on volume was 530 nm. It was measured using a laser diffraction particle size distribution analyzer LA-750 (manufactured by Horiba, Ltd.).

[0257] <Preparation of toner mother particle dispersion liquid 1>

[0258]

[0259] The above components were mixed and dispersed in a round stainless steel flask using a homogenizer "ULTRA-TURRAX (registered trademark) T50" (manufactured by IKA Corporation). Then, while stirring the inside of the flask in a heating oil bath, it was heated to 55 °C. After maintaining at 55 °C for 30 minutes, it was confirmed that aggregated particles with a median diameter (D50) based on volume of 4.8 μm were formed in the solution.

[0260] Furthermore, the temperature of the heating oil bath was increased and maintained at 56 °C for 2 hours, then the median diameter (D50) based on volume became 5.9 μm.

[0261] Then, 1 mol / L sodium hydroxide was added to the system to adjust the pH of the system to 5.0. Then, the stainless steel flask was sealed using a magnetic seal and heated to 98 °C while continuing to stir. By continuing to stir for 6 hours, thermal bonding (fusion) between the toner binder particles was completed to prepare a toner mother particle dispersion liquid. The median diameter (D50) of the toner mother particles in the dispersion liquid based on volume was 6.0 μm.

[0262] <Washing and drying process>

[0263] The toner mother particle dispersion liquid was subjected to solid-liquid separation using a basket-type centrifuge "MARKII I model 60×40" (manufactured by Matsumoto Machinery Sales Co., Ltd.) to form a wet filter cake of toner mother particles.

[0264] The wet filter cake was washed with ion-exchanged water at 45 °C using the above-mentioned basket centrifuge until the conductivity of the filtrate reached 5 μS / cm. Then, it was transferred to a "flash jet dryer" (manufactured by Seishin Enterprise Co., Ltd.) and dried until the moisture content became 0.5% by mass, obtaining toner mother particles 1.

[0265] <Preparation of Toner Mother Particles 2 to 14>

[0266] Except that in the preparation of toner mother particles 1, the toner binder particle dispersion liquid 1 was changed to toner binder particle dispersions 2 to 14 respectively, toner mother particles 2 to 14 were prepared in the same manner.

[0267] <External Additive Treatment of Toner Mother Particles>

[0268] To 100 parts by mass of the toner mother particles obtained above, 1 part by mass of hydrophobic silica (number-average primary particle diameter = 12 nm) and 0.3 part by mass of hydrophobic titanium dioxide (number-average primary particle diameter = 20 nm) were added. Then, they were mixed by a Henschel mixer (registered trademark) to conduct an external additive treatment, manufacturing toners 1 to 14.

[0269] [Preparation of Two-Component Developer]

[0270] The following components were put into a horizontal stirring blade type high-speed stirring device and mixed for 15 minutes under the conditions of the peripheral speed of the stirring blade: 8 m / s and the temperature: 30 °C.

[0271] Ferrite particles (volume-based median diameter: 50 μm (manufactured by Powdertech Co., Ltd.))

[0272] 100 parts by mass

[0273] Methyl methacrylate-cyclohexyl methacrylate copolymer resin (volume-based median diameter of primary particles: 85 nm)

[0274] 4 parts by mass

[0275] Next, the system was heated to 120 °C and stirring was continued for 4 hours. Then, the system was cooled and the fragments of the methyl methacrylate-cyclohexyl methacrylate copolymer resin were removed using a 200-mesh sieve. Thus, a resin-coated carrier was produced.

[0276] The resin-coated carrier was mixed in each of the above toners 1 to 14 to prepare two-component developers 1 to 14 such that the concentration of the toner was 7% by mass based on the total mass of the toner and the carrier.

[0277]

[0278] [Evaluation]

[0279] Using the two-component developer 1 to 14, the fixing property and the chargeability were evaluated as described below. The evaluation results are shown in Table 3.

[0280] (1) Fixing property

[0281] As the image forming apparatus, a commercially available multifunction machine "bizhub PRO C6500" (manufactured by Konica Minolta Business Technologies, Inc.) was used. In this apparatus, the above two-component developer was loaded as the developer. Then, the surface temperature of the fixing heating member in the fixing means of the heat roller fixing method was changed every 5 °C in the range of 80 to 150 °C. For each temperature, in an environment of normal temperature and normal humidity (temperature 20 °C, humidity 50% RH), as the image support, thick paper with a basis weight of 350 g / m 2 was used to form an image, and a solid color image (solid image) with an image density of 0.8 was obtained as a visible image. Then, the fixed solid color image was folded using a folder, and air at 0.35 MPa was sprayed onto it. For the state of the crease, the retention rate of the image density was evaluated in 5 grades according to the following evaluation criteria, and the fixing temperature of grade 3 was set as the lowest fixing temperature. If the lowest fixing temperature indicating the level of grade 3 is 130 °C or lower, it indicates sufficient low-temperature fixing property.

[0282] [Evaluation criteria]

[0283] Grade 5: The retention rate of the image density is 90% or more

[0284] Grade 4: The retention rate of the image density is 75% or more and less than 90%

[0285] Grade 3: The retention rate of the image density is 60% or more and less than 75%

[0286] Grade 2: The retention rate of the image density is 45% or more and less than 60%

[0287] Grade 1: The retention rate of the image density is less than 45%

[0288] (2) Chargeability

[0289] When measuring the charge amount of the toner, the device shown in Figure 1 was used for measurement.

[0290] First, 1 g of the developer measured using a precision balance is placed in a uniform manner on the entire surface of the conductive sleeve (31). A voltage of 2 kV is supplied from the bias power supply (33) to the sleeve (31), and at the same time, the rotational speed of the magnetic roller (32) provided inside the conductive sleeve (31) is set to 1000 rpm. It is left in this state for 30 seconds, and the toner is collected on the cylindrical electrode (34). After 30 seconds, the potential Vm of the cylindrical electrode (34) is measured, and at the same time, the charge amount of the toner is determined. Further, the mass of the collected toner is measured using a precision balance, and the average charge amount is obtained. The value obtained by dividing the average charge amount by the mixing time (mixing for 10 minutes using a vibrator (Yayoi - type New - YS) with a vibration angle of 30° and a vibration frequency of 200 strokes / minute) is used as the chargeability index.

[0291] If the chargeability index is 6.5 μC / g / min or more, sufficient charge amount without problems is exhibited even during high - speed printing output.

[0292]

Table 3

[0293]

[0294] From the above evaluation results, it can be seen that for the toner containing the resin having a structural unit represented by the general formula (1), the fixing property and chargeability are good compared with the comparative examples.

[0295] In addition, it can be seen from this that the resin having a structural unit represented by the general formula (1) has excellent thermal properties and electrical properties.

[0296] Industrial Applicability

[0297] According to the resin of the present invention, the viscosity can be reduced with low energy, and the charge leakage property can be made low. In addition, according to the toner for electrostatic charge image development of the present invention, the low - temperature fixing property can be sufficiently improved and the heat - resistant storage property can be made good. Therefore, the present invention is useful in the field of image formation.

[0298] Although the embodiments of the present invention have been described and illustrated in detail, it is clearly understood that this is only for illustration and example, not for limitation, and the scope of the present invention should be interpreted by the terms of the appended claims.

Claims

1. A resin comprising a structural unit represented by the following general formula (1), In the general formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.

2. The resin according to claim 1, wherein, In the general formula (1), R2 is a methyl group, and R3 and R4 are hydrogen atoms.

3. The resin according to claim 1, wherein, The resin is a copolymer of a first polymerizable monomer having a structure represented by the following general formula (2) and a second polymerizable monomer copolymerizable with the first polymerizable monomer, In the general formula (2), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.

4. The resin according to claim 3, wherein, The content ratio of the structural unit derived from the first polymerizable monomer is 10% by mass to 40% by mass based on all the structural units constituting the resin.

5. The resin according to claim 3, wherein, The second polymerizable monomer includes at least one monomer selected from styrenes, acrylic acid, methacrylic acid, acrylates, and methacrylates.

6. The resin according to claim 5, wherein The second polymerizable monomer includes at least one monomer selected from styrene, acrylic acid, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, n-butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate.

7. A resin composition comprising the resin according to claim 1.

8. A printed image comprising the resin according to claim 1.

9. A toner for electrostatic charge image development comprising the resin according to claim 1.

10. A method for manufacturing a toner for electrostatic charge image development, which is a method for manufacturing a toner for electrostatic charge image development according to claim 9, comprising: a step of preparing a resin comprising a structural unit represented by the following general formula (1), a step of preparing a toner binder particle dispersion from the resin, and a step of aggregating toner binder particles in the toner binder particle dispersion and thermally bonding the particles to each other, In the general formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.

11. The method for manufacturing a toner for developing an electrostatic charge image according to claim 10, wherein, The step of preparing a resin comprising a structural unit represented by the general formula (1) includes a step of polymerizing a first polymerizable monomer having a structure represented by the following general formula (2), In the general formula (2), R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.

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