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

Abstract

To provide: a biomass-derived resin having excellent thermal characteristics and electrical characteristics; and a resin composition, a printed image, a toner for developing an electrostatic image, and a method for producing the electrostatic charge image developing toner that are based on the resin.SOLUTION: The resin comprises a constitutional unit represented by the following general formula (1).SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] The production of industrial useful chemical products from inedible biomass is one of the technologies that can contribute to the realization of a low-carbon society. So far, the chemical products derived from biomass that have been industrialized are mainly aliphatic materials, and the production of aromatic materials that impart functionality such as thermal stability and rigidity to polymers has not been realized.

[0003] One of the aromatic materials that can be highly productively derived from cellulose, an inedible biomass, is phenyl lactic acids. Although this material can be considered for use as a polyester material by polycondensation, it has not yet been put into practical use. If phenyl lactic acids can be induced into (meth)acrylic esters and applied to addition polymerization as monomer raw materials, the target applications of the resulting resin can be significantly expanded without being limited to polycondensation, and the replacement of petroleum-derived aromatic polymer materials and the development of new functional materials can be expected. It is considered that these developments can greatly advance the creation of a low-carbon society.

[0004] Specifically, it is considered that the realization of a low-carbon society can be made a reality by producing polymer materials using phenyl lactic acids as follows. (1) Find a material with high potential for use as a chemical product raw material from among low-molecular-weight phenyl lactic acids produced from glucose. (2) Induce the above phenyl lactic acids into aromatic monomers useful for industry. (3) Produce a polymer material having desired performance from the above aromatic monomers.

[0005] One use of the resin material can be toner used in digital printing. Conventionally, styrene, a petroleum-based material, can be cited as the main raw material of toner. Styrene occupies a large part of the toner resin as a hard segment with a relatively high glass transition temperature. As a biomass monomer that can potentially replace styrene used as this hard segment, methyl biomethacrylate 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. However, it has been difficult to satisfy both the thermal and electrical properties required for toner resin materials. Toner is fixed on paper, which is the medium, by heat, pressure, etc., and output as an image. The amount of electric power consumed as heat during fixing accounts for 70% of the total power consumption of the entire toner image forming apparatus. Therefore, reducing the power consumption during the heat fixing of toner has been a major ongoing issue for reducing the power consumption of toner image formation.

[0006] Conventionally, in response to the problem of reducing such power consumption, the development of resin materials that can be melted with a low amount of energy has been studied (see, for example, Patent Documents 1 to 3). Specifically, reducing the glass transition temperature of the resin and reducing the melt viscosity of the toner by controlling the molecular weight distribution of the resin have been studied.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0008] The glass transition temperature of the resin can be adjusted, for example, in the case of styrene-acrylic resins, by the ratio of the monomers. Specifically, it can be adjusted by the ratio of monomers that form hard segments (high glass transition temperature components) such as styrene and monomers that form soft segments (low glass transition temperature components) such as n-butyl acrylate.

[0009] However, increasing the ratio of the soft segment in the resin has a problem that, for example, when used as a toner, while low-temperature fixing of the toner can be achieved, the fixing and separating properties of the toner deteriorate. In addition, n-butyl acrylate, which is a general-purpose monomer as a soft segment, has a high dielectric loss tangent (tanδ), which is an index of charge leakage. Therefore, when n-butyl acrylate is used, there is also a problem of lowering the charge retention of the toner. The low charge retention leads to low electrification of the toner, and as a result, problems such as internal contamination of the machine due to toner scattering and occurrence of image defects have become apparent.

[0010] In addition, there are other cases where a resin that can reduce viscosity with a low amount of energy and has low charge leakage is required, and a biomass-derived resin that easily reduces viscosity at low temperatures and has excellent charge retention has been demanded.

[0011] The present invention has been made in view of the above problems and situations. The problem to be solved is to provide a biomass-derived resin having excellent thermal and electrical properties, a resin composition using the resin, a printed image, an electrostatic charge image developing toner, and a method for producing an electrostatic charge image developing toner.

Means for Solving the Problems

[0012] The present inventor has found that a resin having a specific structural unit derived from biomass has excellent thermal and electrical properties.

[0013] That is, the above problem can be solved by the following configuration.

[0014] [1] A resin containing a structural unit represented by the following general formula (1). [Chemical formula] (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. R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.)

[0015] [2] The resin according to [1], wherein R2 in the general formula (1) is a methyl group, and R3 and R4 are hydrogen atoms. [1] The resin according to [1].

[0016] [3] 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. [1] The resin according to [1]. [Chemical formula] (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. R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.)

[0017] [4] The content 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. [3] The resin according to [3].

[0018] [5] The second polymerizable monomer contains at least one monomer selected from the group consisting of styrenes, acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters. [3] or [4] The resin according to [3] or [4].

[0019] [6] The second polymerizable monomer contains at least one monomer selected from the group consisting of styrene, acrylic acid, n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, n-butyl methacrylate, iso-butyl methacrylate, and 2-ethylhexyl methacrylate. [3] The resin according to any one of [5].

[0020] [7] A resin composition containing the resin according to any one of [1] to [6].

[0021] [8] A printed image containing the resin according to any one of [1] to [6].

[0022] [9] An electrostatic charge image developing toner containing the resin according to any one of [1] to [6].

[0023]

[10] A method for manufacturing an electrostatic charge image developing toner for manufacturing the electrostatic charge image developing toner according to [9], comprising a step of preparing a resin containing a structural unit represented by the following general formula (1); a step of preparing a toner binder particle dispersion from the resin; a step of aggregating toner binder particles and fusing the particles together in the toner binder particle dispersion; The method for manufacturing an electrostatic charge image developing toner, comprising the above steps.

Chemical formula

[0024]

[11] The step of preparing a resin containing 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).

[10] The method for manufacturing an electrostatic charge image developing toner according to

[10] . [Chemical formula] (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. R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.) [Advantages of the Invention]

[0025] According to the present invention, it is possible to provide a biomass-derived resin excellent in thermal properties and electrical properties, a resin composition using the resin, a printed image, an electrostatic charge image developing toner, and a method for producing an electrostatic charge image developing toner.

[0026] Although the mechanism of expression or the mechanism of action of the effects of the present invention has not been clearly understood, it is presumed as follows. Note that the following mechanism is based on speculation, and the present invention is not limited by the following mechanism at all.

[0027] The control of the thermal properties of an acrylic resin can generally be adjusted by copolymerizing two or more kinds of monomers. Specifically, by adjusting the ratio of a hard segment having a high glass transition temperature and a soft segment having a low glass transition temperature, it is possible to control the thermal properties. For example, as a biomass-derived (meth)acrylic resin raw material, it is possible to produce a resin by copolymerizing methyl methacrylate having a high glass transition temperature and n-butyl acrylate having a low glass transition temperature. However, in this case, microscopically, a homopolymer site is partially formed, and since the steric hindrance of the side chains of each polymer is small, the interaction between the molecular chains of the obtained resin becomes large as a result. Therefore, in such a conventional resin, it is difficult to reduce the viscosity at a low temperature. For example, when used as a toner binder, the sharp meltability required for the toner cannot be realized.

[0028] On the one hand, since the resin of the present invention has a bulky side chain structure, the interaction between molecular chains can be suppressed, and the molecular mobility of the main chain is likely to increase at a relatively low temperature, so the viscosity is likely to decrease. Thus, for example, it is considered that the sharp meltability required for toner can be realized.

[0029] Regarding electrical properties, the charging phenomenon of polymers is still an unexplained phenomenon, and several hypotheses have been proposed. When charging is considered to occur by the movement of electrons to traps such as structural defects existing in the forbidden band, how to control the traps is considered important for charge control. Traps are also considered to consist of electron levels with a double Gaussian distribution of anionic and cationic states caused by the molecular arrangement. The phenyl lactate acrylate skeleton has more polar sites such as carbonyl groups and ester groups compared to styrene and methyl methacrylate, so it is more likely to have a more diverse polarization structure. Therefore, the probabilities of the anionic state and the cationic state are increased, and as a result, it is easy to accept electrons, and it can be estimated that the charging characteristics such as charging rise and charge retention are excellent.

Brief Description of the Drawings

[0030]

Figure 1

Modes for Carrying Out the Invention

[0031] The resin according to the present embodiment is characterized by having a structural unit represented by the above general formula (1). This feature is a technical feature common to or corresponding to the following embodiments.

[0032] As the resin according to the present embodiment, it is preferable that R2 in the general formula (1) is a methyl group, and R3 and R4 are hydrogen atoms. Thereby, the thermal properties and electrical properties become better. Also, the stereoregularity of the lactic acid moiety may be any of the D-form, L-form, and a mixture of D-form and L-form.

[0033] As the resin according to this embodiment, a copolymer of a first polymerizable monomer having a structure represented by the above 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 efficiently exhibited.

[0034] As the resin according to this embodiment, the content 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 properties and electrical properties become better.

[0035] As an embodiment of the resin according to this embodiment, the second polymerizable monomer preferably contains at least one monomer selected from the group consisting of at least styrenes, acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters. Thereby, it becomes easy to adjust the glass transition temperature of the resin.

[0036] As an embodiment of the resin according to this embodiment, the second polymerizable monomer preferably contains at least one monomer selected from the group consisting of 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.

[0037] The resin composition according to this embodiment contains a resin having a structural unit represented by the above general formula (1).

[0038] The printed image according to this embodiment contains a resin having a structural unit represented by the above general formula (1).

[0039] The toner for electrostatic charge image development according to this embodiment contains a resin having a structural unit represented by the above general formula (1).

[0040] The method for manufacturing a toner for electrostatic charge image development 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 fuse the particles together. Thereby, a biomass-derived resin excellent in thermal properties and electrical properties can be manufactured.

[0041] The method for manufacturing a toner for electrostatic charge image development according to this embodiment may include a step of polymerizing a first polymerizable monomer having a structure represented by the above general formula (2) in the step of preparing a resin containing a structural unit represented by the above general formula (1).

[0042] Hereinafter, the present invention, its components, and forms and aspects for implementing the present invention will be described. In the present application, "~" is used in the sense of including the numerical values described before and after it as a lower limit value and an upper limit value.

[0043] [1. Resin having a structural unit represented by general formula (1)] The resin according to this embodiment has a structural unit represented by the following general formula (1).

[0044] [Chemical formula]

[0045] 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. R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.

[0046] Specific examples of R2 include, for example, a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, and a t-butyl group.

[0047] Specific examples of R3 and R4 include, for example, a hydrogen atom, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, and a t-butoxy group.

[0048] From the viewpoint of reducing hydrogen bonding and moderately suppressing the interaction between molecular chains to easily lower the viscosity at a relatively low temperature, R2 is preferably an alkyl group having 1 to 4 carbon atoms. Further, from the viewpoint of reducing the influence of a relatively non-polar alkyl group in addition to lowering the viscosity, increasing the polarity of the resin, and easily lowering the charge leakage property, R2 is more preferably a methyl group. Similarly, from the viewpoints of thermal properties and electrical properties, R3 and R4 are preferably hydrogen atoms.

[0049] 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).

[0050]

Chemical formula

[0051] 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. R3 and R4 each independently represent a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.

[0052] R2, R3, and R4 in the general formula (2) have the same meanings as R2, R3, and R4 in the general formula (1), respectively.

[0053] The first polymerizable monomer can be used alone or in combination of two or more.

[0054] Specific examples of the first polymerizable monomer include the following exemplified compounds M1 to M7. Note that the first polymerizable monomer is not limited thereto.

Chemical formula

[0055] The first polymerizable monomer can be synthesized, for example, according to the following synthetic scheme.

[0056] Synthesis of phenyl lactate esters In a four-necked flask, 275 mmol of phenyl lactic acid was dissolved in 405 ml of dry THF, and 560 mmol (meta) of triethylamine was added. Then, 280 mmol of (meta) acrylic acid 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.

[0057]

Chemical formula

[0058] 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 efficiently 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 another polymerizable monomer copolymerizable with the first polymerizable monomer (also referred to as the "second polymerizable monomer").

[0059] Examples of the second polymerizable monomer include Styrenes such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-acetoxystyrene, m-acetoxystyrene, p-acetoxystyrene; Acrylic esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, isobutyl acrylate (iso-butyl acrylate), n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate; Methacrylic esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate (iso-butyl methacrylate), tert-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; Examples include acrylic acid, methacrylic acid, etc.

[0060] Among these, it is preferably included at least one monomer selected from the group consisting of styrenes, acrylic acid, methacrylic acid, acrylic esters and methacrylic esters. Further, it is preferably selected from one or more of styrene, acrylic acid, n-butyl acrylate, iso-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, n-butyl methacrylate, iso-butyl methacrylate, 2-ethylhexyl methacrylate. More preferably, at least one of styrene and n-butyl acrylate. By using such a polymerizable monomer, it becomes easy to adjust the glass transition temperature of the resin.

[0061] As the second polymerizable monomer, a polymerizable monomer having an ionic dissociable group may be used. The polymerizable monomer having an ionic dissociable group has a group such as a carboxy group, a sulfonic acid group, a phosphoric acid group, etc. Specifically, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, etc. are mentioned. Among these, acrylic acid or methacrylic acid is preferred.

[0062] The second polymerizable monomer can be used alone or in combination of two or more.

[0063] In the resin according to this embodiment, the content 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 still more preferably in the range of 15 to 35% by mass with respect to all the structural units (100% by mass) constituting the resin. When the content of the structural unit derived from the first polymerizable monomer is increased, the chargeability tends to increase. Further, when the content of the structural unit derived from the first polymerizable monomer is 10 to 40% by mass, bulky structural units are appropriately introduced, so that the melt viscosity is likely to be lowered, and when used in toner, the low-temperature fixability tends to increase. Further, when the content of the structural unit derived from the first polymerizable monomer is 15 to 35% by mass, the melt viscosity is more likely to be lowered, and when used in toner, the low-temperature fixability is more likely to increase.

[0064] In the resin according to this embodiment, the content of the structural unit derived from the second polymerizable monomer is not particularly limited and can be appropriately adjusted according to the type of the structural unit.

[0065] For example, when the second polymerizable monomer contains styrenes, the content of the styrenes is preferably in the range of 20 to 80% by mass, more preferably in the range of 30 to 70% by mass with respect to all the structural units (100% by mass) constituting the resin.

[0066] When the second polymerizable monomer contains an acrylate or a methacrylate, the content of the acrylate or the methacrylate is preferably in the range of 5 to 50% by mass, more preferably in the range of 10 to 40% by mass with respect to all the structural units (100% by mass) constituting the resin.

[0067] When the second polymerizable monomer contains a polymerizable monomer 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 with respect to all the structural units (100% by mass) constituting the resin.

[0068] The method for synthesizing the resin according to the present embodiment using the first polymerizable monomer and optionally the second polymerizable monomer is not particularly limited. However, from the viewpoint of easy polymerization, a method of radical polymerizing the monomer using a known oil-soluble or water-soluble radical polymerization initiator is preferable.

[0069] 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. If necessary, for example, known chain transfer agents such as n-octyl mercaptan and n-octyl-3-mercaptopropionate may be used.

[0070] Examples of the polymerization initiator include 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; peroxide-based polymerization initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxydicarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis-(4,4-t-butylperoxycyclohexyl)propane, and tris-(t-butylperoxy)triazine.

[0071] When synthesizing the resin by an emulsion polymerization method, a water-soluble radical polymerization initiator can be used.

[0072] Examples of the water-soluble radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, and hydrogen peroxide.

[0073] The polymerization temperature varies depending on the types of monomers and polymerization initiators used, but is preferably in the range of 50 to 100°C, more preferably in the range of 55 to 90°C.

[0074] The polymerization time varies depending on the types of monomers and polymerization initiators used, but is preferably, for example, 1 to 12 hours.

[0075] The resin according to this embodiment preferably has a peak molecular weight in the range of 3,500 to 35,000 in terms of polystyrene conversion measured by gel permeation chromatography (GPC). More preferably, it is in the range of 10,000 to 30,000. With a peak molecular weight in such a range, the melt viscosity during heating can be set within an appropriate range, and it is easy to improve the handleability of the molten resin. 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 simultaneously.

[0076] The above peak molecular weight is the molecular weight corresponding to the elution time at the peak top in the molecular weight distribution. When there are multiple peaks in the molecular weight distribution, the molecular weight corresponding to the elution time at the peak top with the largest peak area ratio is taken as the peak molecular weight.

[0077] The peak molecular weight of the resin can be measured by the following method. Specifically, the apparatus "HLC-8220" (manufactured by Tosoh Corporation) and the column "TSKguardcolumn + TSKgel SuperHZM-M3 series" (manufactured by Tosoh Corporation) are used. While maintaining the column temperature at 40°C, tetrahydrofuran (THF) is flowed as a carrier solvent at a flow rate of 0.2 ml / min. The measurement sample is dissolved in tetrahydrofuran to a concentration of 1 mg / ml under dissolution conditions where it is treated for 5 minutes using an ultrasonic disperser at room temperature (25°C). The measurement sample dissolved in THF is treated with a membrane filter having 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 the molecular weight distribution of the measurement sample is measured from a calibration curve created from a plurality of standard polystyrene samples using a refractive index detector (RI detector). The peak molecular weight is determined from the said molecular weight distribution.

[0078] [2. Resin Composition] The resin composition according to this embodiment contains a resin having a structural unit represented by the above general formula (1). "Resin composition" refers to a composition containing two or more components including the said resin.

[0079] Examples of the resin composition include a resin dispersion, a resin solution, a mixed resin, etc.

[0080] 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 resins not containing the structural unit represented by the above general formula (1), solvents, dispersants, antioxidants, colorants, defoamers, surfactants, etc.

[0081] The resin composition according to this embodiment can be used for resin molded articles, etc. The resin molded article according to this embodiment is formed using the said resin composition, and thus is easy to mold with low energy and has low charge leakage.

[0082] The melt flow rate (MFR) of the resin composition according to this embodiment at 120°C and a load of 2.16 kg is preferably 0.01 to 200 g / 10 min, more preferably 0.01 to 60 g / 10 min, from the viewpoint of obtaining a thermoplastic resin composition with good moldability. When the MFR of the resin composition is within the above range, the resin composition is easily molded with low energy. Note that the MFR can be measured at 120°C in accordance with JIS K 7210 (ISO1133).

[0083] The dielectric tangent at 100 kHz measured at 25°C of the components of the resin composition according to this embodiment is preferably 0.001 to 0.01. If the dielectric tangent of the resin composition is within the above range, the charge leakage property is likely to be low. The dielectric tangent of the resin composition can be obtained from S-parameter methods such as the capacitance method, free space S-parameter method, and corrugated circular waveguide S-parameter method, and cavity resonance methods such as the balanced disk resonator method, Fabry-Perot open resonator method, split cylinder cavity resonator method, split post dielectric resonator method, cylindrical cavity resonator perturbation method, and cutoff cylindrical waveguide method. From the viewpoint of ease of measurement values, in this application, the value obtained by the capacitance method is used.

[0084] The resin molded product according to this embodiment can be obtained by melting and molding the above resin composition in various molding machines. The molding method can be appropriately selected according to the form and use of the molded product. For example, injection molding, extrusion molding, compression molding, blow molding, calender molding, inflation molding, etc. can be mentioned. Further, for sheet-like or film-like molded products obtained by extrusion molding, calender molding, etc., secondary molding such as vacuum forming or pressure-air forming may be performed.

[0085] The use of the resin molded product according to this embodiment is not particularly limited, and examples include parts (electrical and electronic parts, electrical components, exterior parts, interior parts, etc.) in the fields of home appliances and automobiles, various packaging materials, household goods, office supplies, pipes, agricultural materials, etc.

[0086] [3. Toner for electrostatic charge image development] The toner for electrostatic charge image development according to this embodiment (hereinafter, also simply referred to as "toner") contains a resin having a structural unit represented by the general formula (1).

[0087] In the present application, "toner" refers to an aggregate of toner particles. "Toner particles" can be composed of toner base particles and external additives. "Toner base particles" can be composed of a toner binder, a release agent, a colorant, a charge control agent, and the like.

[0088] <Toner binder> The toner according to this embodiment contains a resin containing a structural unit represented by the general formula (1) as a toner binder constituting the toner base particles.

[0089] The toner binder may contain other resins other than the above resin. As other resins, resins generally used as toner binders constituting toner base particles can be used without limitation.

[0090] Specifically, for example, an acrylic resin not containing a structural unit represented by the general formula (1), a methacrylic resin not containing a structural unit represented by the general formula (1), a polyester resin, a silicone resin, a polyolefin resin, a polyamide resin, or an epoxy resin can be mentioned. These other resins can be used alone or in combination of two or more.

[0091] The polyester resin is a resin obtained by a polycondensation reaction of a dicarboxylic acid having a valence of 2 or more (polyvalent carboxylic acid component) and an alcohol having a valence of 2 or more (polyvalent alcohol component). The polyester resin may be amorphous or crystalline.

[0092] The valences of the polyvalent carboxylic acid component and the polyvalent alcohol component are preferably 2 to 3, respectively, and particularly preferably 2, respectively. Therefore, a particularly preferred form in which the valences are both 2 (that is, a dicarboxylic acid component and a diol component) will be described.

[0093] Examples of the dicarboxylic acid component include saturated aliphatic dicarboxylic acids such as 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; unsaturated aliphatic dicarboxylic acids such as methylene succinic acid, fumaric acid, maleic acid, 3-hexenedioic acid, 3-octenedioic acid, dodecenyl succinic acid; unsaturated aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, t-butylisophthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-phenylenediacetic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, anthracenedicarboxylic acid; and the like. Further, lower alkyl esters and acid anhydrides of these can also be used. The dicarboxylic acid component may be used alone or in admixture of two or more.

[0094] In addition, polyvalent carboxylic acids having a valence of 3 or more such as trimellitic acid and pyromellitic acid, anhydrides of the above carboxylic acid compounds, or alkyl esters having 1 to 3 carbon atoms can also be used.

[0095] Examples of the diol component include saturated aliphatic diols such as 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; unsaturated aliphatic diols such as 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; bisphenols such as bisphenol A and bisphenol F, and aromatic diols such as alkylene oxide adducts of these bisphenols, such as ethylene oxide adducts and propylene oxide adducts. Derivatives of these can also be used. The diol component may be used alone or in admixture of two or more.

[0096] The method for producing the polyester resin is not particularly limited. The polyester resin can be produced by polycondensing (esterifying) a polyvalent carboxylic acid component and a polyvalent alcohol component using a known esterification catalyst.

[0097] Examples of the catalyst that can be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium; compounds containing Group 2 elements such as magnesium and calcium; compounds of metals such as aluminum, zinc, manganese, antimony, titanium, tin, zirconium, and germanium; phosphorous acid compounds; phosphoric acid compounds; and amine compounds. Specifically, examples of the tin compound include dibutyltin oxide, tin octylate, dioctyltin, and salts thereof.

[0098] Examples of the titanium compound include titanium alkoxides such as tetra-n-butyl titanate (Ti(O-n-Bu)4), tetraisopropyl titanate, tetramethyl titanate, and tetrastearyl titanate; titanium acylates such as polyhydroxy titanium stearate; and titanium chelates such as titanium tetraacetylacetonate, titanium lactate, and titanium triethanolamine. Examples of the germanium compound include germanium dioxide. Examples of the aluminum compound include polyaluminum hydroxide, aluminum alkoxide, and tributylaluminate. These may be used alone or in combination of two or more.

[0099] The polymerization temperature is not particularly limited, but is preferably in the range of 70 to 250°C. Also, the polymerization time is not particularly limited, but is preferably 0.5 to 10 hours. During the polymerization, the inside of the reaction system may be depressurized as necessary.

[0100] The above polyester resin may be a hybrid polyester resin having a graft copolymer structure of a polyester polymerization segment and a graft of a styrene-acrylic polymerization segment.

[0101] The content of the resin containing the structural unit represented by the general formula (1) in the toner binder is preferably in the range of 5 to 100% by mass, more preferably in the range of 5 to 50% by mass, and even more preferably in the range of 10 to 40% by mass, with the total mass of the toner binder being 100% by mass.

[0102] <Release agent> The toner according to this embodiment preferably contains a release agent in the toner base particles. The release agent is preferably a fatty acid ester.

[0103] Examples of fatty acid esters include, for example, behenyl behenate (behenyl behenate), stearyl stearate (stearyl stearate), behenyl stearate, stearyl behenate, butyl stearate, propyl oleate, hexadecyl palmitate (hexadecyl palmitate), methyl lignocerate (methyl lignocerate), glycerin monostearate (glyceryl stearate), diglyceryl distearate (diglyceryl distearate), pentaerythritol tetrabehenate (pentaerythritol tetrabehenate), diethylene glycol monostearate, dipropylene glycol distearate, sorbitan monostearate, cholesteryl stearate, trimethylolpropane tribehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, tristearyl trimellitate (tristearyl trimellitate), distearyl maleate, methyl triacontanate (methyl triacontanate), and the like. These fatty acid esters can be used alone or in combination of two or more.

[0104] As the fatty acid ester, a commercially available product or a synthetic product may be used.

[0105] 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, and the like.

[0106] More preferable release agents include at least one of behenyl behenate (behenyl behenate, the fatty acid ester has 22 carbon atoms), pentaerythritol tetrabehenate (pentaerythritol tetrabehenate ester, the fatty acid ester has 22 carbon atoms), ethylene glycol distearate (ethylene glycol distearate ester, the fatty acid ester has 18 carbon atoms), methyl lignocerate (the fatty acid ester has 24 carbon atoms), and cetyl palmitate (the fatty acid ester has 16 carbon atoms). In particular, behenyl behenate (behenyl behenate), pentaerythritol tetrabehenate ester or ethylene glycol distearate ester is preferable.

[0107] The release agent may be a wax other than a fatty acid ester. Examples of waxes other than fatty acid esters include polyolefin waxes such as low molecular weight polyethylene and low molecular weight polypropylene, branched 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 ethylenediamine behenylamide and tris stearylamide trimellitate.

[0108] From the viewpoint of the balance between fixing property and offset resistance, the content ratio of the release agent is preferably in the range of 1 to 25% by mass, more preferably in the range of 5 to 20% by mass, based on 100% by mass of the total mass of the resin containing the structural unit represented by the general formula (1).

[0109] <Colorant> The toner according to this embodiment may contain a colorant in the toner base particles. As the colorant, generally known dyes and pigments can be used.

[0110] Examples of colorants for obtaining black toner include carbon black, magnetic materials, iron-titanium composite oxide black, etc. Examples of the carbon black include channel black, furnace black, acetylene black, thermal black, lamp black, etc. Examples of the magnetic materials include ferrite, magnetite, etc.

[0111] Examples of colorants for obtaining yellow toner include dyes such as C.I. Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162; and pigments such as C.I. Pigment Yellow 14, 17, 74, 93, 94, 138, 155, 180, 185.

[0112] Examples of colorants for obtaining magenta toner include dyes such as C.I. Solvent Red 1, 49, 52, 58, 63, 111, 122; and pigments such as C.I. Pigment Red 5, 48:1, 53:1, 57:1, 122, 139, 144, 149, 166, 177, 178, 222.

[0113] Examples of colorants for obtaining cyan toner include dyes such as C.I. Solvent Blue 25, 36, 60, 70, 93, 95; and pigments such as C.I. Pigment Blue 1, 7, 15, 60, 62, 66, 76.

[0114] For each color of toner, the colorants for obtaining the toner of each color can be used alone or in combination of two or more.

[0115] The content ratio of the colorant is preferably in the range of 0.5 to 20% by mass, more preferably in the range of 2 to 10% by mass, with the total mass of the toner base particles being 100% by mass.

[0116] <Charge control agent> The toner according to this embodiment may contain a charge control agent in the toner base particles.

[0117] The charge control agent used is a substance that can impart positive or negative charge by triboelectrification, and is not particularly limited as long as it is colorless. Therefore, various known positive charge control agents and negative charge control agents can be used as the charge control agent.

[0118] Specifically, examples of the positive charge control agent include nigrosine 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.) and "Copy Charge PX VP435" (manufactured by Hoechst Japan Ltd.), alkoxylated amines, alkylamides, molybdate chelate pigments, and imidazole compounds such as "PLZ1001" (manufactured by Shikoku Kasei Kogyo Co., Ltd.).

[0119] Examples of the negative charge control agent include metal complexes such as "Bontron (registered trademark) S-22", "Bontron (registered trademark) S-34", "Bontron (registered trademark) E-81", "Bontron (registered trademark) E-84" (all manufactured by Orient Chemical Industries, Ltd.) and "Spiro Black TRH" (manufactured by Hodogaya Chemical Co., Ltd.), 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.

[0120] As the metal complex used as the negative charge control agent, in addition to those shown above, those having various structures such as oxycarboxylic acid metal complexes, dicarboxylic acid metal complexes, amino acid metal complexes, diketone metal complexes, diamine metal complexes, azo group-containing benzene-benzene derivative skeleton metal complexes, and azo group-containing benzene-naphthalene derivative skeleton metal complexes can be used.

[0121] By configuring the toner base particles to contain a charge control agent in this way, the chargeability of the toner is improved.

[0122] The content ratio of the charge control agent is preferably in the range of 0.01 to 30% by mass, more preferably in the range of 0.1 to 10% by mass, with the total mass of the toner base particles being 100% by mass.

[0123] <Morphology of toner base particles> The morphology of the toner base particles is not particularly limited, and for example, it can take forms such as a so-called single-layer structure, a core-shell structure, a multilayer structure of three or more layers, a domain-matrix structure, etc. Note that the single-layer structure refers to a homogeneous structure that is not of the core-shell type.

[0124] <External additives> External additives such as a fluidizing agent and a cleaning aid, which are so-called post-treatment agents, may be added to the toner base particles to constitute the toner according to this embodiment. By adding such external additives, the fluidity, chargeability, cleaning property, etc. of the toner can be improved.

[0125] Examples of the 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.

[0126] These inorganic particles may be surface-treated with a silane coupling agent, a titanium coupling agent, a higher fatty acid, a silicone oil, etc. to improve heat-resistant storage stability and environmental stability.

[0127] The addition amount of the external additive 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, based on 100 parts by mass of the toner base particles.

[0128] <Median Diameter of Toner Particles> 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. When the volume-based median diameter (D50) is within the above range, the transfer efficiency is increased, the image quality of halftones is improved, and the image quality of thin lines, dots, etc. is improved.

[0129] In the present embodiment, the volume-based median diameter (D50) of the toner particles is measured and calculated using a measuring device connected to a computer system (manufactured by Beckman Coulter, Inc.) equipped with "Software V3.51" for data processing in a "Coulter Counter 3" (manufactured by Beckman Coulter, Inc.).

[0130] Specifically, 0.02 g of a measurement sample (toner) is added to 20 mL of a surfactant solution and allowed to mix well. The surfactant solution is, for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing toner particles.

[0131] Thereafter, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion. This toner dispersion is pipetted into a beaker containing "ISOTON II" (manufactured by Beckman Coulter, Inc.) in a sample stand until the display concentration of the measuring device reaches 8%.

[0132] Here, by setting this concentration range, reproducible measurement values can be obtained. In the measuring device, the number of measured particles is set to 25,000, the aperture diameter is set to 50 μm, and the frequency values are calculated by dividing the measurement range of 1 to 30 μm into 256 segments. Then, the particle diameter at which the volume integration fraction is 50% from the larger side is defined as the volume-based median diameter (D50).

[0133] [4. Method for Manufacturing Toner] The method for manufacturing toner is not particularly limited. For example, toner can be manufactured by the following emulsion aggregation method. Alternatively, the resin according to the present embodiment and, if necessary, a release agent, a colorant, etc. can be melt-kneaded, and then pulverized, classified, etc. to manufacture toner.

[0134] As the emulsion aggregation method, the methods described in JP-A-5-265252, JP-A-6-329947, JP-A-9-15904, etc. can be adopted. Further, a manufacturing method using the suspension polymerization method described in JP-A-2010-191043 may also be used. Among them, from the viewpoint that it is easy to control the particle diameter and shape and the energy cost during production can be reduced, a manufacturing method using the emulsion aggregation method is preferable.

[0135] The manufacturing method using such an emulsion aggregation method preferably includes the following steps. (1A) Toner binder particle dispersion preparation step of preparing a dispersion of toner binder particles (1B) Colorant particle dispersion preparation step of preparing a dispersion of colorant particles (1C) Release agent particle dispersion preparation step of preparing a dispersion of release agent particles (2) Aggregation step of adding a coagulant to an aqueous medium in which toner binder particles, colorant particles, and release agent particles are present, advancing salting out, and performing aggregation and fusion at the same time to form aggregated particles (3) Aging step of forming toner mother particles by controlling the shape of the aggregated particles (4) Filtration and washing step of filtering out toner mother particles from the aqueous medium and removing a surfactant, etc. from the toner mother particles (5) Drying step of drying the washed toner mother particles (6) External additive addition step of adding an external additive to the dried toner mother particles

[0136] Hereinafter, the steps (1A) to (1C) will be described.

[0137] (1A) Toner binder particle dispersion preparation step In this process, resin particles are formed by conventional known emulsion polymerization or the like, and these resin particles are aggregated and fused to form toner binder particles. As an example, polymerizable monomers (the first polymerizable monomer and the second polymerizable monomer) constituting the toner binder are introduced into an aqueous medium and dispersed, and these polymerizable monomers are polymerized with a polymerization initiator. Thereby, a dispersion of toner binder particles is prepared.

[0138] In addition, as a method for obtaining a dispersion of toner binder particles, in addition to the method of polymerizing polymerizable monomers with a polymerization initiator in the above 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 of dissolving a polymer in an organic solvent such as ethyl acetate to form a solution, emulsifying and dispersing the solution in an aqueous medium using a disperser, and then performing a solvent removal treatment can be mentioned.

[0139] At this time, if necessary, the toner binder may be pre-containing a release agent. Also, for dispersion, it is also preferable to polymerize in the presence of a known surfactant as appropriate. Examples of the known surfactant include anionic surfactants such as sodium polyoxyethylene(2) dodecyl ether sulfate, sodium dodecyl sulfate, and sodium dodecylbenzenesulfonate.

[0140] The volume-based median diameter of the toner binder particles in the dispersion is preferably in the range of 50 to 300 nm. The median diameter can be measured by the dynamic light scattering method using "Microtrac UPA-150" (manufactured by Nikkiso Co., Ltd.).

[0141] (1B) Coloring Agent Particle Dispersion Preparation Step This coloring agent particle dispersion preparation step is a step of dispersing a coloring agent in a fine particle state in an aqueous medium to prepare a dispersion of coloring agent particles. The dispersion of the coloring agent can be performed using mechanical energy. The volume-based median diameter of the coloring agent particles in the dispersion is preferably in the range of 10 to 300 nm, and more preferably in the range of 50 to 200 nm. The volume-based median diameter of the colorant particles in the dispersion can be measured by the dynamic light scattering method using "Microtrac UPA-150" (manufactured by Nikkiso Co., Ltd.) in the same manner as described above.

[0142] (1C) Release agent particle dispersion preparation step This release agent particle dispersion preparation step is a step of dispersing a release agent in a particulate form in an aqueous medium to prepare a dispersion of release agent 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, and 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, for example, by a laser diffraction particle size distribution analyzer LA-750 (manufactured by Horiba, Ltd.).

[0143] (Aqueous medium) The aqueous medium used in the steps (1A) to (1C) is water, or an aqueous medium having water as a main component (50% by mass or more) and containing water-soluble solvents such as alcohols and glycols, and optional components such as surfactants and dispersants. Preferably, an aqueous medium obtained by mixing water and a surfactant is used.

[0144] Examples of the above water-soluble solvents include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, tetrahydrofuran, etc. Among these, alcohols such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve polymers, are preferred.

[0145] Examples of surfactants include cationic surfactants, anionic surfactants, nonionic surfactants, and the like. Examples of cationic surfactants include dodecylammonium chloride, dodecylammonium bromide, dodecyltrimethylammonium bromide, dodecylpyridinium chloride, dodecylpyridinium bromide, hexadecyltrimethylammonium bromide, and the like. Examples of anionic surfactants include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and the like. Examples of nonionic surfactants include polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, monodecanoyl sucrose, and the like.

[0146] Such surfactants can be used alone or in combination of two or more. Among the surfactants, anionic surfactants are preferably used, and more preferably sodium dodecylbenzenesulfonate and sodium dodecyl sulfate are used.

[0147] The addition amount of the surfactant is preferably in the range of 0.01 to 10 parts by mass, more preferably in the range of 0.04 to 2 parts by mass, based on 100 parts by mass of the aqueous medium.

[0148] (2) The steps from the aggregation step to the external additive addition step (6) can be carried out according to various conventionally known methods.

[0149] The flocculant used in the (2) aggregation step is not particularly limited, but those selected from metal salts are preferably used.

[0150] Examples of the metal salts used as the flocculant include monovalent metal salts such as salts of alkali metals such as sodium, potassium, and lithium; divalent metal salts such as calcium, magnesium, manganese, and copper; trivalent metal salts such as iron and aluminum.

[0151] Specific examples of the metal salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, zinc chloride, copper sulfate, magnesium sulfate, manganese sulfate, polyaluminum chloride, and the like. Among these, it is particularly preferable to use divalent or trivalent metal salts because flocculation can proceed with a smaller amount. These can be used alone or in combination of two or more.

[0152] The amount of the flocculant used is not particularly limited, but from the viewpoint of controlling the toner particle size with respect to the solid content of the toner binder, it is preferably 2% to 30% by mass.

[0153] [5. Developer] The toner according to this embodiment can be used as a one-component developer alone or mixed with carrier particles to be used as a two-component developer.

[0154] When used as a one-component developer, the toner may be a magnetic toner containing a magnetic substance or a non-magnetic toner not containing a magnetic substance. As the magnetic substance, for example, magnetite, γ-hematite, or various ferrites can be used.

[0155] As the carrier particles constituting the two-component developer, magnetic particles made of conventionally known materials such as metals such as iron, steel, nickel, cobalt, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead can be used.

[0156] As the carrier particles, it is preferable to use coated carrier particles in which the surface of the magnetic particles is coated with a coating agent such as resin, or so-called resin-dispersed carrier particles in which magnetic powder is dispersed in a binder resin.

[0157] As the resin for coating, there is no particular limitation, and for example, olefin resin, styrene resin, styrene-acrylic resin, silicone resin, polyester resin, or fluororesin can be used.

[0158] The resin for constituting 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, phenol resin, etc. can be used.

[0159] 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.

[0160] 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. Examples of the laser diffraction particle size distribution measuring device include "HELOS" (manufactured by SYMPATEC).

[0161] The mixing amount of the toner particles with respect to the carrier particles is preferably in the range of 2 to 10 mass% with the total mass of the toner particles and the carrier particles being 100 mass%.

[0162] [6. Image forming method using toner] The toner according to the present embodiment can be suitably used in an image forming method including a fixing step by a thermal pressure fixing method that can apply pressure and heat. In particular, it can be suitably used in an image forming method in which the fixing temperature in the fixing step is relatively low. The fixing temperature is a temperature in the range of 115 to 140 °C, preferably 115 to 130 °C, at the surface temperature of the heating member in the fixing nip portion.

[0163] The toner according to this embodiment can also be suitably used in a high-speed fixing image forming method in which the fixing linear speed is in the range of 200 to 600 mm / sec.

[0164] In an image forming method including a fixing step by a thermo-pressure fixing method, for example, first, an electrostatic charge image formed on a photoreceptor is developed with toner to obtain a toner image. This toner image is transferred from the photoreceptor onto an image support. Then, the toner image transferred onto the image support is fixed to the image support by a fixing process of the thermo-pressure fixing method. Thereby, a printed matter on which a visible image is formed is obtained.

[0165] Also, the toner according to this embodiment can be used in a monochrome image forming method or a full-color image forming method. In the full-color image forming method, it can be applied to a 4-cycle image forming method configured by four types of color developing devices each related to yellow, magenta, cyan, and black, and one photoreceptor. Further, it can also be applied to a tandem image forming method in which image forming units each having a color developing device and a photoreceptor related to each color are mounted separately for each color. The toner according to this embodiment can be applied to any of the above image forming methods.

[0166] [7. Ink] The resin of this embodiment having the structural unit represented by the general formula (1) can also be contained in ink. The ink may contain, in addition to the resin according to this embodiment, a coloring material, a solvent, other resins, various additives, and the like.

[0167] The ink containing the resin according to this embodiment can form an image excellent in light resistance and adhesiveness to a medium.

[0168] 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 the resin, the resin absorbs ultraviolet rays, making it difficult for the coloring material to be affected by ultraviolet rays. Due to such an action, the image formed using the ink containing the resin according to this embodiment has good light resistance.

[0169] In addition, since the resin according to the present embodiment has a polar group, an image formed using the ink containing the resin according to the present embodiment has good adhesiveness to a medium such as paper.

[0170] Examples of the ink application method in image formation using ink include a spray method, a mangle method (pad method or dipping method), a coating method, an inkjet method, and the like. When forming a high-precision image, the inkjet method is preferable.

[0171] [8. Printed Image] The printed image according to the present embodiment is characterized by containing a resin having a structural unit represented by the above general formula (1).

[0172] The said printed image can be formed using the toner and ink mentioned above.

[0173] The said printed image is excellent in light resistance and adhesiveness to a medium by containing a resin having a structural unit represented by the above general formula (1).

Examples

[0174] Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the following examples, unless otherwise specified, the operations were carried out at room temperature (25 °C). Also, unless otherwise specified, “%” and “parts” mean “mass %” and “parts by mass”, respectively.

[0175] [Polymerizable Monomer] As the first polymerizable monomer having a structural unit represented by the general formula (2), the above-exemplified compounds M1 to M7 were used.

[0176] Also, as a comparative compound, M8 having the following structure was used.

[0177] [Chemical Formula]

[0178] In M1 to M8, R1, R2, R3, and R4 in the general formula (2) are as shown in the following table.

[0179]

Table 1

[0180] The abbreviations listed in Table 1 represent the following atoms or substituents, respectively. H: Hydrogen atom Me: Methyl group Et: Ethyl group n-Bu: n-Butyl group n-Hex: n-Hexyl group OMe: Methoxy group O-t-Bu: t-Butoxy group O-n-Hex: n-Hexoxy group Also, the following compounds were used as the second polymerizable monomer. St: Styrene MMA: Methyl methacrylate nBA: n-Butyl acrylate iBA: Iso-butyl acrylate 2EHA: 2-Ethylhexyl acrylate MAA: Methacrylic acid AA: Acrylic acid

[0181] [Synthesis of Resin] A surfactant solution was prepared by dissolving 8 g of sodium dodecyl sulfate in 3 L of ion-exchanged water. The surfactant solution was charged into a 5 L stainless steel kettle (SUS kettle) equipped with a stirring device, a temperature sensor, a condenser, and a nitrogen introduction device. Then, while stirring at a stirring speed of 230 rpm under a nitrogen stream, the liquid temperature was raised to 80°C.

[0182] To this surfactant solution, an initiator solution prepared by dissolving 10 g of potassium persulfate in 200 g of ion-exchanged water was added, and the temperature was set to 80°C. Then, polymerizable monomers were added at the addition ratios shown in Table 2 below to prepare respective mixtures such that the solid content concentration of the resulting resin particle dispersion was 20% by mass, and each of these mixtures was added dropwise to the above surfactant solution over 100 minutes. The polymerization of the polymerizable monomers was carried out by heating and stirring this system at 80°C for 2 hours.

[0183] 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 100% by mass.

[0184] In this way, resin particle dispersions 1 to 14 with a solid content concentration of 20% by mass were prepared respectively. The resins contained in resin particle dispersions 1 to 14 are referred to as resin 1 to resin 14, respectively.

[0185] The peak molecular weights of resins 1 to 14 are as shown in Table 2. The peak molecular weight was measured as follows. The apparatus "HLC-8220" (manufactured by Tosoh Corporation) and the column "TSKguardcolumn + TSKgel SuperHZM-M3 series" (manufactured by Tosoh Corporation) were used. While maintaining the column temperature at 40°C, tetrahydrofuran (THF) was flowed as the carrier solvent at a flow rate of 0.2 ml / min. Next, the measurement sample was dissolved in tetrahydrofuran to a concentration of 1 mg / ml under dissolution conditions where it was treated with an ultrasonic disperser for 5 minutes at room temperature (25°C). Then, 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 carrier solvent. Then, the molecular weight distribution of the measurement sample was detected using a refractive index detector (RI detector). The peak molecular weight was determined from the molecular weight distribution.

[0186] The volume-based median diameters of the resin particles in resin particle dispersions 1 to 14 were all 128 nm. The median diameter was measured by the dynamic light scattering method using "Microtrac UPA-150" (manufactured by Nikkiso Co., Ltd.).

[0187] [Preparation of Toner] Using Resin Particle Dispersions 1 to 14 as toner binder particle dispersions, toner was prepared as follows.

[0188] [Preparation of Colorant Dispersion] Colorant: Carbon black (Mogul (registered trademark) L, manufactured by Cabot Corporation) 10 parts by mass Anionic surfactant (20% aqueous solution of sodium dodecylbenzenesulfonate) 1.5 parts by mass Ion-exchanged water 90 parts by mass

[0189] The above components were mixed and dispersed with an SC mill to obtain a colorant dispersion. 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.).

[0190] [Preparation of Release Agent Dispersion] Behenyl behenate 100 parts by mass Sodium dodecyl sulfate 5 parts by mass Ion-exchanged water 240 parts by mass

[0191] The above components were dispersed in a round stainless steel flask using a homogenizer "Ultra Turrax (registered trademark) T50" (manufactured by IKA) for 10 minutes. Thereafter, dispersion treatment was performed with a pressure discharge type homogenizer to obtain a release agent dispersion.

[0192] The volume-based median diameter of the release agent particles in the release agent dispersion was 530 nm. It was measured with a laser diffraction particle size distribution analyzer LA-750 (manufactured by Horiba, Ltd.).

[0193] [Preparation of Toner Base Particle Dispersion 1] Toner Binder Particle Dispersion 1 237 parts by mass Colorant Dispersion 42 parts by mass Release Agent Dispersion 18 parts by mass 1.8 parts by mass of polyaluminum chloride 600 parts by mass of ion-exchanged water

[0194] The above components were mixed and dispersed in a round stainless-steel flask using a homogenizer "Ultra Turrax (registered trademark) T50" (manufactured by IKA). Then, while stirring the inside of the flask in an oil bath for heating, it was heated to 55 °C. After holding at 55 °C for 30 minutes, it was confirmed that aggregated particles with a median diameter (D50) of 4.8 μm based on volume were generated in the solution.

[0195] Furthermore, when the temperature of the oil bath for heating was raised and held at 56 °C for 2 hours, the median diameter (D50) based on volume became 5.9 μm.

[0196] Thereafter, 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 stirring. By continuing stirring for 6 hours, the fusion (bonding) between toner binder particles was completed, and a toner mother particle dispersion was prepared. The median diameter (D50) based on volume of the toner mother particles in the dispersion was 6.0 μm.

[0197] <Washing and drying process> The toner mother particle dispersion was subjected to solid-liquid separation using a basket-type centrifuge "MARKIII Model Number 60×40" (manufactured by Matsumoto Machinery Sales Co., Ltd.) to form a wet cake of toner mother particles.

[0198] The wet cake was washed with ion-exchanged water at 45 °C using the above basket-type centrifuge until the electrical 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 to obtain toner mother particles 1.

[0199] <Preparation of toner mother particles 2 to 14> In the preparation of the toner base particles 1, toner base particles 2 to 14 were prepared in the same manner except that the toner binder particle dispersion liquid 1 was changed to the toner binder particle dispersion liquids 2 to 14, respectively.

[0200] <External additive treatment of toner base particles> To 100 parts by mass of the toner base 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 titania (number average primary particle diameter = 20 nm) were added. Then, they were mixed by a Henschel mixer (registered trademark) to perform an external additive treatment, and toners 1 to 14 were manufactured.

[0201] [Preparation of two-component developer] The following components were put into a horizontal stirring blade type high-speed stirring device and mixed for 15 minutes under the conditions of a peripheral speed of the stirring blade: 8 m / s and a temperature: 30°C.

[0202] Ferrite particles (volume-based median diameter: 50 μm (manufactured by Powdertech Co., Ltd.)) 100 parts by mass Methyl methacrylate-cyclohexyl methacrylate copolymer resin (volume-based median diameter of primary particles: 85 nm) 4 parts by mass

[0203] Next, the system was heated to 120°C and stirring was continued for 4 hours. Then, the system was cooled and fragments of the methyl methacrylate-cyclohexyl methacrylate copolymer resin were removed using a 200-mesh sieve. Thereby, a resin-coated carrier was produced.

[0204] This resin-coated carrier was mixed with each of the above toners 1 to 14 so that the toner concentration was 7% by mass based on the total mass of the toner and the carrier, and two-component developers 1 to 14 were prepared.

[0205]

Table 2

[0206] [Evaluation] Using two-component developers 1 to 14, the fixability and chargeability were evaluated as follows. The evaluation results are as shown in Table 3.

[0207] (1) Fixability As an image forming apparatus, a commercially available multifunction machine "bizhub PRO C6500" (manufactured by Konica Minolta Business Technologies Inc.) was used. The above two-component developer was mounted on this apparatus as the developer. Then, the surface temperature of the fixing heating member in the fixing means of the heat roll fixing method was changed in 5°C increments in the range of 80 to 150°C. For each temperature, under the environment of normal temperature and normal humidity (temperature 20°C, humidity 50%RH), image formation was performed using thick paper with a basis weight of 350 g / m2 as the image support, and a solid image with an image density of 0.8 was obtained as a visible image. Then, the fixed solid image was folded using a folding machine, and air at 0.35 MPa was blown onto it. The state of the fold was evaluated in five grades according to the following evaluation criteria in terms of the retention rate of the image density, and the fixing temperature of rank 3 was taken as the minimum fixing temperature. If the minimum fixing temperature indicating the rank 3 level is 130°C or lower, it shows sufficient low-temperature fixability.

[0208] 〔Evaluation criteria〕 Rank 5: The retention rate of the image density is 90% or more Rank 4: The retention rate of the image density is 75% or more and less than 90% Rank 3: The retention rate of the image density is 60% or more and less than 75% Rank 2: The retention rate of the image density is 45% or more and less than 60% Rank 1: The retention rate of the image density is less than 45%

[0209] (2) Chargeability When measuring the charge amount of the toner, it was measured using the apparatus shown in FIG. 1. First, 1 g of the developer weighed with a precision balance was placed evenly on the entire surface of the conductive sleeve (31). A voltage of 2 kV was supplied from the bias power supply (33) to the sleeve (31), and the rotational speed of the magnet roll (32) provided inside the conductive sleeve (31) was set to 1000 rpm. The toner was collected on the cylindrical electrode (34) after leaving it in this state for 30 seconds. After 30 seconds, the potential Vm of the cylindrical electrode (34) was read, and the charge amount of the toner was determined. Further, the mass of the collected toner was measured with a precision balance, and the average charge amount was determined. The value obtained by dividing the average charge amount by the mixing time (mixed for 10 minutes using a shaker (Yayoi type New-YS) with a shaking angle of 30° and a shaking frequency of 200 strokes / min) was used as the chargeability index.

[0210] If the chargeability index is 6.5 μC / g / min or more, it shows a sufficient charge amount without problems even during high-speed print output.

[0211] [Table 3]

[0212] From the above evaluation results, it can be seen that the toner containing the resin having the structural unit represented by the general formula (1) has better fixability and chargeability compared to the comparative examples.

[0213] Also, from this, it can be seen that the resin having the structural unit represented by the general formula (1) is excellent in thermal properties and electrical properties.

Industrial Applicability

[0214] According to the resin of the present invention, it is possible to reduce the viscosity with a low amount of energy and make it have low charge leakage. Also, according to the electrostatic charge image developing toner of the present invention, the low-temperature fixability can be sufficiently enhanced and the heat-resistant storage property can be made good. Therefore, the present invention is useful in the field of image formation.

Explanation of Signs

[0215] 31 Conductive sleeve 32 Magnet Roll 33 Bias Power Supply 34 Cylindrical Electrode

Claims

1. A resin containing a structural unit represented by the following general formula (1). 【Chemical 1】 (In the general formula (1), R １ represents a hydrogen atom or a methyl group. R ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ３ , R ４ each independently represents a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.)

2. R in the general formula (1) ２ is a methyl group, and R ３ , R ４ is a hydrogen atom. The resin according to Claim 1.

3. 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. The resin according to Claim 1. 【Chemical 2】 (In the general formula (2), R １ represents a hydrogen atom or a methyl group. R ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ３ , R ４ each independently represents a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.)

4. The content of the structural unit derived from the first polymerizable monomer is 10% by mass to 40% by mass with respect to all the structural units constituting the resin. The resin according to Claim 3.

5. The second polymerizable monomer contains at least one monomer selected from the group consisting of styrenes, acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters. The resin according to Claim 3.

6. The second polymerizable monomer contains at least one monomer selected from the group consisting of styrene, acrylic acid, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, n-butyl methacrylate, isobutyl methacrylate, and 2-ethylhexyl methacrylate. The resin according to Claim 5.

7. A resin composition containing the resin according to any one of Claims 1 to 6.

8. A printed image containing the resin according to any one of Claims 1 to 6.

9. An electrostatic charge image developing toner containing the resin according to any one of Claims 1 to 6.

10. A method for manufacturing an electrostatic charge image developing toner for manufacturing the electrostatic charge image developing toner according to Claim 9, A step of preparing a resin containing a structural unit represented by the following general formula (1), A step of preparing a toner binder particle dispersion from the resin, A step of aggregating toner binder particles and fusing the particles together in the toner binder particle dispersion, A method for manufacturing an electrostatic charge image developing toner, including the above steps. 【Chemical Formula 3】 (In the general formula (1), R １ represents a hydrogen atom or a methyl group. R ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ３ , R ４ each independently represents a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.)

11. The step of preparing a resin containing 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). The method for manufacturing an electrostatic charge image developing toner according to Claim 10. 【Chemical Formula 4】 (In the general formula (2), R １ represents a hydrogen atom or a methyl group. R ２ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ３ , R ４ each independently represents a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms.)

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