toner

Abstract

To provide a toner that has an excellent tinting power, hot offset resistance, and electrification stability.SOLUTION: A toner has toner particles containing a binder resin, a coloring agent, and a resin composition. The resin composition contains a polyolefin unit and a unit represented by the following formula (1). The coloring agent is an organic pigment. (n represents 3≤n≤10. R1 and R2 each independently represent H or CH3.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system. [Background technology]

[0002] 2. Description of the Related Art In recent years, as electrophotographic full-color copying machines have become widespread, there has been a demand for even higher speeds, higher image quality, and higher productivity. To achieve high image quality, it is important to improve the pigment dispersibility in toner particles and maximize the pigment's coloring power. However, pigments commonly used in toners have primary particles of several to several tens of nanometers in size, and the primary particles tend to have strong cohesion, which makes them prone to insufficient dispersion in media such as molten resins. As a means for improving the dispersibility of pigments in toner particles, a pigment dispersant may be added. Patent Document 1 describes an example in which a salicylic acid-based resin is used as a pigment dispersant. However, in order to meet the recent demand for high image quality, the coloring power of pigments has not been maximized, and there is still room for improvement. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-68947 Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a toner that solves the above problems, specifically, to provide a toner that has excellent coloring power, high-temperature offset resistance, and charge stability. [Means for solving the problem]

[0005] As a result of extensive research, the present inventors have found that by using the constitution of the present invention, it is possible to provide a toner having excellent coloring power, high-temperature offset resistance, and charge stability. The toner of the present invention is a toner having toner particles containing a binder resin, a colorant, and a resin composition, The resin composition contains a polyolefin unit and a unit represented by the following formula (1): The toner is characterized in that the colorant is an organic pigment.

[0006] [ka] (n represents 3≦n≦10. R1 and R2 each independently represent H or CH3.) [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a toner having excellent coloring power, high-temperature offset resistance, and charge stability. DETAILED DESCRIPTION OF THE INVENTION

[0008] In the present invention, the expressions "xx or more and xx or less" and "xx to xx" indicating a numerical range mean a numerical range including the lower and upper limits, which are the endpoints, unless otherwise specified.

[0009] The present inventors have conducted extensive research with the aim of further improving excellent coloring power, hot offset resistance, and charging stability, and have found that by using a resin composition containing a unit represented by the following general formula (1) and a toner containing toner particles containing an organic pigment as a colorant, it is possible to obtain unprecedentedly excellent coloring power, high-temperature offset resistance, and charging stability.

[0010] [ka] (n represents 3≦n≦10. R1 and R2 each independently represent H or CH3.)

[0011] The authors believe that the reason why the effects of the present invention are obtained is as follows.

[0012] To improve the coloring power of a toner, it is necessary to maximize the coloring power of the pigment in the toner particles. The reason for the decline in the coloring power of the pigment in the toner particles is thought to be that the primary particles of the pigment, which are several nanometers to several tens of nanometers in size, have a strong cohesive force, which results in insufficient dispersion of the primary particles of the pigment in the toner particles.

[0013] The molecular structure of the pigment is thought to be a factor in the strong cohesive force of primary pigment particles. Many organic pigments commonly used in toners have a structure in which a nitrogen atom is bonded to an aromatic ring. This structure changes the light absorption wavelength of pigments, and by having an absorption range in the visible light wavelength range, pigments exhibit a variety of coloring power. On the other hand, a structure in which a nitrogen atom is bonded to an aromatic ring is thought to cause intramolecular polarization due to the nitrogen atom's lone electron pair forming a resonance structure with the aromatic ring. This intramolecular polarization generates electrostatic attraction between the polarized particles. As a result, it is thought that strong cohesive force is generated between primary pigment particles due to the electrostatic attraction generated by the intramolecular polarization on the surface of the primary particles.

[0014] As a result of extensive research, the present inventors have found that a toner having superior coloring power not previously available can be obtained by using a resin composition containing a unit represented by the above general formula (1) and a toner containing toner particles containing an organic pigment as a colorant.

[0015] The unit represented by the general formula (1) above is a unit containing multiple ether bonds. The ether bond is composed of a carbon atom and an oxygen atom. Because carbon atoms and oxygen atoms have different electronegativities, weak polarization occurs within the ether bond. In other words, it is believed that the polarization on the surface of the primary particles of the organic pigment and the polarization within the ether bond in the general formula (1) above interact with each other, selectively stabilizing the resin composition around the primary particles of the pigment. As a result, the resin composition enters between the primary particles of the pigment, suppressing the electrostatic attraction between the primary particles of the pigment, thereby achieving the effect of dispersing the primary particles of the pigment.

[0016] Furthermore, the resin composition is characterized by having a polyolefin unit. The polyolefin unit is a material with little electrical bias and is thought to have relatively weak intermolecular interactions. When the resin composition is stabilized around primary particles of a pigment, the unit of the resin composition represented by the general formula (1) is biased toward the pigment due to differences in polarization, and the polyolefin unit is thought to be biased toward the outside of the resin composition surrounding the pigment. Because the polyolefin unit has weak intermolecular interactions, it is thought to function to stabilize the dispersion state of the primary particles of the pigment (suppress re-aggregation).

[0017] From the above, it is believed that when the resin composition and an organic pigment are contained as a colorant, the dispersion stability of the primary particles of the pigment is improved, and the coloring power of the toner is improved.

[0018] <Resin composition> The resin composition used in the toner of the present invention will be described.

[0019] The resin composition used in the toner of the present invention is characterized by containing a polyolefin unit and a unit represented by the following formula (1).

[0020] [ka] (n represents 3≦n≦10. R1 and R2 each independently represent H or CH3.)

[0021] The polyolefin unit and the unit represented by formula (1) are chemically bonded molecules, and the polymer is preferably a graft polymer having the polyolefin unit as the backbone and the unit represented by formula (1) as the branch. By using a graft polymer, the radius of gyration of the resin composition is reduced, which makes it possible to suppress aggregation of primary particles that occurs when one molecule of the resin composition bridges between multiple primary particles of the pigment, improving the dispersion stability of the primary particles of the pigment and enhancing the coloring power of the toner.

[0022] The method for obtaining the graft polymer is not particularly limited, and any conventionally known method can be used.

[0023] The unit represented by formula (1) has ethylene glycol where n is 3 or more and 10 or less, and therefore interacts with the primary particles of the pigment, resulting in an effect of improving the dispersibility of the pigment.

[0024] Examples of the unit represented by formula (1) in which n is 3 or more and 10 or less include units derived from the following monomers.

[0025] Examples thereof include polyethylene glycol methacrylates (n=3 to 10), polyethylene glycol acrylates (n=3 to 10), methoxypolyethylene glycol methacrylates (n=3 to 10), and methoxypolyethylene glycol acrylates (n=3 to 10).

[0026] In formula (1), n ​​is preferably 5 or more and 8 or less, and by setting it within this range, the dispersibility of the pigment becomes better.

[0027] The content of the unit represented by formula (1) in the resin composition is preferably 4% by mass or more and 19% by mass or less, and more preferably 7% by mass or more and 13% by mass or less. By being within this range, the content of the unit represented by formula (1) interacts with the pigment and facilitates stabilization of dispersion, thereby improving the coloring power of the toner. Furthermore, the dispersibility of the release agent in the toner particles is improved, thereby improving hot offset resistance.

[0028] The polyolefin unit is preferably contained in the resin composition in an amount of 10% by mass to 30% by mass, more preferably 10% by mass to 20% by mass. By being contained within the above range, the polyolefin unit interacts with the pigment and facilitates stabilization of dispersion, thereby improving the coloring power of the toner. Furthermore, the dispersibility of the release agent in the toner particles is improved, thereby improving hot offset resistance.

[0029] The weight average molecular weight of the polyolefin unit is 0.9×10 4 Over 7.0 x 10 4 Preferably, it is 3.0 x 10 or less. 4 Over 6.0 x 10 4 It is more preferable that the toner has a molecular weight of 1000 or less. By being in the above range, the toner can easily stabilize dispersion while interacting with the pigment, thereby improving the coloring power of the toner. In addition, the dispersibility of the release agent in the toner particles is improved, thereby improving hot offset resistance.

[0030] The polyolefin unit is preferably at least one selected from the group consisting of hydrocarbon waxes such as polyethylene, polypropylene, and alkylene copolymers, of which polyethylene and polypropylene are preferred, and polypropylene is more preferred from the viewpoint of charge retention because it can suppress the molecular mobility of the hydrocarbon unit.

[0031] In order to stabilize the dispersion of the primary pigment particles in the toner particles, it is important to balance the content of the unit represented by formula (1) and the olefin unit. This balance can be evaluated by infrared absorption spectroscopy (FT-IR spectroscopy). FT-IR spectroscopy shows that the peak at 2800 cm -1 More than 2900cm -1 The maximum absorption peak intensity in the following range is P1, 1050 cm -1 More than 1150cm -1When the maximum absorption peak intensity in the following range is P2, the ratio of P1 to P2 (P2 / P1) is preferably in the range of 1.3 or more and 3.0 or less, and more preferably in the range of 1.4 or more and 2.5 or less (details of the measurement method will be described later).

[0032] The resin composition may be a copolymer of the unit represented by formula (1) and the styrene unit together with other monomers.

[0033] The resin composition preferably contains 50% by mass or more, more preferably 60% by mass or more, of the styrene unit, which suppresses molecular mobility of the resin composition having the styrene-acrylic unit and improves charge retention.

[0034] Examples of the monomer that forms the styrene unit include styrene-based monomers such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, and benzylstyrene.

[0035] Other monomers include vinyl ester monomers such as vinyl acetate; vinyl ether monomers such as vinyl methyl ether; halogen-containing vinyl monomers such as vinyl chloride; diene monomers such as butadiene and isobutylene; cycloalkyl group-containing vinyl monomers such as cyclohexyl acrylate; acid value-adding monomers such as acrylic acid, methacrylic acid, maleic anhydride, and maleic acid half ester, and combinations of these.

[0036] The weight average molecular weight of the resin composition is 1.5 × 10 4 Over 5.0 x 10 5 Preferably, it is 1.5 x 10 or less. 4 Over 5.0 x 10 4When the weight average molecular weight is within the above range, the dispersibility in the polyester resin is improved and the interaction with the pigment is facilitated, thereby improving the coloring power of the toner.

[0037] The content of the resin composition is preferably 3 parts by mass or more and 20 parts by mass or less, and more preferably 5 parts by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the binder resin. When the content of the resin composition is within the above range, the dispersibility in the polyester resin is improved and the interaction with the pigment is facilitated, thereby improving the coloring power of the toner.

[0038] <Binder resin> The binder resin used in the toner of the present invention will be described.

[0039] The toner of the present invention preferably contains 30% by mass or more of amorphous polyester as a binder resin, more preferably 50% by mass or more, and particularly preferably 70% by mass or more. When the content of amorphous polyester is within the above range, it becomes easier to control pigment dispersibility from the viewpoint of affinity with the binder resin, pigment, and resin composition, and the coloring power of the toner becomes good.

[0040] In the present invention, the binder resin may be used in combination with other resins as long as the amorphous polyester is within the above range.

[0041] As the other resin, known binder resins can be used, for example, the following binder resins:

[0042] Styrene-based resins, styrene-based copolymer resins, polyol resins, polyvinyl chloride resins, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, and petroleum-based resins.Preferably used resins include styrene-based copolymer resins, polyester resins, and hybrid resins in which polyester resins and styrene-based copolymer resins are mixed or partially reacted.

[0043] The toner particles of the present invention may contain a crystalline polyester resin. Known resins can be used as the crystalline polyester resin. The term "crystalline" refers to a resin that exhibits a clear melting point in differential scanning calorimetry.

[0044] The components constituting the amorphous polyester are described in detail below. The following components may be used singly or in combination depending on the type and application.

[0045] Examples of the divalent acid component constituting the amorphous polyester include the following dicarboxylic acids and derivatives thereof.

[0046] benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or their anhydrides or lower alkyl esters; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or their anhydrides or lower alkyl esters; alkenylsuccinic acids or alkylsuccinic acids having an average carbon number of 1 to 50, or their anhydrides or lower alkyl esters; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or their anhydrides or lower alkyl esters. Examples of the alkyl group in the lower alkyl ester include methyl, ethyl, propyl, and isopropyl groups.

[0047] On the other hand, examples of the dihydric alcohol component constituting the amorphous polyester include the following.

[0048] Ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanedimethanol (CHDM), hydrogenated bisphenol A, bisphenols represented by formula (I-1) and derivatives thereof, and diols represented by formula (I-2).

[0049] [ka] (In formula (I-1), R represents an ethylene group or a propylene group, x and y each represent an integer of 0 or more, and the average value of x+y is 0 or more and 10 or less.)

[0050] [ka] (In formula (I-2), R' is an ethylene group or a propylene group, x' and y' are each an integer of 0 or more, and the average value of x'+y' is 0 or more and 10 or less.)

[0051] The constituent components of the amorphous polyester may contain, in addition to the above-mentioned divalent carboxylic acid compound and divalent alcohol compound, a trivalent or higher carboxylic acid compound and a trivalent or higher alcohol compound as constituent components.

[0052] The trivalent or higher carboxylic acid compound is not particularly limited, but examples thereof include trimellitic acid, trimellitic anhydride, pyromellitic acid, etc. Furthermore, the trivalent or higher alcohol compound includes trimethylolpropane, pentaerythritol, glycerin, etc.

[0053] In addition to the above-mentioned compounds, the constituent components of the amorphous polyester may also contain monocarboxylic acid compounds and monoalcohol compounds as constituent components. Specific examples of monocarboxylic acid compounds include palmitic acid, stearic acid, arachidic acid, and behenic acid. Other examples include cerotic acid, heptacosanoic acid, montanic acid, melissic acid, lacteric acid, tetracontanoic acid, and pentacontanoic acid.

[0054] Examples of the monohydric alcohol compound include behenyl alcohol, ceryl alcohol, melissyl alcohol, and tetracontanol.

[0055] The method for producing the amorphous polyester is not particularly limited, and known methods can be used.

[0056] For example, the above-mentioned divalent carboxylic acid compound and divalent alcohol compound may be polymerized through an esterification reaction or transesterification reaction and a condensation reaction to produce an amorphous polyester.

[0057] The polymerization temperature is not particularly limited, but is preferably in the range of 180°C or higher and 290°C or lower.

[0058] In polymerizing the amorphous polyester, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide can be used.

[0059] The softening point (hereinafter also simply referred to as Tm) of the binder resin in the present invention is preferably 85°C or higher and 155°C or lower, and more preferably 100°C or higher and 155°C or lower.

[0060] When the softening point of the binder resin is within the above range, the high-temperature offset resistance is improved.

[0061] The glass transition temperature (Tg) of the binder resin is preferably 50°C or higher and 65°C or lower, and more preferably 55°C or higher and 60°C or lower.

[0062] When the glass transition temperature (Tg) of the binder resin is within the above range, molecular mobility in a high-temperature, high-humidity environment is suppressed, and the charge retention of the toner is improved.

[0063] <Coloring agent> The colorant usable in the present invention is characterized by being an organic pigment, which facilitates interaction between the intramolecular polarization of the colorant and the resin composition, thereby improving pigment dispersibility.

[0064] The colorant can be one or more known organic pigments. Examples of the organic pigment include yellow pigments (CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154) and the like. , 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, CI Vat Yellow 1, 3, 20), cyan pigments (CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 16, 17, 60, 62, 66, etc., CI Vat Blue 6, CI Acid Blue 45), magenta pigments (CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57, 57:1, 58, 60, 63, 64, 68, 81, 81:1, Examples of organic pigments include CI Pigment Blue 15:3, CI Pigment Red 122, and CI Pigment Red 150. These organic pigments include CI Pigment Blue 15:3, CI Pigment Red 122, and CI Pigment Red 150. These organic pigments are also useful for improving pigment dispersibility in toners. CI Pigment Blue 15:3, CI Pigment Red 122, and CI Pigment Red 150 are more preferred for improving pigment dispersibility.

[0065] The toner of the present invention can be used in combination with known inorganic pigments and dyes other than the above organic pigments.

[0066] Inorganic pigments and dyes that can be used in combination include carbon blacks such as furnace black, channel black, acetylene black, thermal black, and lamp black, as well as magnetic powders such as magnetite and ferrite, yellow dyes (CI Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, etc.), cyan dyes (CI Solvent Blue 25, 36, 60, 70, 93, 95, etc.), and magenta dyes (CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, etc.). , 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc., CI Disperse Red 9, CI Solvent Violet 8, 13, 14, 21, 27, etc., CI Disperse Violet 1, etc.; basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, etc., CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28, etc.).

[0067] The content of the colorant is preferably 1 part by mass or more and 20 parts by mass or less relative to 100 parts by mass of the binder resin, and more preferably 4 parts by mass or more and 15 parts by mass or less relative to 100 parts by mass of the binder resin.

[0068] Furthermore, the ratio (X2 / X1) of the parts by mass of the pigment (X2) to the parts by mass of the resin composition (X1) is preferably 0.2 or more and 3.0 or less, and more preferably 0.5 or more and 2.0 or less. By setting it in this range, the pigment dispersibility and hot offset resistance are improved.

[0069] <Release agent> The toner of the present invention may contain a release agent (wax) in order to impart releasability to the toner.

[0070] Examples of waxes that can be used in the present invention include: aliphatic hydrocarbon waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, olefin copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxidized aliphatic hydrocarbon waxes such as oxidized polyethylene wax; waxes containing fatty acid esters as the main component such as carnauba wax, behenyl behenate, and montan acid ester wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax. Furthermore, saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and valinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexamethylene bisstearic acid amide; ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N Examples of suitable esters include unsaturated fatty acid amides such as N,N'-dioleyl adipamide and N,N'-dioleyl sebacamide; aromatic bisamides such as m-xylene bisstearamide and N,N'-distearyl isophthalamide; fatty metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl copolymerizable monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxy groups obtained by hydrogenating vegetable oils and fats.

[0071] Waxes particularly preferred for use in the present invention are aliphatic hydrocarbon waxes. Examples include low-molecular-weight hydrocarbons obtained by radical polymerization of alkylenes under high pressure or polymerization using a Ziegler catalyst or a metallocene catalyst under low pressure; Fischer-Tropsch wax synthesized from coal or natural gas; olefin polymers obtained by thermal decomposition of high-molecular-weight olefin polymers; synthetic hydrocarbon waxes obtained from the distillation residue of hydrocarbons obtained by the Arge process from synthesis gas containing carbon monoxide and hydrogen, or synthetic hydrocarbon waxes obtained by hydrogenating these. Furthermore, hydrocarbon waxes fractionated by press sweating, solvent method, vacuum distillation, or fractional crystallization are more preferred. Waxes synthesized by methods other than alkylene polymerization are particularly preferred in terms of their molecular weight distribution.

[0072] The wax may be added during toner production or during binder resin production. These waxes may be used singly or in combination of two or more. The wax is preferably added in an amount of 1 to 20 parts by mass per 100 parts by mass of binder resin.

[0073] <Charge control agent> The toner of the present invention can use a known charge control agent as the charge control agent. Examples of known charge control agents include azo iron compounds, azo chromium compounds, azo manganese compounds, azo cobalt compounds, azo zirconium compounds, chromium compounds of carboxylic acid derivatives, zinc compounds of carboxylic acid derivatives, aluminum compounds of carboxylic acid derivatives, and zirconium compounds of carboxylic acid derivatives. The carboxylic acid derivative is preferably an aromatic hydroxycarboxylic acid. Charge control resins can also be used. If necessary, one or more types of charge control agents may be used in combination. The charge control agent is preferably added in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the binder resin.

[0074] <Career> The toner of the present invention may be used as a magnetic one-component developer, a non-magnetic one-component developer, or a two-component developer by mixing with a carrier. As the carrier, a carrier such as a normal ferrite or magnetite, or a resin-coated carrier may be used. A binder-type carrier core in which magnetic powder is dispersed in a resin may also be used.

[0075] Resin-coated carriers consist of carrier core particles and a coating material, which is a resin that coats the surfaces of the carrier core particles. Examples of resins used for the coating material include styrene-acrylic resins such as styrene-acrylate copolymers and styrene-methacrylate copolymers; acrylic resins such as acrylate copolymers and methacrylate copolymers; fluorine-containing resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymers, and polyvinylidene fluoride; silicone resins; polyester resins; polyamide resins; polyvinyl butyral; and aminoacrylate resins. Other examples include ionomer resins and polyphenylene sulfide resins. These resins can be used alone or in combination.

[0076] <External additives> In the toner of the present invention, it is preferable to externally add silica fine powder to the toner particles in order to improve the charge stability, developability, fluidity, and durability. The silica fine powder has a specific surface area of ​​30 m2 as measured by the BET method using nitrogen adsorption. 2 / g or more 500m 2 / g or less, and 2 / g or more 400m 2 The silica fine powder is preferably used in an amount of 0.01 parts by mass or more and 8.00 parts by mass or less, and more preferably 0.10 parts by mass or more and 5.00 parts by mass or less, relative to 100 parts by mass of toner particles.

[0077] The BET specific surface area of ​​the silica fine powder can be calculated using the BET multipoint method by adsorbing nitrogen gas onto the surface of the silica fine powder using, for example, a specific surface area measuring device such as Autosorb 1 (manufactured by Yuasa Ionics), GEMINI 2360 / 2375 (manufactured by Micrometilik), or Tristar 3000 (manufactured by Micrometilik).

[0078] If necessary, the silica fine powder is preferably treated with a treating agent such as unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, a silane coupling agent, a silane compound having a functional group, or other organosilicon compounds, or with a combination of various treating agents, for the purpose of hydrophobizing or controlling triboelectric charging.

[0079] Furthermore, other external additives may be added to the toner of the present invention as needed. Examples of such external additives include resin particles and inorganic fine powders that function as charge adjuvants, conductivity imparting agents, fluidity imparting agents, caking inhibitors, release agents for heat roller fixing, lubricants, abrasives, etc. Examples of charge adjuvants include metal oxides such as titanium oxide, zinc oxide, and alumina. Examples of lubricants include polyethylene fluoride powder, zinc stearate powder, and polyvinylidene fluoride powder. Examples of abrasives include cerium oxide powder, silicon carbide powder, and strontium titanate powder.

[0080] <Manufacturing method> The method for producing the toner particles in the present invention is not particularly limited, and they can be produced by known methods, such as a pulverization method, an emulsion aggregation method, a suspension polymerization method, and a dissolution suspension method.

[0081] Toner particles produced by the pulverization method are produced, for example, as follows: A binder resin, a resin composition, a colorant, and, if necessary, other additives are thoroughly mixed using a mixer such as a Henschel mixer or a ball mill. The mixture is melt-kneaded using a thermal mixer such as a twin-screw kneading extruder, a heated roll, a kneader, or an extruder. Wax, magnetic iron oxide particles, and a metal-containing compound may also be added during this process. The melt-kneaded mixture is cooled and solidified, and then pulverized and classified to obtain toner particles. The average circularity of the toner particles can be controlled by adjusting the exhaust temperature during pulverization. If necessary, the toner particles and external additives can be mixed using a mixer such as a Henschel mixer to obtain a toner.

[0082] Examples of mixers include the following: Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); Super mixer (manufactured by Kawata Corporation); Ribocone (manufactured by Okawara Manufacturing Co., Ltd.); Nauta mixer, Turbulizer, Cyclomix (manufactured by Hosokawa Micron Corporation); Spiral pin mixer (manufactured by Pacific Machinery Works Co., Ltd.); and Lödige mixer (manufactured by Matsubo Corporation).

[0083] Examples of kneaders include the following: KRC kneader (manufactured by Kurimoto Iron Works); Buss-Co kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by The Japan Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three-roll mill, mixing roll mill, kneader (manufactured by Inoue Manufacturing Co., Ltd.); Kneadex (manufactured by Mitsui Mining Co., Ltd.); MS-type pressure kneader, Kneader-Ruder (manufactured by Moriyama Manufacturing Co., Ltd.); and Banbury mixer (manufactured by Kobe Steel, Ltd.).

[0084] Examples of pulverizers include the following: Counter Jet Mill, Micron Jet, Innomizer (manufactured by Hosokawa Micron Corporation); IDS-type mill, PJM jet pulverizer (manufactured by Nippon Pneumatic Mfg. Co., Ltd.); Cross Jet Mill (manufactured by Kurimoto Iron Works Co., Ltd.); Urmax (manufactured by Nisso Engineering Co., Ltd.); SK Jet-O-Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); Turbo Mill (manufactured by Turbo Industrial Co., Ltd.); and Super Rotor (manufactured by Nisshin Engineering Co., Ltd.).

[0085] Furthermore, if necessary, after pulverization, the toner particles may be surface-treated using a Hybridization System (manufactured by Nara Machinery Works), Nobilta (manufactured by Hosokawa Micron Corporation), Mechanofusion System (manufactured by Hosokawa Micron Corporation), Faculty (manufactured by Hosokawa Micron Corporation), Innomizer (manufactured by Hosokawa Micron Corporation), Theta Composer (manufactured by Tokuju Kogyosho Co., Ltd.), Mechanomill (manufactured by Okada Seiko Co., Ltd.), or Meteor Rainbow MR Type (manufactured by Nippon Pneumatic Co., Ltd.) to control the average circularity of the toner particles.

[0086] Examples of classifiers include the following: Cruseal, Micron Classifier, and Spedic Classifier (manufactured by Seishin Enterprise Co., Ltd.); Turbo Classifier (manufactured by Nisshin Engineering Co., Ltd.); Micron Separator, Turboplex (ATP), and TSP Separator (manufactured by Hosokawa Micron Corporation); Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), and Dispersion Separator (manufactured by Nippon Pneumatic Industry Co., Ltd.); and YM Microcut (manufactured by Yaskawa Corporation).

[0087] Examples of sieving devices used to sift out coarse particles include Ultrasonic (manufactured by Koei Sangyo Co., Ltd.), Resonaseave, Gyrosifter (manufactured by Tokuju Kogyosho Co., Ltd.), Vibrasonic System (manufactured by Dalton Co., Ltd.), Soniclean (manufactured by Shinto Kogyo Co., Ltd.), Turbo Screener (manufactured by Turbo Industry Co., Ltd.), Microsifter (manufactured by Makino Sangyo Co., Ltd.), and circular vibrating sieves.

[0088] <Methods for measuring various physical properties> Next, the measurement methods for the raw materials and toner according to the present invention will be described.

[0089] (Measurement of toner particle size distribution) In the "Change Standard Measurement Method (SOM)" screen of the dedicated software, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value obtained using "Standard Particles 10.0 μm" (Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement."

[0090] In the dedicated software's "Pulse to particle size conversion setting screen," set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

[0091] The specific measurement method is as follows. (1) Pour approximately 200 ml of the electrolyte solution into a 250 ml round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Approximately 30 ml of the above-mentioned aqueous electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and approximately 0.3 ml of a dilution obtained by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant. (3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser, "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.), which has two built-in oscillators with an oscillation frequency of 50 kHz and a phase difference of 180 degrees and an electrical output of 120 W, and approximately 2 ml of the Contaminon N is added to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) While ultrasonic waves are irradiated to the electrolyte solution in the beaker in (4), approximately 10 mg of toner particles are added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C. (6) Using a pipette, the (5) electrolytic solution in which the toner particles have been dispersed is dropped into the (1) round-bottom beaker placed in the sample stand, and the measurement concentration is adjusted to about 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device to calculate the weight-average particle size (D4). Note that when the dedicated software is set to Graph / Volume %, the "Average diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4).

[0092] (Method for measuring average circularity) The average circularity of the toner particles is measured using a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions at the time of calibration work.

[0093] The specific measurement method is as follows. First, approximately 20 mL of ion-exchanged water, from which impurities such as solids have been removed, is placed in a glass container. Approximately 0.2 mL of a solution prepared by diluting "Contaminon N" (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) approximately three times by weight with ion-exchanged water is added. Approximately 0.02 g of the measurement sample is then added, and the mixture is dispersed for 2 minutes using an ultrasonic disperser to obtain the dispersion for measurement. The dispersion is then cooled appropriately so that its temperature is between 10°C and 40°C. A tabletop ultrasonic cleaner disperser ("VS-150" manufactured by Vervoclear Co., Ltd.) with an oscillation frequency of 50 kHz and an electrical output of 150 W is used as the ultrasonic disperser. A predetermined amount of ion-exchanged water is placed in the water tank, and approximately 2 mL of the Contaminon N is added to the water tank.

[0094] For the measurement, the flow-type particle image analyzer equipped with a standard objective lens (10x magnification) was used, and the particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure was introduced into the flow-type particle image analyzer, and 3,000 toner particles were measured in HPF measurement mode and total count mode. The binarization threshold for particle analysis was set to 85%, and the analyzed particle diameter was limited to a circle-equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles was determined.

[0095] Before starting the measurement, automatic focus adjustment is performed using standard latex particles (Duke Scientific's "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" diluted with ion-exchanged water). After that, it is preferable to perform focus adjustment every two hours from the start of the measurement.

[0096] In the examples of the present application, a flow-type particle image analyzer was used that had been calibrated by Sysmex Corporation and had a calibration certificate issued by Sysmex Corporation. Measurements were carried out under the same measurement and analysis conditions as when the calibration certificate was received, except that the particle diameters to be analyzed were limited to equivalent-circle diameters of 1.985 μm or more and less than 39.69 μm.

[0097] (Measurement of glass transition temperature (Tg) of binder resin and toner) The glass transition temperature of the resin is measured using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments) in accordance with ASTM D3418-82.

[0098] The melting points of indium and zinc are used to correct the temperature of the detector, and the heat of fusion of indium is used to correct the amount of heat.

[0099] Specifically, about 3 mg of resin or toner is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is carried out under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 30℃ Measurement end temperature: 180℃

[0100] Measurements are performed in the measurement range of 30 to 180°C at a heating rate of 10°C / min. The temperature is raised to 180°C once and held for 10 minutes, then lowered to 30°C, and then raised again. During this second heating process, the specific heat change is obtained in the temperature range of 30 to 100°C. The point at which the line midpoint between the baselines before and after the specific heat change intersects with the differential thermal curve is taken as the glass transition temperature (Tg) of the resin.

[0101] (Measurement of the softening point (Tm) of the binder resin) In the present invention, the softening point (Tm) of the resin can be measured using a constant load extrusion type capillary rheometer "Flow characteristic evaluation device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation).

[0102] The CFT-500D is an instrument that applies a constant load from above using a piston, while heating and melting the measurement sample filled in a cylinder and forcing it out through a capillary hole at the bottom of the cylinder, and can graph a flow curve from the piston's descent (mm) and temperature (°C).

[0103] In the present invention, the "melting temperature in the 1 / 2 method" described in the manual attached to the "flow property evaluation device, flow tester CFT-500D" is taken as the softening point (Tm).

[0104] The melting temperature in the 1 / 2 method is calculated as follows.

[0105] First, calculate half the difference between the amount of piston descent when the outflow ends (end of outflow, Smax) and the amount of piston descent when the outflow starts (lowest point, Smin) (this is called X; X = (Smax - Smin) / 2). Then, determine the melting temperature in the 1 / 2 method as the temperature on the flow curve when the amount of piston descent is the sum of X and Smin.

[0106] The measurement sample is prepared by compressing 1.2 g of resin at 10 MPa for 60 seconds using a tablet press (e.g., a standard manual Newton press NT-100H, manufactured by NPA Systems Co., Ltd.) at 25°C to form a cylindrical shape with a diameter of 8 mm.

[0107] The specific procedures for measurement are carried out according to the manual attached to the device.

[0108] The measurement conditions for the CFT-500D are as follows: Test mode: Temperature rising method Starting temperature: 40℃ Achieved temperature: 200℃ Measurement interval: 1.0℃ Heating rate: 4.0℃ / min Piston cross-sectional area: 1.000cm 2 Test load (piston load): 5.0 kgf Preheat time: 300 seconds Die hole diameter: 1.0mm Die length: 1.0mm

[0109] (Measurement of weight average molecular weight) The weight average molecular weight of the resin composition is measured using gel permeation chromatography (GPC) as follows.

[0110] First, the sample is placed in tetrahydrofuran (THF) and left at 25°C for several hours, then shaken thoroughly to mix well with the THF, and left to stand for another 12 hours or more until the sample no longer aggregates.

[0111] The solution is left in the THF for 24 hours, and then passed through a sample treatment filter (pore size 0.2 μm to 0.5 μm, for example, Myshoridisc H-25-2 (manufactured by Tosoh Corporation)) to prepare a GPC sample.

[0112] The sample concentration is adjusted to 0.5 mg / ml or more and 5.0 mg / ml or less. Measurement is performed using this sample solution under the following conditions.

[0113] The column is stabilized in a heat chamber at 40°C, and tetrahydrofuran (THF) as a solvent is passed through the column at this temperature at a flow rate of 1 ml per minute, and about 100 µl of the sample solution is injected and measured.

[0114] The column is a combination of several commercially available polystyrene gel columns. For example, a combination of Shodex GPC KF-801, 802, 803, 804, 805, 806, 807, and 800P manufactured by Showa Denko Co., Ltd., or a combination of TSKgel G1000H (H manufactured by Tosoh Corporation) is used. XL ), G2000H(H XL ), G3000H(H XL ), G4000H(H XL ), G5000H(H XL ), G6000H(H XL ), G7000H(H XL ) and a combination of TSKguard column are used.

[0115] When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithm of the calibration curve prepared using several monodisperse polystyrene standard samples and the count value.

[0116] The standard polystyrene samples used to create the calibration curve were those manufactured by Tosoh Corporation or Showa Denko Co., Ltd., with a molecular weight of 1 × 10 2 ~1×10 7 At least 10 standard polystyrene samples are used. An RI (refractive index) detector is used.

[0117] (Measurement of Acid Value of Binder Resin and Resin Composition) The acid value of the binder resin and the resin composition is measured by the following method. The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of sample. The acid value of the polyester resin is measured in accordance with JIS K 0070-1992. Specifically, the following procedure is followed.

[0118] (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95 vol%) and add deionized water to make 100 ml to obtain a phenolphthalein solution.

[0119] Dissolve 7 g of special-grade potassium hydroxide in 5 ml of deionized water and add ethyl alcohol (95 vol%) to make 1 liter. Place in an alkali-resistant container to avoid contact with carbon dioxide and leave for 3 days, then filter to obtain potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by placing 25 ml of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution, and then determining the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0120] (2) Operation (A) Main test A 2.0 g sample of crushed polyester resin was weighed accurately into a 200 ml Erlenmeyer flask, and 100 ml of a 2:1 toluene:ethanol mixture was added and allowed to dissolve for 5 hours. A few drops of the phenolphthalein solution were then added as an indicator, and the solution was titrated with the potassium hydroxide solution. The titration endpoint was determined when the indicator's light red color persisted for approximately 30 seconds.

[0121] (B) Blank test The titration is carried out in the same manner as above, except that no sample is used (i.e., only the toluene:ethanol (2:1) mixed solution is used).

[0122] (3) The obtained results are substituted into the following formula to calculate the acid value. A=[(CB)×f×5.61] / S where A is the acid value (mgKOH / g), B is the amount of potassium hydroxide solution added for the blank test (ml), C is the amount of potassium hydroxide solution added for the main test (ml), f is the factor of the potassium hydroxide solution, and S is the sample (g).

[0123] (Measurement of infrared absorption spectrum) FT-IR spectra by the ATR method were obtained using a Spectrum One (Fourier transform infrared spectrometer) manufactured by PerkinElmer equipped with a Universal ATR Sampling Accessory.

[0124] The incident angle of the infrared light was set to 45°.

[0125] The prism used in the ATR measurement was a Ge ATR crystal (refractive index = 4.0).

[0126] Other conditions are as follows: Range Start: 4000cm -1 End: 600cm -1 (Ge ATR crystal) Duration Scan number: 4 Resolution: 4.00cm -1 Advanced: CO2 / H2O correction

[0127] The specific measurement procedure is as follows.

[0128] How to calculate the ratio (P2 / P1): (1) A Ge ATR crystal (refractive index = 4.0) is attached to the device. (2) Set the Scan type to Background and Units to EGY and measure the background. (3) Set Scan type to Sample and Units to A. (4) 0.01 g of sample is precisely weighed onto the ATR crystal. (5) Pressurize the sample with the pressure arm (Force Gauge is 100). (6) Measure the sample. (7) The obtained FT-IR spectrum is baseline corrected using Automatic Correction. (8) 1050cm -1 More than 1150cm -1 Calculate the maximum absorption peak intensity in the following range: (P2) (9) 2800 cm -1 More than 2900cm -1 Calculate the maximum absorption peak intensity in the following range: (P1) (10) Calculate the ratio (P2 / P1). [Example]

[0129] The basic configuration and features of the present invention have been described above. The present invention will now be described in detail based on examples. However, the present invention is not limited to these examples. Unless otherwise specified, parts are by weight.

[0130] <Production example of binder resin PL1> Bisphenol A ethylene oxide (2.2 mole adduct): 50.0 mole parts Bisphenol A propylene oxide (2.2 mole adduct): 50.0 mole parts Terephthalic acid: 90.0 parts by mole Trimellitic anhydride: 10.0 parts by mole 100 parts of the monomers constituting the polyester unit were mixed together with 500 ppm of titanium tetrabutoxide in a 5-liter autoclave.

[0131] A reflux condenser, water separator, N2 gas inlet tube, thermometer, and stirrer were attached to the autoclave, and a condensation polymerization reaction was carried out at 230°C while introducing N2 gas into the autoclave. The reaction time was adjusted to obtain the desired softening point, and after the reaction was completed, the resin was removed from the vessel, cooled, and pulverized to obtain binder resin PL1. The binder resin PL1 had a Tm of 102°C, a Tg of 55°C, and no melting point.

[0132] <Production example of binder resin PL2> Binder resin PL2 was obtained in the same manner as in the production example for binder resin PL1, except that the type and amount of monomer were changed and Tm and Tg were changed by adjusting the reaction time as shown in Table 1. The physical properties of the obtained binder resin PL2 are shown in Table 1.

[0133] <Manufacturing example of binder resin PL3> 70 parts styrene 24 parts n-monobutyl acrylate Monobutyl maleate 6 parts 2,2-bis(4,4-di-t-butyloxycyclohexyl)propane 1 part While stirring 200 parts of xylene in a four-neck flask, the atmosphere in the flask was thoroughly replaced with nitrogen and the temperature was raised to 120°C, after which the above components were added dropwise to the four-neck flask over 3.5 hours. Polymerization was then completed under reflux with xylene, and the solvent was removed by distillation under reduced pressure to obtain binder resin PL3, a vinyl resin. The physical properties of the obtained binder resin PL3 are shown in Table 1.

[0134] <Production example of binder resin PH1> Bisphenol A ethylene oxide (2.2 mole adduct): 50.0 mole parts Bisphenol A propylene oxide (2.2 mole adduct): 50.0 mole parts Terephthalic acid: 90.0 parts by mole The above materials were weighed and placed in a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet, and a thermocouple. 500 ppm of titanium tetrabutoxide was then added to the reaction vessel. The atmosphere in the flask was then replaced with nitrogen gas, and the temperature was gradually raised while stirring. The mixture was allowed to react for 2 hours at 200°C while stirring.

[0135] Furthermore, the pressure inside the reaction vessel was reduced to 8.3 kPa and maintained at that level for 1 hour, after which the vessel was cooled to 180°C and returned to atmospheric pressure (first reaction step). Trimellitic anhydride: 10.0 parts by mole Thereafter, the above materials and 0.003 molar part of tert-butylcatechol (polymerization inhibitor) were added to the reaction vessel, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160°C. After confirming that the softening point measured in accordance with ASTM D36-86 reached 151°C, the temperature was reduced to stop the reaction (second reaction step), thereby obtaining binder resin PH1. The obtained binder resin PH1 had a softening point (Tm) of 151°C, a glass transition temperature (Tg) of 59°C, and no melting point.

[0136] [Table 1]

[0137] <Production Example of Resin Composition PA1> In an autoclave reactor equipped with a thermometer and a stirrer, 300.0 parts of xylene, 100.0 parts of polypropylene (weight average molecular weight 3.8 x 10 4 After purging with nitrogen, a mixed solution of 63.74 parts of styrene, 4.72 parts of cyclohexyl methacrylate, 3.54 parts of methacrylic acid, 13.0 parts of methoxypolyethylene glycol acrylate, and 250.0 parts of xylene was added dropwise at 180°C for 3 hours to polymerize. The mixture was then held at this temperature for an additional 30 minutes to remove the solvent, yielding resin composition PA1. The ATR index (P1 / P2), acid value, and weight-average molecular weight of the resulting resin composition PA1 are shown in Table 2.

[0138] <Production Examples of Resin Compositions PA2 to PA9> Resin compositions PA2 to 9 were obtained in the same manner as resin composition PA1, except that the components and amounts were changed as shown in Table 2. The ATR index (P1 / P2), acid value, and weight average molecular weight of the obtained resin compositions PA2 to 9 are shown in Table 2.

[0139] [Table 2]

[0140] Example 1 (Toner 1 manufacturing example) 70 parts of PL1 binder resin 30 parts of binder resin PH1 ·Resin composition PA1 10 parts Fischer-Tropsch wax (FNP0090, melting point: 90°C) 6 parts CI Pigment Blue 15:3 5 parts The above materials were premixed in a Henschel mixer, and then melt-kneaded at 160°C in a twin-screw kneading extruder.

[0141] The resulting kneaded product was cooled, coarsely pulverized in a hammer mill, and then finely pulverized in a turbo mill.

[0142] The resulting finely pulverized product was classified using a multi-division classifier utilizing the Coanda effect to obtain negatively triboelectrically charged toner particles having a weight average particle size (D4) of 6.5 μm and an average circularity of 0.952.

[0143] For 100 parts of the toner particles, hydrophobized silica fine particles (specific surface area measured by nitrogen adsorption using the BET method is 140 m 2 The mixture was sieved through a mesh with 150 μm openings to obtain toner 1.

[0144] The above toner 1 and the magnetic carrier were mixed in a V-type mixer (V-10 type: Tokuju Manufacturing Co., Ltd.) for 0.5 seconds so that the toner concentration became 10% by mass. -1 The mixture was mixed under the condition of 1000 W, 1000 W, and a rotation time of 5 minutes to prepare Developer 1. The magnetic carrier used was magnetic ferrite carrier particles (number average particle size: 38 μm) whose surfaces were coated with acrylic resin.

[0145] The resulting developer 1 was subjected to the following evaluations.

[0146] [Evaluation of toner coloring power] The image density of the images prepared under the following conditions was evaluated: The image density was measured using an X-Rite color reflection densitometer (500 series, manufactured by X-Rite Corporation). Paper: OK-TOP coated paper (basis weight 128.0g / m 2 ) Toner amount: 0.35 mg / cm 2 Evaluation image: 5cm on paper 2 More solid images Image fixing environment: Temperature 25°C / Humidity 50%RH Fixing speed: 360mm / sec Fixing temperature: 180℃

[0147] The image density was measured at three points on the same image, and the coloring power of the toner was calculated from the average value.

[0148] (Evaluation criteria) A: Image density 1.40 or higher B: Image density 1.30 or more and less than 1.40 C: Image density 1.20 or more and less than 1.30 D: Image density less than 1.20

[0149] [High temperature offset resistance evaluation] An unfixed image was formed under the following conditions: A modified imagePRESSC910 was used as the image forming apparatus. Paper: CS-680 (68.0g / m 2 ) Toner loading: 0.08 mg / cm 2 Image Processing: Error Diffusion The unfixed image prepared above was passed through a fixing unit in an environment of 23°C temperature and 5% humidity. The process speed was fixed at 360 mm / sec, and the temperature of the fixing belt was set in 5°C increments from 120°C to 230°C. The average reflectance Dr (%) of the evaluation paper before image output and the reflectance Ds (%) of the white background area after the fixing test were measured using a reflectometer (REFLECTOMETER MODEL TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.), and the fog was calculated using the following formula. From the obtained fog, the fixing temperature at which the fog value became 0.5% was calculated as the high-temperature offset occurrence temperature, and high-temperature offset resistance was evaluated. Fog (%) = Dr (%) - Ds (%)

[0150] (Evaluation criteria) A: High temperature offset occurs at 180°C or higher B: High temperature offset occurs at temperatures between 160°C and 180°C C: High temperature offset occurs at temperatures between 140°C and 160°C D: High temperature offset occurs at temperatures below 140°C

[0151] [Charging stability evaluation] A modified imagePRESSC910 was used as the image forming apparatus. Developer 1, which had been left in a high-temperature, high-humidity environment (temperature 32.5°C, humidity 80% RH) for 24 hours, was placed in the developing machine, and the amount of developer placed on the electrostatic latent image carrier was adjusted to 0.40 mg / cm. 2 The developing machine was allowed to idle for 2 minutes inside the main body, and the developing bias was adjusted so that the density of the solid image would be 1.35.

[0152] With the power of the main unit still on, the developing unit was removed from the machine and left for two weeks in an environment with a temperature of 32.5°C and a humidity of 80%RH. After leaving it, the developing unit was returned to the main unit, a solid image was printed, and the density was measured.

[0153] The image density before the storage was set at 100%, and the density maintenance rate after the storage was calculated and evaluated.

[0154] (Evaluation criteria) A: Concentration maintenance rate 95% or more B: Concentration maintenance rate: 90% or more but less than 95% C: Concentration maintenance rate: 85% or more but less than 90% D: Concentration maintenance rate less than 85%

[0155] In all of the above evaluation items, Developer 1 was rated A.

[0156] [Examples 2 to 16, Comparative Examples 1 to 3] (Toner 2 to 19 manufacturing examples) Toners 2 to 19 were obtained in the same manner as in the production example of Toner 1, except that the types and amounts of binder resin and colorant were changed as shown in Table 3.

[0157] [Table 3]

[0158] (Production examples of developers 2 to 19) Developers 2 to 19 were obtained in the same manner as in the production example of developer 1, except that the toner was changed as shown in Table 4. Furthermore, evaluations were carried out in the same manner as for developer 1. The evaluation results are shown in Table 4.

[0159] [Table 4]

Claims

1. A toner having toner particles containing a binder resin, a colorant, and a resin composition, The resin composition contains a polyolefin unit and a unit represented by the following formula (1): The toner is characterized in that the colorant is an organic pigment. 【Chemical 1】 (n represents 3≦n≦10. R1 and R2 each independently represent H or CH 3 Represents.)

2. 2. The toner according to claim 1, wherein the organic pigment is any one of C. I. Pigment Blue 15:3, C. I. Pigment Red 122, and C. I. Pigment Red 150.

3. 3. The toner according to claim 1, wherein the toner particles contain the resin composition in an amount of 3 parts by mass to 20 parts by mass relative to 100 parts by mass of the binder resin.

4. 4. The toner according to claim 1, wherein the binder resin is a polyester.

5. 5. The toner according to claim 1, wherein the resin composition is a polymer in which a styrene-acrylic unit is grafted onto the polyolefin unit.

6. 6. The toner according to claim 5, wherein the styrene acrylic unit contains a unit derived from methoxypolyethylene glycol acrylate.

7. The resin composition exhibited the following FT-IR spectrum measured by an ATR method using Ge as an ATR crystal at an incident angle of infrared light of 45°: 2800 cm -1 More than 2900cm -1 The maximum absorption peak intensity in the following range is P1, 1050cm -1 1150cm or more -1 The maximum absorption peak intensity in the following range is P2 7. The toner according to claim 1, wherein the ratio of P1 to P2 (P2 / P1) is 1.3 or more and 3.0 or less.

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