Toner

Abstract

To provide a toner that has stable charging characteristics irrespective of a print speed and environment, reduces image fogging, and can provide prints with less density variation and less hue variation from the first print to the last print.SOLUTION: A toner contains toner particles. The toner particles each have a toner base particle having a binder resin and a coloring agent, and a silicon-titanium polymer complex present on the surface of the toner base particle. The silicon-titanium polymer complex contains a silicon polymer portion and a titanium chelate portion. The silicon-titanium polymer complex has a peak attributed to Ti-O-Si expansion and contraction vibration according to infrared spectroscopic analysis. When the ratio of the number of titanium atoms is defined as Ti-E, and the ratio of the number of silicon atoms is defined as Si-E, which are obtained in X-ray electron spectroscopic analysis on the toner, Ti-E and Si-E satisfy the specific relationships.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to toners for use in recording methods utilizing electrophotography, electrostatic recording, and toner jet recording. [Background technology]

[0002] Methods of visualizing image information via electrostatic latent images, such as electrophotography, are applied to copiers, multifunction machines, and printers, and in recent years, there has been a demand for further cost reduction and higher image quality. In particular, the required level of image quality has been increasing year by year regardless of print speed, and toners that can achieve high image quality are in demand. Furthermore, with the expansion of the global printer market, printers are used in a variety of environments, and there is a demand for printers that can maintain high image quality in a variety of environments.

[0003] After being transported onto the toner carrier, the toner is frictionally charged by rubbing against a charge-providing member, and then electrostatically propagates from the toner carrier to an electrostatic latent image on an electrostatic latent image carrier (hereinafter referred to as an electrophotographic photoreceptor or photoreceptor), forming an image.

[0004] In order to improve image quality, it is necessary to faithfully reproduce the latent image with toner, and therefore precise control of the charge of the toner is required. If the charge control of the toner is insufficient, various problems occur, such as fogging caused by low-charged toner being developed in non-image areas, fogging caused by poor regulation of toner on the toner transport member due to over-charged toner firmly adhering to the toner carrier, and further, image density change caused by change in the charge amount of the toner between the beginning and end of printing, which are factors that hinder faithful reproduction of the latent image.

[0005] Conventionally, the method of controlling the charge of toner has been to use inorganic fine particles with high insulation such as silica and inorganic fine particles with low insulation such as titania as external additives in combination, and to make the charge uniform by uniformly attaching these inorganic fine particles to the surface of toner particles to improve the fluidity of the toner. However, there was a concern that the charging characteristics would deteriorate due to continuous use or leaving in a high-temperature and high-humidity environment. In order to solve the above problems, Patent Document 1 uses silica-titania composite particles that combine the properties of silica and titania. Patent Document 2 uses silica composite particles that contain silicon oxide and titanium. Furthermore, Patent Document 3 uses composite particles of all metal elements belonging to Groups 3 to 13 and an organosilicon compound. In this way, methods for controlling the charge of toner have been proposed. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2011-118210 A [Patent Document 2] JP 2014-021214 A [Patent Document 3] JP 2019-128515 A Summary of the Invention [Problem to be solved by the invention]

[0007] For example, in Patent Document 1, titania has a core-shell structure covered with silica, which controls the zeta potential, improves the maintenance and rise of charge, and suppresses fogging. However, the toner described in Patent Document 1 contains a large amount of titania, which makes it easy to generate excessive conductive paths. Therefore, in printers with slow printing speeds, charge leakage occurs due to the conductive paths, and the amount of charge is large at the beginning and end of continuous printing. Since the charge density of the image varies greatly, there may be a variation in the image density due to charging.

[0008] In Patent Document 2, by using composite particles of silicon oxide and titanium element with irregular shapes, the composite particles are prevented from migrating from the toner to members, improving density fluctuation and fogging. However, the toner in Patent Document 2 has a large amount of exposed titanium element on the surface, so there remains an issue with fogging in high temperature and high humidity environments.

[0009] In Patent Document 3, metal atoms derived from polyvalent metal salts are unevenly distributed on the outermost surface of the toner, resulting in many moisture adsorption sites, and the exposed polyvalent metal salts act as charge leakage points. Therefore, the charge leakage is not sufficiently suppressed to meet the increased process speed under high temperature and high humidity conditions, and sufficient charging properties may not be obtained to suppress fogging under high temperature and high humidity conditions.

[0010] None of the above-mentioned inventions can simultaneously solve all of the problems of density fluctuation and fogging in harsh environments regardless of printing speed, and therefore further toner charge control technology is required. This disclosure is directed to a toner that has stable charging characteristics regardless of printing speed or environment, has little image fog, and can provide printed matter with little density and color variation from the first page to the last print. [Means for solving the problem]

[0011] The present disclosure provides a toner comprising toner particles, The toner particles are toner base particles having a binder resin and a colorant; a silicon-titanium polymer composite present on the surface of the toner base particle; The silicon-titanium polymer composite contains a silicon polymer moiety and a titanium chelate moiety; The silicon-titanium polymer composite has a 900 cm peak attributable to Ti-O-Si stretching vibration in a spectrum obtained by infrared spectroscopy. -1 ~1000cm -1 It has a peak at When the ratio of the number of titanium atoms to the sum of the numbers of carbon atoms, oxygen atoms, silicon atoms, phosphorus atoms, and titanium atoms obtained by X-ray photoelectron spectroscopy of the toner is defined as Ti-E and the ratio of the number of silicon atoms is defined as Si-E, The toner relates to a toner in which the Ti-E and the Si-E satisfy the following formulas (1) and (2). 1.0×10 -3≦Ti-E≦ 2.5×10 -2 (1) 1.0×10 -2 ≦Ti-E / Si-E≦ 7.0×10 -2 (2) Effect of the Invention

[0012] The present disclosure makes it possible to provide a toner that has stable charging characteristics regardless of printing speed or environment, has little image fog, and can produce printed matter with little density and color variation from the first page to the last print. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" expressing a numerical range means a numerical range including a lower limit and an upper limit, which are fractions, unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined. In addition, in the present disclosure, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ.

[0014] The present disclosure will be described in detail below. The toner of the present disclosure is characterized in that it contains, as toner particles, a silicon-titanium polymer composite in which a silicon polymer moiety and a titanium chelate moiety are chemically bonded and the titanium chelate moiety is covered to a specific extent by the silicon polymer moiety. -1 ~1000cm -1 It can be confirmed that the silicon polymer moiety and the titanium chelate moiety are bonded by having a peak at 1000 nm. In addition, it is considered that the titanium chelate moiety is covered to a certain extent by the silicon polymer moiety by satisfying the formulas (1) and (2) described below.

[0015] Silicon polymer compounds have a high volume resistivity, so charges can accumulate due to friction or an external electric field, which can cause the toner to become overcharged. On the other hand, titanium chelate has a structure in which titanium and chelate form a cross-linked structure. Chelates tend to receive electron pairs and become negatively charged, and the cross-linked structure promotes the movement of electrons. Therefore, although titanium chelate is a material with excellent dielectric and conductive properties, it has excellent conductive properties by itself, so charges generated by friction or an external electric field leak through the titanium chelate, which can result in low charge of the toner.

[0016] Conventionally, there have been silicon oxide-titanium composite particles such as silicon oxide and titania or titanium alkoxide, but as a result of extensive research by the present inventors, it has been discovered that by using a titanium chelate, which is a titanium compound that has excellent dielectric properties and conductive properties, and further chemically bonding this with a silicon polymer that has excellent insulating properties, and coating the titanium chelate site, it is possible to achieve excellent charge build-up properties and environmental stability.

[0017] In a printer, the toner is charged by rubbing against a triboelectric charging member or carrier, which has a lower volume resistivity than the toner. This charged toner is carried by a developing roller in the case of a one-component development system, or by a carrier in the case of a two-component development system. The carried toner moves to the latent image area of ​​the photoconductor in the development section due to the influence of an external electric field, forming an image.

[0018] As mentioned above, titanium chelate has high dielectric properties, so it is polarized by the influence of the external electric field in the development section. On the other hand, it also has high conductive properties, so the polarized charge leaks out of the titanium chelate and even into the toner carrier. In response to such issues, the present disclosure uses a silicon-titanium polymer composite in which silicon and titanium chelate are chemically bonded, thereby achieving good charge rise properties. It is believed that the use of a silicon-titanium polymer composite in which silicon and titanium chelate are chemically bonded produces the following two effects.

[0019] The first effect is that the silicon-titanium polymer composite has lower conductivity than the titanium chelate alone. This effect makes it possible to suppress leakage of charge to the toner carrier. The second effect is that the bias during development causes the polarized charge in the titanium chelate portion to be electrostatically induced in the silicon polymer portion, thereby providing a charge in a manner other than frictional charging. As a result, it is believed that the silicon-titanium polymer composite is able to reach a saturated charge amount more quickly than the silicon polymer alone.

[0020] Furthermore, in printers with slow printing speeds, the time from when the toner is charged to when it is developed is long, so that charge leakage to the toner carrier is likely to occur. Therefore, by controlling the amount of titanium chelate near the surface of the silicon-titanium polymer composite, charge leakage to the toner carrier is suppressed, and charge rise property can be maintained.

[0021] In addition, when titanium alkoxide is used instead of titanium chelate, titanium atoms are finely dispersed inside the silicon-titanium polymer composite due to the high reactivity of titanium alkoxide, which makes the silicon-titanium polymer composite more likely to undergo a conductive phenomenon, and is therefore more likely to cause fogging after long-term storage under high temperature and high humidity. In addition, when titanium oxide is used, the electrostatic induction effect derived from the chelating site cannot be obtained, and therefore sufficient conductivity cannot be obtained. As a result, the charge distribution of the toner becomes broad in a low-temperature, low-humidity environment, and fogging derived from the low-charge component is likely to occur.

[0022] Furthermore, environmental stability is improved by controlling the amount of titanium on the surface of the silicon-titanium polymer composite. Titanium compounds such as titania and titanium chelate, which are generally used in toners, are materials that easily adsorb moisture. Therefore, when the amount of titanium derived from these materials on the toner surface is large, the effect of moisture adsorption on the toner becomes large. As a result, when the silicon-titanium polymer composite is left in a high humidity environment for a long period of time, the conductive properties of the silicon-titanium polymer composite are increased by adsorbing water, and the charge of the toner obtained by friction or the influence of an external electric field is easily leaked to the toner carrier by electrostatic induction, so that the charge amount of the toner is reduced.

[0023] In response to this, the present inventors have investigated the conditions for the state of titanium in a silicon-titanium polymer composite from the viewpoint of improving the environmental stability, and as a result have found that it is important to satisfy the following formulas (1) and (2). 1.0×10 -3 ≦Ti-E≦ 2.5×10 -2 (1) 1.0×10 -2 ≦Ti-E / Si-E≦ 7.0×10 -2 (2) The values ​​of Ti-E and Si-E in formulas (1) and (2) are obtained based on X-ray electron spectroscopy (ESCA) of the toner. The ratio of the number of titanium atoms to the total number of carbon atoms, oxygen atoms, silicon atoms, phosphorus atoms, and titanium atoms is Ti-E, and the ratio of the number of silicon atoms is Si-E.

[0024] In formula (1), Ti-E indicates the proportion of titanium element near the surface. The lower the Ti-E value, the fewer titanium chelate sites near the surface. -3 If the Ti-E is less than 2.5×10, the excessive charge cannot be leaked to the toner carrier, so the toner is likely to be charged up in a low humidity environment, and image fogging is likely to occur. -2If it exceeds this value, there will be many titanium chelate sites near the surface, so that leakage of charge to the toner carrier will be likely to occur, and the charge amount will decrease, particularly in a high-temperature, high-humidity environment, which may result in image fogging. Ti-E is preferably 4.0×10 -3 ~ 2.0×10 -2 and more preferably 5.0×10 -3 ~ 1.5×10 -2 It is.

[0025] In formula (2), Ti-E / Si-E represents the ratio of titanium to silicon on the surface. A small Ti-E / Si-E ratio means that most of the surface is occupied by silicon polymer sites, and the charging sites of the toner particles are strongly influenced by the properties of the silicon polymer. Ti-E / Si-E is 1.0×10 -2 When the Ti-E / Si-E ratio is less than 7.0×10, the charge sites on the surface of the toner particles are strongly affected by the insulating properties of the silicon polymer, and therefore charges tend to accumulate in the toner, especially in low-humidity environments, causing image fogging. -2 If the toner particle surface charge ratio exceeds 100%, the charge sites on the toner particle surface become strongly affected by the characteristics of titanium chelate, and are strongly affected by moisture adsorption under high temperature and high humidity conditions, for example, and the toner charge amount decreases after long-term storage, causing image fogging. Ti-E / Si-E is preferably 2.0×10 -2 ~ 6.0×10 -2 and more preferably 2.5×10 -2 ~ 5.5×10 -2 It is.

[0026] In order to satisfy the above formulas (1) and (2), a method of controlling the dispersion state of the titanium compound can be mentioned. In general, reactive titanium compounds include alkoxides and acylates in addition to chelates. However, since alkoxide and acylate titanium compounds are more reactive than chelates, when reacted with silicon compounds, the titanium compound may be finely dispersed in the silicon polymer, causing percolation, or vice versa, resulting in the formation of a thin film of titanium. Titanium compounds often aggregate, resulting in a large amount of titanium on the surface. In the present disclosure, it is preferable to use titanium chelate because it has a gentle reactivity and is easy to control the reaction by pH and temperature. In addition, the use of titanium chelate results in the presence of chelate crosslinks in the silicon-titanium composite particles, which is preferable from the viewpoint of the charge balance. More preferred aspects of the present disclosure are described below.

[0027] The titanium chelate in the titanium chelate moiety preferably comprises at least one titanium chelate selected from the group consisting of titanium phosphate chelate, titanium lactate, titanium ammonium lactate, titanium dodecylbenzenesulfonate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, and titanium octylene glycolate.

[0028] The titanium chelate more preferably contains at least one titanium chelate selected from the group consisting of titanium phosphate, titanium lactate, titanium ammonium lactate, and titanium dodecylbenzenesulfonate. In the silicon-titanium polymer composite, these titanium chelate compounds bond with the silicon polymer moiety with one molecule and one coordination, and can efficiently form Ti-O-Si bonds while leaving the chelate moiety, so they are preferable in terms of charge rise. The titanium chelate more preferably contains at least one titanium chelate selected from the group consisting of titanium lactate and titanium ammonium lactate. These titanium chelates may be used alone or in combination. In addition, inorganic fine particles with low volume resistivity, such as titania and alumina, may be used in combination with the titanium chelate.

[0029] From the viewpoint of charge rise, the content of the titanium chelate, that is, the amount of Ti element in the toner, is preferably 1.000 to 5.000 mmol, and more preferably 1.100 to 5.000 mmol, per 100 g of toner base particles.

[0030] In addition, the cross section of the toner observed by a transmission electron microscope is analyzed by an energy dispersive X-ray spectrometer (EDS) to obtain an EDS mapping image of the constituent elements of the cross section of the toner. In the EDS mapping image, when the ratio of the number of titanium atoms to the total number of silicon atoms and titanium atoms in the region outside the contour of the toner mother particle is MX (number of titanium atoms / number of silicon atoms and titanium atoms), it is preferable that MX satisfies the following formula (3). 0.50×10 -4 ≦MX≦1.50×10 -1 (3)

[0031] MX represents the detectable titanium chelate moiety in the silicon-titanium polymer composite, and when MX is within the above range, it is possible to promote polarization of the charge caused by the titanium chelate moiety. Therefore, it is easier to maintain a high charge amount throughout durability. In addition, MX is 1.00×10 -2 ~8.00×10 -2 More preferably, it is 1.50×10 -2 ~5.00×10 -2 It is even more preferable that: MX can be increased by increasing the amount of Ti raw material added or by slowing down the timing of addition of the Si monomer or the condensation rate, and can be decreased by speeding up the timing of addition of the Si monomer or the condensation rate.

[0032] In the infrared spectrum of silicon-titanium polymer composites, the 900 cm peak attributable to the Ti-O-Si stretching vibration was -1 ~1000cm -1 The maximum peak of the P_Ti peak is the 1000 cm peak that is assigned to the Si-O-Si stretching vibration. -1 ~1100cm -1 When the maximum value of the peak is defined as P_Si, it is preferable that P_Ti and P_Si satisfy the following formula (4). 0.06 ≦ P_Ti / P_Si ≦ 0.15 (4)

[0033] P_Ti / P_Si represents the ratio of chemically bonded Ti-O-Si, and by falling within the above range, the polarization effect of the charge caused by the titanium chelate moiety can be increased regardless of the printing speed, making it easier to suppress image fog. P_Ti / P_Si is more preferably 0.07 to 0.14. P_Ti / P_Si can be increased by adjusting the timing of adding Ti raw material and the pH at the beginning of the reaction to conditions that make it easy to make the reaction active. Also, P_Ti / P_Si can be decreased by adjusting the pH at the beginning of the reaction to conditions that make it difficult for the Ti raw material to react and increase the condensation rate of the Si monomer.

[0034] In the toner, it is preferable that the silicon-titanium polymer composite is fixed in a convex shape on the surface of the toner base particle. When the number average height of the convex portion measured by a scanning probe microscope is H, H is preferably 25 to 100 nm, more preferably 40 to 80 nm, and even more preferably 50 to 70 nm. When H is within the above range, it is possible to further suppress the change in the charge amount of the toner and the contamination of the charging member. As a result, it is possible to further suppress the image density fluctuation in a printer capable of mass printing, and to more easily maintain high image quality.

[0035] As a means for adhering the silicon-titanium polymer composite in a convex shape to the surface of the toner base particles, for example, the raw materials of the silicon-titanium polymer composite are added to the toner base particles in a dispersed state in an aqueous medium, and a condensation reaction is carried out at the interface of the toner base particles, thereby adhering the silicon-titanium polymer composite in a convex shape to the surface of the toner base particles. The number-average height H of the convex portions can be increased by increasing the amount of Si monomer added or by slowing down the condensation rate and controlling the time to ensure thorough condensation. The number-average height H of the convex portions can be decreased by using conditions that allow a fast condensation rate, for example, strong alkalinity such as pH 10.

[0036] In addition, the silicon polymer portion in the silicon-titanium polymer composite preferably has a structure (T3 unit structure) represented by the following formula (5), which can further improve the dielectric properties of the toner particles, making it easier to maintain the charge of the toner after a large amount of printing on poor quality paper. R-SiO 3 / 2 (5) In formula (5), R is an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2, and even more preferably 1) or a phenyl group. The silicon polymer portion is SiO 4 / 2 For example, the silicon polymer moiety may have a structure represented by formula (5) and SiO 4 / 2 The present invention has at least one structure selected from the group consisting of the structures represented by the following formula:

[0037] As the content of the silicon polymer portion, the amount of Si element in the toner is preferably 25.00 to 40.00 mmol, and more preferably 30.00 to 36.00 mmol, per 100 g of toner base particles.

[0038] The silicon-titanium polymer composite may be in the form of fine particles of the silicon-titanium polymer composite as an external additive. For example, the toner may have toner base particles having a binder resin and a colorant, and fine particles of the silicon-titanium polymer composite. The above-mentioned effects can be obtained even when the silicon-titanium polymer composite is used as an external additive. When the silicon-titanium polymer composite is used as an external additive, the number average particle size is preferably from 25 nm to 100 nm, more preferably from 40 nm to 60 nm. The number average particle diameter is measured by the following method.

[0039] The particle size distribution of the silicon-titanium polymer composite in the aqueous medium is calculated using a dynamic light scattering microtrack particle size distribution analyzer [UPA-150] (Nikkiso Co., Ltd.). The measurement is performed while controlling the temperature of the cell so that the temperature of the aqueous medium used for the measurement is the same as that of the measurement cell. The particle size measurement is performed at 25°C. (1) After pouring 3.0 g of RO water into the cell, perform a background check. Confirm that the sample loading is 0.0010 or less. (2) After pouring 3.0 g of RO water into the cell, perform Set Zero. The Set Zero condition is a time of 60 s. (3) Enter the following conditions. Measurement time: 30 s, Number of measurements: 2 Particle conditions: transparent, refractive index: 1.47, shape: non-spherical, density: 2.0 Solvent conditions: Select WATER Refractive index: 1.47 Viscosity at high temperature: 0.797 (30℃), Viscosity at low temperature: 1.002 (20℃) Display Settings: Select Standard Distribution display: Select volume (4) 3.0 g of the aqueous medium containing the silicon-titanium polymer composite is placed in the measurement cell, and the measurement is started. (5) The measurement data is analyzed using the dedicated software provided with the device, and the number-average particle size (D1) is calculated.

[0040] The binder resin contained in the toner mother particles is not particularly limited and may be any known one. For example, polystyrene; homopolymers of styrene substitutes such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-α-methyl chloromethacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, and styrene-acrylonitrile-indene copolymers; acrylic resins; methacrylic resins; polyvinyl acetate; silicone resins; polyester resins; polyamide resins; furan resins; epoxy resins; xylene resins, etc. may be used alone or in combination.

[0041] The binder resin preferably contains at least one selected from the group consisting of a styrene-based copolymer, which is a copolymer of styrene and another vinyl monomer, and a polyester resin, and more preferably contains a styrene-based copolymer. As the main component of the binder resin, a polyester resin and / or a styrene-based copolymer are preferred in terms of developability and fixability. The main component refers to a component whose content is 50% by mass or more. The binder resin more preferably contains a styrene-acrylic acid ester copolymer.

[0042] The monomer composition of the polyester resin is not particularly limited. Comonomers for the styrene monomer in styrene-based copolymers include monocarboxylic acids having a double bond or substituted products thereof, such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, and acrylamide; dicarboxylic acids having a double bond or substituted products thereof, such as maleic acid, butyl maleate, methyl maleate, and dimethyl maleate; vinyl esters, such as vinyl chloride, vinyl acetate, and vinyl benzoate; ethylene, propylene, and butylene. ethylene-based olefins such as vinyl methyl ketone and vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether. These vinyl monomers can be used alone or in combination of two or more.

[0043] The styrene copolymer is preferably crosslinked with a crosslinking agent in order to expand the fixing temperature range of the toner and improve the offset resistance. As the crosslinking agent, a compound having two or more polymerizable double bonds is used. Examples of the crosslinking agent include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.

[0044] The toner base particles may contain a colorant. Examples of the colorant include various conventionally known colorants such as dyes and pigments. Examples of magenta coloring pigments include CI Pigment Red 3, 5, 17, 22, 23, 38, 41, 112, 122, 123, 146, 149, 150, 178, 179, 190, and 202, and CI Pigment Violet 19 and 23. These pigments may be used alone, or a dye and a pigment may be used in combination. Examples of color pigments for cyan include CI Pigment Blue 15, 15:1, and 15:3, and copper phthalocyanine pigments having one to five phthalimidomethyl groups substituted on the phthalocyanine skeleton. Examples of color pigments for yellow include CI Pigment Yellow 1, 3, 12, 13, 14, 17, 55, 74, 83, 93, 94, 95, 97, 98, 109, 110, 154, 155, 166, 180, and 185. As the black colorant, carbon black, aniline black, acetylene black, titanium black, and those toned to black using the above-mentioned yellow / magenta / cyan colorants can be used.

[0045] The toner can also be used as a magnetic toner, in which case the following magnetic materials are used: iron oxides such as magnetite, maghemite, and ferrite, or iron oxides containing other metal oxides; metals such as Fe, Co, and Ni, or alloys of these metals with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Ca, Mn, Se, and Ti, and mixtures thereof. More specifically, iron oxide black (Fe3O4), iron sesquioxide (γ-Fe2O3), zinc iron oxide (ZnFe2O4), copper iron oxide (CuFe2O4), neodymium iron oxide (NdFe2O3), barium iron oxide (BaFe 12 O 19 ), magnesium iron oxide (MgFe2O4), and manganese iron oxide (MnFe2O4). The above-mentioned magnetic materials can be used alone or in combination of two or more. Particularly suitable magnetic materials are fine powders of iron tetraoxide or gamma-iron sesquioxide.

[0046] The average particle diameter of these magnetic materials is preferably 0.1 μm or more and 2 μm or less, and more preferably 0.1 μm or more and 0.3 μm or less. The magnetic properties at an applied current of 795.8 kA / m (10 kOersted) are a coercive force (Hc) of 1.6 kA / m or more and 12 kA / m or less (20 Oersted or more and 150 Oersted or less), a saturation magnetization (σs) of 5 Am 2 / kg or more 200Am 2 / kg or less, preferably 50Am 2 / kg or more 100Am 2 / kg or less. The residual magnetization (σr) is 2Am 2 / kg or more 20Am 2 / kg or less is preferred. The magnetic material is preferably used in an amount of from 10 to 200 parts by mass, more preferably from 20 to 150 parts by mass, per 100 parts by mass of the binder resin.

[0047] The toner base particles may contain a release agent. Examples of the release agent include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; block copolymers of aliphatic hydrocarbon waxes; waxes mainly composed of fatty acid esters such as carnauba wax, sazol wax, and montan acid ester wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax, partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

[0048] The molecular weight distribution of the release agent preferably has a main peak in a region of molecular weight of 400 or more and 2400 or less, more preferably in a region of 430 or more and 2000 or less. This makes it possible to impart desirable thermal properties to the toner. The amount of the release agent added is preferably 2.5 parts by mass or more and 40.0 parts by mass or less, more preferably 3.0 parts by mass or more and 15.0 parts by mass or less, relative to 100 parts by mass of the binder resin. These release agents may be used alone or in combination of two or more kinds, and it is preferable to use a combination of a hydrocarbon wax and an ester wax from the viewpoint of fixability.

[0049] In order to stably maintain the chargeability of the toner, it is preferable to use a charge control agent in the toner. The following substances are used to control the chargeability of the toner to be negatively charged. For example, organic metal compounds and chelate compounds are effective, as well as monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid-based metal compounds.Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarenes, and resin-based charge control agents.

[0050] The following substances are used to control the toner to have a positive charge. Nigrosine and nigrosine modified with fatty acid metal salts, etc.; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts analogous thereto, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (lake agents include phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; diorgano tin oxides such as dibutyltin oxide, dioctyltin oxide, and dicyclohexyltin oxide; diorgano tin borates such as dibutyltin borate, dioctyltin borate, and dicyclohexyltin borate; resin-based charge control agents, etc. These can be used alone or in combination of two or more.

[0051] The toner can be used as a one-component developer or a two-component developer in any development system. For example, in the case of a magnetic toner containing a magnetic material as a one-component developer, a magnet built into a developing sleeve is used to transport and charge the magnetic toner. In the case of a non-magnetic toner containing no magnetic material, a blade or a fur brush is used to frictionally charge the toner and cause it to adhere to the developing roller.

[0052] When used as a two-component developer, the magnetic carrier to be mixed with the toner may be selected from elements such as iron, copper, zinc, nickel, cobalt, manganese, and chromium. Or it is composed of a composite ferrite state. The shape of the magnetic carrier used in this case may be spherical, flat, amorphous, etc., and further, the magnetic carrier may be used with the fine structure of the surface state (for example, surface unevenness) appropriately controlled. In addition, a resin-coated carrier whose surface is coated with a resin may also be suitably used. The average particle size of the carrier used is preferably 10 to 100 μm, more preferably 20 to 50 μm. In addition, when these carriers and toner are mixed to prepare a two-component developer, the toner concentration in the developer is preferably about 2 to 15% by mass.

[0053] The method for producing the toner is not particularly limited, and a known method can be adopted. It is preferable to produce the toner base particles in an aqueous medium and form a silicon-titanium polymer composite on the surface of the toner base particles. The method for producing the toner base particles is not particularly limited, and suspension polymerization, dissolution suspension, emulsion aggregation, pulverization, etc. can be used. Among them, suspension polymerization is preferable.

[0054] First, a polymerizable monomer capable of producing a binder resin and various additives as necessary are mixed, and the materials are dissolved or dispersed using a disperser to prepare a polymerizable monomer composition. The polymerizable monomer may be any of those described above in the description of the styrene-based copolymer. Examples of the various additives include colorants, release agents, plasticizers, charge control agents, polymerization initiators, and chain transfer agents. Examples of the dispersing machine include a homogenizer, a ball mill, a colloid mill, and an ultrasonic dispersing machine.

[0055] Next, the polymerizable monomer composition is added to an aqueous medium containing poorly water-soluble inorganic fine particles, and droplets of the polymerizable monomer composition are prepared using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser (granulation process). Thereafter, the polymerizable monomer in the droplets of the polymerizable monomer composition is polymerized to obtain toner base particles (polymerization step).

[0056] Next, a method for producing a silicon-titanium polymer composite will be described using a silane coupling agent as an organosilicon compound. As mentioned above, titanium chelate itself has excellent dielectric and conductive properties, and is a material with mild reactivity that is easy to control by pH and temperature. In addition, the reaction characteristics of titanium chelate and silane coupling agents are different, so it is possible to control the location of titanium by utilizing these characteristics.

[0057] First, in order to disperse the titanium chelate inside the composite, the two are mixed at a pH that makes the titanium chelate easily reactive and suppresses the reaction of the silane coupling agent. At that time, it is preferable to have a coordinating polyvalent acid such as phosphoric acid in the system so that the titanium chelate maintains its chelate state and easily reacts. Then, gradually increase the temperature or pH to make the silane coupling agent more reactive than the titanium chelate, and by doing so, it is possible to prepare silicon-titanium polymer composites with controlled titanium state, i.e., Ti-E and Ti-E / Si-E.

[0058] In preparing the silicon-titanium polymer composite, the pH should be adjusted from the following viewpoints. In order to minimize the amount of titanium on the surface, a pH of 2.0 to 8.0, at which the reactivity of the silane coupling agent is low and the reactivity of the titanium chelate is high, is preferred, and a pH of 3.0 to 6.0 is more preferred. Conversely, if it is desired to slightly increase the amount of titanium on the surface, a pH of 8.5 to 10.5, at which the silane coupling agent is easily reactive, is preferred.

[0059] If you want to include other materials, add titanium chelate to the dispersion liquid in which the other materials are dispersed. By appropriately adjusting the pH and temperature of the dispersion during the dropping, and further the pH and temperature after the dropping, it is possible to produce a silicon-titanium polymer composite in which the state of titanium is controlled.

[0060] When obtaining toner particles having toner base particles and a silicon-titanium polymer composite present on the surface of the toner base particles, the following manufacturing method is preferred. By using the following manufacturing method, it is possible to precipitate the silicon-titanium polymer composite on the surface of the toner base particles. Therefore, for example, it is possible to obtain an embodiment in which the silicon-titanium polymer composite is fixed to the surface of the toner base particles. First, a toner base particle dispersion liquid is obtained in which the toner base particles are dispersed in an aqueous medium. For example, the dispersion liquid after the polymerization step described above in the suspension polymerization method may be used.

[0061] (Preparation of silicon compound liquid) On the other hand, it is preferable to hydrolyze a silane coupling agent as a silicon compound in advance. The silane coupling agent and water are mixed and hydrolyzed at a pH suitable for hydrolysis to obtain a silicon compound liquid. The pH when hydrolyzing may be appropriately changed depending on the type of silicon compound. For example, the pH of the aqueous medium is preferably 2.0 to 6.0, more preferably 4.0 to 6.0. As conditions for hydrolysis, the temperature is preferably 15 to 80°C and the time is preferably 30 to 600 minutes.

[0062] (First step) The toner base particle dispersion liquid and the silicon compound liquid are mixed to obtain a mixed liquid. The amount of silicon compound added is preferably within the range of the amount of Si element (mmol) per 100 g of the toner base particles described above. As the condition at this time, it is preferable to set the pH suitable for hydrolysis, as in the preparation of the silicon compound liquid. For example, the pH of the mixed liquid is preferably 2.0 to 6.0, more preferably 4.0 to 6.0. The temperature is preferably, for example, 20 to 60°C. In the first step, the toner base particle dispersion liquid and the silicon compound liquid may be mixed and the mixed liquid may be held. The holding time is preferably 1 to 300 minutes, more preferably 1 to 120 minutes.

[0063] Regarding the pH in the first step, for example, when the titanium chelate is titanium lactate, the pH of the mixture is preferably 3.0 or more and less than 5.5, more preferably 3.5 to 5.2. When titanium lactate is added in the subsequent second step, if the pH of the mixture is 5.5 or more, the reaction activity of titanium lactate is not sufficiently increased, the condensation of the silane coupling agent takes precedence, and Ti is difficult to be incorporated into the silicon-titanium polymer composite. Therefore, even if titanium lactate reacts in the subsequent step, it is considered that Ti is likely to exist only on the surface of the silicon-titanium polymer composite. In Patent Document 3, the pH when titanium lactate is added is 5.5 or more, so titanium lactate is difficult to react, and in the final acid treatment, titanium lactate reacts with phosphate ions, and Ti precipitates in large amounts on the toner surface. Therefore, it is considered that Ti-E and Ti-E / Si-E exceed the upper limits of formulas (1) and (2).

[0064] (Second process) The mixture obtained in the first step is mixed with titanium chelate to form a silicon-titanium polymer composite on the surface of the toner base particles. The amount of titanium chelate added is preferably within the range of the amount of Ti element (mmol) per 100 g of the toner base particles described above. At this time, it is preferable to adjust the pH. From the viewpoint of minimizing the amount of titanium on the surface and reducing Ti-E and Ti-E / Si-E, a pH of about 2.0 to 8.0 at which the reactivity of the silane coupling agent is low and the reactivity of the titanium chelate is high can be mentioned. Conversely, when the amount of titanium on the surface is slightly increased and Ti-E and Ti-E / Si-E are increased, it is preferable to set the pH at 8.5 to 10.5, which is a condition under which the silane coupling agent is easily reactive. From the viewpoint of controlling Ti-E and Ti-E / Si-E, the pH in the second step is preferably 7.9 to 10.2.

[0065] In the second step, the pH adjustment time when adjusting the pH of the mixture in the first step to the above pH range is preferably 1 to 90 minutes, more preferably 1 to 40 minutes. By changing the pH during the above adjustment time, the reactivity of the silane coupling agent is increased, and the formation of the particle shape is promoted.

[0066] In the above description, the silicon compound liquid is added in the first step, and the titanium chelate is mixed in the second step, but this order may be reversed. That is, a mixed liquid may be obtained by mixing the toner base particle dispersion liquid and the titanium chelate in the first step, and the mixed liquid may be mixed with the silicon compound liquid in the second step. By adopting such a process, it is possible to adjust the Ti-O-Si bond.

[0067] (Third step) If necessary, the second step may be followed by a third step in which the mixture is maintained at a pH of preferably 8.5 to 10.5, at a temperature of preferably 40 to 60° C., and for preferably 1 to 5 hours. The time for pH adjustment when adjusting the pH of the mixture in the second step to the pH range of the third step is preferably 1 to 90 minutes, more preferably 1 to 40 minutes. By employing such a step, it is possible to adjust the distance between the silicon-titanium polymer composites on the surface of the toner base particles.

[0068] (Washing process / classification process) After the second step (or the third step, if necessary), washing and classification may be performed as necessary to obtain toner particles. The pH during washing is, for example, 1.0 to 3.0. The obtained toner particles may be used as they are as a toner. External additives may be added to the obtained toner particles to make a toner.

[0069] The number average particle diameter (D1) of the toner is preferably from 4.0 to 12.0 μm, more preferably from 5.0 to 8.0 μm, and the weight average particle diameter (D4) of the toner is preferably from 4.0 to 12.0 μm, more preferably from 6.0 to 9.0 μm.

[0070] In the above-mentioned first to third steps, Ti-E and Ti-E / Si-E can also be controlled by means other than pH adjustment. For example, Ti-E can be increased by increasing the amount of Ti chelate added, adjusting the pH between the time of adding Ti chelate and the time of adding silane coupling agent to a pH where the silane coupling agent is easily reactive, or by lengthening the time of the acid washing process. Also, Ti-E / Si-E can be increased by increasing the amount of Ti chelate added or lengthening the time of the acid washing process. For example, Ti-E can be reduced by reducing the amount of Ti chelate added or by accelerating the timing of adding the Ti chelate, and Ti-E / Si-E can be reduced by carrying out a long reaction under pH conditions where the Ti chelate reacts easily and the silane coupling agent does not react easily.

[0071] When producing fine particles of a silicon-titanium polymer composite, the following method is preferred. By the following method, a silicon-titanium polymer composite can be obtained as fine particles. By reacting a titanium chelate and a silicon compound liquid in the absence of toner base particles, an oligomer is formed, which becomes hydrophobic and precipitates in an aqueous medium, and a condensation reaction proceeds to obtain fine particles. When the toner base particles are present in an aqueous medium, the titanium chelate and the silicon compound liquid tend to gather around the resin of the toner base particles, and therefore the silicon-titanium polymer is formed on the surface of the toner base particles. In this case, it is believed that as the condensation proceeds, the hydrophobic condensates tend to gather together and form a convex shape.

[0072] (Preparation of silicon compound liquid) The silicon compound liquid may be prepared in the same manner as in the production of the toner particles described above.

[0073] (First step) While stirring the aqueous medium, the titanium chelate and silicon compound liquid are added to react the titanium chelate and silicon compound. The pH when the titanium chelate and silicon compound liquid are added is preferably 2.0 to 6.0, more preferably 2.5 to 5.0. The reaction time is, for example, 30 to 300 minutes. It is preferable to adjust the pH. That is, from the viewpoint of minimizing the amount of titanium on the surface and decreasing Ti-E and Ti-E / Si-E, the pH should be about 2.0 to 8.0, which is a pH at which the reactivity of the silane coupling agent is low and the reactivity of the titanium chelate is high. Conversely, when the amount of titanium on the surface is increased slightly and Ti-E and Ti-E / Si-E are increased, the pH should be set to 8.5 to 10.5, which is a condition under which the silane coupling agent is easily reactive. The time for adjusting the pH is preferably 1 to 90 minutes, more preferably 1 to 40 minutes. From the viewpoint of controlling Ti-E and Ti-E / Si-E, the pH after the pH adjustment in the first step is preferably 7.9 to 10.2. The amount of titanium chelate added relative to 100 parts by mass of the silicon compound is preferably 5 to 20 parts by mass, and more preferably 11 to 17 parts by mass.

[0074] (Second process) Thereafter, from the viewpoint of facilitating control of Ti-E and Ti-E / Si-E, a second step may be carried out. In the second step, a titanium chelate and a silicon compound solution are further added, and the solution is maintained at a pH of preferably 8.5 to 10.5, at a temperature of preferably 40 to 60° C., and for preferably 1 to 5 hours. In the second step, the amount of titanium chelate added relative to 100 parts by mass of the silicon compound is preferably 0.1 to 2.0 parts by mass, and more preferably 0.1 to 0.5 parts by mass.

[0075] The silicon polymer moiety in the silicon-titanium polymer composite is preferably a condensation polymer of an organosilicon compound, and more preferably a condensation polymer of an organosilicon compound having a structure represented by the following formula (Y): In other words, the silicon-titanium polymer composite is preferably a reaction product of a titanium chelate and an organosilicon compound having a structure represented by formula (Y). TIFF2025043947000001.tif37153

[0076] In formula (Y), Ra, Rb, Rc and Rd are each independently a halogen atom, a hydroxyl group, an acetoxy group, or an alkoxy group (hereinafter, these are also referred to as reactive groups), or Ra represents an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2, and even more preferably 1) or a phenyl group (similar to R in formula (5)), and Rb, Rc, and Rd each independently represent a halogen atom, a hydroxyl group, an acetoxy group, or an alkoxy group. Ra is preferably an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and more preferably a methyl group.

[0077] The reactive group undergoes hydrolysis, addition polymerization, and condensation polymerization to form a crosslinked structure. From the viewpoint of mild hydrolysis at room temperature and deposition onto the surface of the toner base particle, the reactive group is preferably an alkoxy group having 1 to 3 carbon atoms, and more preferably a methoxy group or an ethoxy group. When Ra, Rb, Rc and Rd are reactive groups, the compound of formula (Y) is preferably tetraethoxysilane. When Ra is an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2, and even more preferably 1) or a phenyl group, and Ra, Rb, Rc, and Rd are reactive groups, i.e., trifunctional, the compound of formula (Y) is preferably the following, more preferably methyltrimethoxysilane.

[0078] Examples of the trifunctional compound represented by the above formula (Y) include the following. Trifunctional methylsilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, and methyldiethoxyhydroxysilane. Trifunctional silanes such as ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, and hexyltrihydroxysilane. Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

[0079] Hereinafter, methods for measuring various physical properties according to the present disclosure will be described. <Measurement of Ti-E and Si-E on the toner surface> The ratio of the number of silicon atoms and the ratio of the number of titanium atoms to the total number of carbon atoms, oxygen atoms, silicon atoms, phosphorus atoms, and titanium atoms on the toner surface are calculated as follows: Elemental analysis of the toner surface is performed using the following device under the following conditions. Measurement device: Quantum2000 (product name, manufactured by ULVAC-PHI, Inc.) X-ray source: Monochrome Al Kα ·Xray Setting:100μmφ(25W(15KV)) Photoelectron take-off angle: 45 degrees Neutralization Condition: Use Neutralization Gun and Ion Gun together ·Analysis area: 300×200μm Pass Energy: 58.70eV Step size: 1.25eV Analysis software: Maltipak (PHI) Here, the atomic numbers (atomic %) of silicon atoms and titanium metal atoms are calculated using the peaks of C 1c (BE280-295 eV), O 1s (BE525-540 eV), Si 2p (BE95-113 eV), P 2p (BE129-138 eV), and Ti 2p (BE456-470 eV). The sum of the atomic numbers of carbon atoms, oxygen atoms, silicon atoms, phosphorus atoms, and titanium atoms is calculated. The ratio of the number of silicon atoms to the sum of these atomic numbers is Si-E, and the ratio of the number of titanium atoms is Ti-E. That is, Si-E=(the number of silicon atoms) / (the sum of the numbers of carbon atoms, oxygen atoms, silicon atoms, phosphorus atoms, and titanium atoms). In addition, Ti-E=(the number of titanium atoms) / (the sum of the numbers of carbon atoms, oxygen atoms, silicon atoms, phosphorus atoms, and titanium atoms). From the obtained Ti-E and Si-E, Ti-E / Si-E is calculated.

[0080] <Measurement of MX on toner cross section> First, the toner is spread on a cover glass (Matsunami Glass Co., Ltd., square cover glass No. 1) so that it becomes a single layer, and then an Os film (5 nm) and a naphthalene film (20 nm) are applied to the toner as a protective film using an osmium plasma coater (Filgen Co., Ltd., OPC80T). Next, a PTFE tube (inner diameter 1.5 mm × outer diameter 3 mm × 3 mm) is filled with photocurable resin D800 (JEOL Co., Ltd.), and the cover glass is gently placed on top of the tube so that the toner is in contact with the photocurable resin D800. In this state, the resin is irradiated with light to harden it, and then the cover glass and tube are removed to form a cylindrical resin with toner embedded in its outermost surface. Using an ultrasonic ultramicrotome (Leica, UC7), a cutting speed of 0.6 mm / s is used to cut the length of the toner radius (4.0 μm when the weight average particle size (D4) is 8.0 μm) from the outermost surface of the cylindrical resin to expose the cross section of the toner. Next, cutting is performed to a film thickness of 100 nm, and a thin sample of the toner cross section is produced. By cutting in this manner, a cross section of the center of the toner can be obtained. This thin sample was observed in STEM mode of a scanning transmission electron microscope (JEOL, JEM2800) connected to an EDS analyzer (energy dispersive X-ray analyzer) at a magnification of 400,000 times, in a field of view where the outermost surface of the toner could be confirmed.

[0081] The constituent elements of the cross-section of the observed toner were collected by an EDS analyzer to obtain a spectrum, and an EDS mapping image was prepared. Spectral collection and analysis were performed using an NSS (Thermo Fischer Scientific). The collection conditions were an acceleration voltage of 200 kV, a probe size of 1.0 nm or 1.5 nm appropriately selected so that the dead time was 15 to 30, a mapping resolution of 256 x 256, and a frame number of 500. EDS mapping images were obtained for 30 cross-sections of the toner. By analyzing the EDS mapping image obtained in this manner, the ratio of the number of titanium atoms to the total number of silicon atoms and titanium atoms in the silicon-titanium polymer composite can be calculated.

[0082] First, press the "Extract from line" button in NSS and select the analysis range freehand. Specifically, trace the interface between the toner base particle and the silicon polymer composite present on the surface of the toner base particle to draw a baseline, and then draw a parallel line 200 nm away from the baseline toward the outer edge of the toner. The range between the baseline and the parallel line is selected as the analysis range, and this range will be the area outside the outline of the toner base particle. Once the toner analysis range is selected, pressing the "Spectrum Quantitation" button will automatically calculate the ratio (atomic %) of silicon atoms and titanium atoms in the selected range. At this time, select silicon and titanium as the elements to be analyzed. The silicon atoms displayed in the quantitative results Based on the values ​​of the ratio (atomic %) of silicon atoms and the ratio (atomic %) of titanium atoms, the ratio MX of the number of titanium atoms to the total number of silicon atoms and titanium atoms in the silicon-titanium polymer composite can be calculated. That is, MX=(number of titanium atoms) / (sum of numbers of silicon atoms and titanium atoms). The arithmetic average value of 30 cross sections of the toner is used.

[0083] <Infrared spectroscopic analysis of silicon-titanium polymer composite> When measuring the silicon-titanium polymer composite, a sample is prepared by carrying out the following process in advance to isolate the silicon-titanium polymer composite. The following description is given for the case where the sample is a toner, but other samples may also be isolated in the same manner.

[0084] (When silicon-titanium polymer composite particles are added as an external additive) When silicon-titanium polymer composite particles are added as an external additive: Toner particles and silicon-titanium polymer composite particles (external additive) are recovered from the toner by the following method. Add 160 g of sucrose (Kishida Chemical) to 100 mL of ion-exchanged water and dissolve in a hot water bath to prepare a concentrated sucrose solution. Place 31 g of the concentrated sucrose solution and 6 mL of Contaminon N in a centrifuge tube to prepare a dispersion. Add 1 g of toner to this dispersion and break up any clumps of toner with a spatula or similar.

[0085] The centrifuge tube is shaken for 20 minutes at 350 reciprocations per minute in a KM Shaker (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd. After shaking, the solution is transferred to a glass tube for a swing rotor (50 mL) and centrifuged at 3500 rpm for 30 minutes in a centrifuge. After centrifugation, the toner particles are present in the top layer in the glass tube, and silicon-titanium polymer composite particles (external additive) are present in the aqueous solution in the lower layer, so these are separated. If necessary, shaking and centrifugation can be repeated to ensure sufficient separation. By repeating these operations, the required amount of toner particles or external additives can be collected.

[0086] (When the toner particles have a toner base particle and a silicon-titanium polymer composite present on the surface of the toner base particle) When the toner particles have a toner base particle and a silicon-titanium polymer composite present on the surface of the toner base particle, the silicon-titanium polymer composite is recovered by the following procedure. When an external additive to be removed is present, the toner particles from which the external additive has been removed may be obtained by the above-mentioned procedure. The method for recovering silicon-titanium polymer composite from toner particles is explained below. 10.0 g of toner particles are weighed out and mixed with 100 mL of N,N-dimethylformamide (DMF) for 60 minutes by stirring. If necessary, the mixture may be heated up to 80°C during stirring. After 60 minutes of stirring, the mixture is returned to room temperature and transferred to a glass tube (50 mL) for a swing rotor, and centrifuged at 3500 rpm for 30 minutes in a centrifuge. After centrifugation, DMF insoluble matter containing silicon-titanium polymer composite is present in the lower layer of the glass tube. This insoluble matter is recovered. This operation is repeated three times. The recovered insoluble matter is then dispersed in 100 mL of RO water, and centrifuged again in a centrifuge at 3500 rpm for 30 minutes. The insoluble matter in the lower layer of the glass tube is recovered and dried to obtain the silicon-titanium polymer composite.

[0087] (Infrared spectroscopy) The silicon-titanium polymer composite particles or silicon-titanium polymer composite obtained by the above procedure are used as a sample to carry out analysis according to the following procedure. FT-IR analysis was performed using a Fourier transform infrared spectrometer equipped with a Universal ATR Sampling Accessory. (Frontier: PerkinElmer, software: Spectrum10) was used and measurements were made using the ATR method. The specific measurement procedures are as follows. The specific measurement procedures and method for calculating P_Ti / P_Si are as follows. The angle of incidence of infrared light (λ=5μm) is set to 45°. A Ge ATR crystal (refractive index: 4.0) is used as the ATR crystal. Other conditions are as follows. The measurement range when Ge is used as the ATR crystal is approximately 200nm from the sample surface. Range Start: 4000cm -1 End: 650cm -1 (ATR crystal of Ge) Duration Scan number: 16 Resolution:4.00cm -1 Advanced: With CO2 / H2O correction

[0088] [Calculation method of P_Ti / P_Si] (1) A Ge ATR crystal is attached to the apparatus. (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) Accurately weigh out 0.01 g of the sample onto the ATR crystal. (5) Pressurize the sample with the pressure arm (Force Gauge is 45). (6) Measure the sample. (7) The obtained FT-IR spectrum is baseline corrected using Automatic Correction.

[0089] (8) 926 cm -1 Confirm that there is a peak in the vicinity. This absorption peak is due to the stretching vibration of the Ti-O-Si bond, and calculate this peak value (this is designated as T1). (9) 900 cm -1 and 1000cm -1 Calculate the average absorption intensity (this is called T2) (10)T1-T2=P_Ti, where P_Ti is defined as the maximum absorption peak intensity corresponding to the stretching vibration of Ti-O-Si.

[0090] (11) 1000cm -1 ~1100cm -1 The maximum value of the absorption peak intensity in the range is calculated (this is designated as S1). (12) 1,000 cm -1 and 1100cm -1 Calculate the average absorption intensity (this is called S2) (13) S1-S2 = P_Si. P_Si is the 1000 cm corresponding to the Si-O-Si stretching vibration. -1 and 1100cm-1 It is defined as the maximum absorption peak intensity in the following range. (14) Using the P_Ti and P_Si calculated above, calculate P_Ti / P_Si by dividing P_Ti by P_Si.

[0091] <Method for measuring the average height H of protrusions on the surface of a toner particle> The protrusions on the surfaces of the toner particles are observed by the following method. The force curves are measured and derived for the convex portions on the surface of the toner particles and the surface layer of the toner core particles using a scanning probe microscope (SPM) "AFM5500M" manufactured by Hitachi High-Technologies Corporation. The cantilever (hereinafter also referred to as a probe) used in the measurement is "SI-DF3P2" sold by Hitachi High-Tech Fielding Corporation.

[0092] The SPM used for the measurement is calibrated in advance for position accuracy in the XYZ directions. The radius of curvature of the tip of the probe is measured in advance. Any method may be used to measure the radius of curvature of the tip of the probe, but it can be measured, for example, using a probe evaluation sample "TGT1-NT-MDT" sold by Hitachi High-Tech Fielding. The value of the tip radius of curvature may be any value that allows the surface layer of a toner particle to be measured without contacting the protrusions, but it is preferable that the value is 20 nm or less in order to ensure resolution. In this disclosure, it is 10 nm.

[0093] The cantilever used for the measurements is an SI-DF3P2, and the measurements are performed in dynamic force mode. To measure toner particles, first, conductive double-sided tape is attached to the sample stage, and toner particles are sprayed onto it. Excess toner particles are then removed from the sample stage by air blowing. The shape of this sample is measured with an AFM5500M within an area of ​​1 μm x 1 μm on the toner particle surface, and the protrusions on the toner particle surface are observed. Toner particles with a particle size equal to the weight average particle size (D4) are selected as the measurement subject.

[0094] After the measurement, the slope of the obtained 1 μm×1 μm measurement data is corrected, and then the maximum surface height Sp is calculated. Sp means the maximum height from the outermost surface of a toner particle to the apex of a protrusion in 1 μm×1 μm. The maximum heights h1 to h50 of the apex of the protrusions of 50 toner particles are obtained using the above method, and the arithmetic mean value of h1 to h50 is taken as the average height H (nm) of the protrusions.

[0095] <Measurement of toner particle size> The particle size of the toner particles can be measured by the pore electrical resistance method. For example, it can be measured and calculated using the "Coulter Counter Multisizer 3" and the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). A precision particle size distribution measuring device using the pore electrical resistance method (product name: Coulter Counter Multisizer 3) and dedicated software (product name: Beckman Coulter Multisizer 3 Version 3.51, manufactured by Beckman Coulter, Inc.) are used. The aperture diameter is 100 μm, and measurements are made with an effective number of measurement channels of 25,000. The measurement data is then analyzed and calculated. The aqueous electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately 1 mass %, for example ISOTON II (trade name) manufactured by Beckman Coulter. Before carrying out the measurements and analyses, the dedicated software is set up as follows.

[0096] In the "Change Standard Measurement Method (SOM) screen" of the dedicated software, set the total count number in the control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using (standard particle 10.0 μm, Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. In addition, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II (trade name), and check the aperture tube flush after measurement. In the "Pulse to particle size conversion setting screen" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm.

[0097] The specific measurement method is as follows. (1) Pour about 200 mL of the electrolyte solution into a 250 mL round-bottom glass beaker made exclusively for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, remove dirt and air bubbles from inside the aperture tube using the "Aperture Tube Flush" function of the dedicated software. (2) About 30 mL of the above electrolyte solution is placed in a 100 mL flat-bottom glass beaker. Contaminon N (trade name) (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, manufactured by Wako Pure Chemical Industries, Ltd.) is added to the beaker. Add 0.3 mL of a diluted solution prepared by diluting 100% ethanol (manufactured by Epson Corporation) with ion-exchanged water three times by mass. (3) An ultrasonic disperser with two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees, and an electrical output of 120 W (product name: Ultrasonic Dispersion System Tetora150, manufactured by Nikkaki Bios Co., Ltd.) Add a specified amount of ion-exchanged water and 2 mL of Contaminon N (trade name) to the water tank. (4) The beaker (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolyte solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, 10 mg of toner (particles) is added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10°C or higher and 40°C or lower. (6) Using a pipette, add the electrolytic solution (5) in which the toner (particles) is dispersed to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight average particle size (D4) is calculated. 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). When the dedicated software is set to Graph / Number %, the "Average diameter" on the "Analysis / Number Statistics (Arithmetic Mean)" screen is the number average particle size (D1).

[0098] The measurement sample was prepared by placing approximately 4 g of toner in a special aluminum ring for pressing, flattening it, and then pressing it at 20 MPa for 60 seconds using a tablet molding compression machine "BRE-32" (manufactured by Maekawa Test Machinery Manufacturing Co., Ltd.) to form a pellet with a thickness of approximately 2 mm and a diameter of approximately 39 mm. Measurements are performed under the above conditions, and elements are identified based on the peak positions of the obtained X-rays, and their concentrations are calculated from the counting rate (unit: cps), which is the number of X-ray photons per unit time.

[0099] <Method for determining the amount of Ti element and Si element in toner> The following is an example for silicon. For titanium, the value can be calculated by changing SiO2 to TiO2. For 100 parts by mass of particles that have the same composition as the toner particles but do not contain silicon or titanium elements and have the same particle size, 0.05 parts by mass of silica (SiO2) fine powder of 10 nm or less is added and thoroughly mixed using a coffee mill. Similarly, 0.25 parts by mass and 0.50 parts by mass of 10 nm silica fine powder are mixed with the toner particles, respectively, and these are used as samples for the calibration curve.

[0100] For each sample, a pellet of the calibration curve sample is prepared as described above using a tablet press, and the count rate (unit: cps) of the Si-Kα ray observed at a diffraction angle (2θ) = 109.08° when PET is used as the analyzing crystal is measured. In this case, the acceleration voltage and current value of the X-ray generator are 24 kV and 100 mA, respectively. A linear function calibration curve is obtained by plotting the obtained X-ray count rate on the vertical axis and the amount of SiO2 added in each calibration curve sample on the horizontal axis. Next, the toner particles to be analyzed are pelletized as described above using a tablet molding machine, and the count rate of the Si-Kα radiation is measured. Then, the amount of Si in mmol per 100 g of toner base particles converted into SiO2 in the toner is calculated from the above calibration curve. EXAMPLES

[0101] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the following examples. Note that parts and % in the formulations of the examples and comparative examples are all by mass unless otherwise specified.

[0102] (Toner Production Example 1) <Preparation Example of Toner Base Particle Dispersion 1> 11.2 parts of sodium phosphate (12-hydrate) was added to a reaction vessel containing 350.0 parts of ion-exchanged water, and the mixture was kept at 65°C for 1.0 hours while purging with nitrogen. The mixture was stirred at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). While maintaining the stirring, an aqueous calcium chloride solution in which 7.4 parts of calcium chloride (2-hydrate) was dissolved in 10.0 parts of ion-exchanged water was added to the reaction vessel all at once to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 1.0 mol / L of hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 5.0, and aqueous medium 1 was prepared.

[0103] (Preparation of Polymerizable Monomer Composition) Styrene 60.0 parts ·CIPigment Blue15:3 6.3 parts The above materials were placed in an attritor (manufactured by Nippon Coke & Engineering Co., Ltd.), and further dispersed using zirconia particles having a diameter of 1.7 mm at 220 rpm for 5.0 hours to prepare a colorant dispersion in which the pigment was dispersed.

[0104] The following materials were then added to the colorant dispersion: Styrene 12.0 parts ・28.0 parts n-butyl acrylate Polyester resin 5.0 parts (Polymerization product of terephthalic acid and 2 moles of propylene oxide adduct of bisphenol A, weight average molecular weight Mw=10000, acid value: 8.2mgKOH / g) HNP51 (melting point: 76°C, manufactured by Nippon Seiro Co., Ltd.) 6.0 parts The above materials were kept at 65° C. and uniformly dissolved and dispersed at 500 rpm using a TK homomixer to prepare a polymerizable monomer composition.

[0105] (granulation process) While maintaining the temperature of the aqueous medium 1 at 70° C. and the rotation speed of the stirring device at 12,000 rpm, the polymerizable monomer composition was charged into the aqueous medium 1, and 8.0 parts of t-butyl peroxypivalate as a polymerization initiator was added. Granulation was continued for 5 minutes while maintaining the stirring speed at 12,000 rpm.

[0106] (Polymerization process) The high-speed stirrer was changed to a stirrer equipped with a propeller stirring blade, and polymerization was carried out for 5.0 hours while maintaining 70°C with stirring at 200 rpm, and then the temperature was raised to 85°C and heated for 2.0 hours to carry out a polymerization reaction. The temperature was then raised to 98°C and heated for 3.0 hours to remove residual monomers, and a 1 mol / L aqueous solution of HCl or NaOH and ion-exchanged water were added to adjust the toner base particle concentration in the dispersion to 30.0 mass% and the pH to 5.0, obtaining toner base particle dispersion 1 in which toner base particles 1 are dispersed. The toner base particles 1 had a number average particle size (D1) of 6.2 μm and a weight average particle size (D4) of 6.9 μm.

[0107] <Preparation Example of Toner Base Particle Dispersion Liquid 2> Toner base particle dispersion 2 was obtained in the same manner as toner base particle dispersion 1, in which toner base particles 2 were dispersed, with the toner base particle concentration adjusted to 30.0 mass % and the pH adjusted to 4.0. The toner base particles 2 had a number average particle size (D1) of 6.2 μm and a weight average particle size (D4) of 6.9 μm.

[0108] <Preparation Example of Toner Base Particle Dispersion Liquid 3> Toner base particle dispersion 2 was prepared in the same manner as toner base particle dispersion 1, in which toner base particles 3 were dispersed, with the toner base particle concentration adjusted to 30.0% by mass and the pH adjusted to 3.5. The toner base particles 3 had a number average particle size (D1) of 6.2 μm and a weight average particle size (D4) of 6.9 μm.

[0109] <Example of preparation of silicon compound liquid 1> 50.0 parts ion-exchanged water Methyltrimethoxysilane 50.0 parts The above materials were weighed into a 200 mL beaker, and the pH was adjusted to 5.0 with 10% hydrochloric acid. After that, the mixture was stirred for 2.0 hours while being heated to 30° C. in a water bath, to prepare silicon compound liquid 1.

[0110] <Production example of silicon compound liquid 2> Silicon compound liquid 2 was prepared in the same manner as silicon compound liquid 1, except that methyltrimethoxysilane (MTMS) in silicon compound liquid 1 was changed to tetraethoxysilane (TEOS).

[0111] <Toner 1 Manufacturing Example> (First step) Toner base particle dispersion liquid 1 300.00 parts Silicon compound liquid 1 9.68 parts The above samples were weighed into a reaction vessel and mixed using a propeller impeller. Next, the pH of the resulting mixture was adjusted to 5.0 using 1 mol / L HCl or NaOH aqueous solution, and the temperature of the mixture was increased to 50°C, after which it was held for 30 minutes while being mixed using a propeller impeller.

[0112] (Second process) Titanium lactate 44% aqueous solution (TC-315: Matsumoto Fine Chemical Co., Ltd.) 1.05 copies Next, the above sample was weighed and mixed in a reaction vessel, and then the pH of the resulting mixture was adjusted to 9.0 using a 1 mol / L NaOH aqueous solution over 30 minutes, and maintained for 5.0 hours.

[0113] (Washing ~ classification process) Next, the temperature was lowered to 25°C, the pH was adjusted to 1.5 with 1 mol / L hydrochloric acid, and the mixture was stirred for 15 minutes, and then the mixture was washed with ion-exchanged water while being filtered to obtain toner particles 1 having protrusions of a silicon-titanium composite. The production conditions of toner particles 1 are shown in Tables 1-1 and 1-2. The obtained toner particles 1 were used as they were as toner 1. The physical properties of the obtained toner 1 are shown in Table 2.

[0114] <Toner 2 Manufacturing Example> (First step) Toner base particle dispersion liquid 1 300.00 parts Silicon compound liquid 1 7.09 parts The above samples were weighed into a reaction vessel and mixed using a propeller impeller. Next, the pH of the resulting mixture was adjusted to 5.0 using 1 mol / L HCl or NaOH aqueous solution, and the temperature of the mixture was increased to 50°C, after which it was held for 30 minutes while being mixed using a propeller impeller.

[0115] (Second process) Titanium lactate 44% aqueous solution (TC-315: Matsumoto Fine Chemical Co., Ltd.) 0.58 parts Next, the above sample was weighed and mixed in a reaction vessel, and then the pH of the resulting mixture was adjusted to 8.0 using a 1 mol / L NaOH aqueous solution over 30 minutes, and was maintained for 1.0 hour.

[0116] (Third step) The pH of the mixture obtained after the second step was adjusted to 10.0 using a 1 mol / L NaOH aqueous solution over 30 minutes, and the mixture was maintained for 4.0 hours.

[0117] (Washing ~ classification process) Next, the temperature was lowered to 25°C, the pH was adjusted to 1.5 with 1 mol / L hydrochloric acid, and the mixture was stirred for 15 minutes, and then the mixture was washed with ion-exchanged water while being filtered to obtain toner particles 2 having protrusions of a silicon-titanium composite. The production conditions for toner particles 2 are shown in Tables 1-1 and 1-2. The obtained toner particles 2 were used as they were as toner 2. The physical properties of the obtained toner 2 are shown in Table 2.

[0118] <Toner 3, 4, 14, 16, 20, 22, 25 Manufacturing Examples> Except for changing the materials and conditions of toner particle 2 shown in the production example of toner 2 to those shown in Tables 1-1 and 1-2, the same procedure as in the production example of toner 2 was carried out to obtain toners 3, 4, 14, 16, 20, 22, and 25. The physical properties of the obtained toners are shown in Table 2.

[0119] <Production examples of toners 5-13, 15, 17-19, 21, 23, 24, and 26> Except for changing the materials and conditions of toner particle 1 shown in the production example of toner 1 to those shown in Tables 1-1 and 1-2, toners 5 to 13, 15, 17 to 19, 21, 23, 24, and 26 were obtained in the same manner as in the production example of toner 1. The physical properties of the obtained toners are shown in Table 2.

[0120] <Toner 27 Manufacturing Example> (First step) A reaction vessel was charged with 300 parts of toner base particle dispersion 1 and 0.01 parts of sodium chloride, and the pH was adjusted to 9.0 using a 1 mol / L NaOH aqueous solution while stirring at 10,000 rpm using a Clearmix. Next, 0.045 parts of titanium oxide with a number average particle size of 25 nm was charged, and the mixture was stirred at 50°C for 10 minutes.

[0121] (Second process) The stirrer in the reaction vessel was changed from Clearmix to a propeller stirrer. Then, the following samples were weighed and dropped into the reaction vessel over 30 minutes. Silicon compound liquid 1 9.69 parts The mixture was stirred at 50°C for 5 hours.

[0122] (Washing ~ classification process) Next, the temperature was lowered to 25°C, the pH was adjusted to 1.5 with 1 mol / L hydrochloric acid, and the mixture was stirred for 15 minutes, and then the mixture was washed with ion-exchanged water and filtered to obtain toner particles 27 having protrusions of a silicon-titanium composite. Toner particles 27 were named toner 27. The physical properties of the obtained toner 27 are shown in Table 2.

[0123] [Table 1-1]

[0124] [Table 1-2] In the table, the materials used as additives are as follows: TC-315: Titanium lactate (component concentration 44% by mass) Matsumoto Fine Chemical Co., Ltd. TC-335: Titanium lactate ammonium salt (component concentration 35% by mass) Matsumoto Fine Chemical Co., Ltd. TA-30: Titanium tetra-2-ethylhexoxide (component concentration 99% by mass) Matsumoto Fine Chemical Co., Ltd.

[0125] [Table 2] In the toners 1 to 26, the spectrum obtained by infrared spectroscopy of the silicon-titanium polymer composite shows a 900 cm peak attributable to the Ti-O-Si stretching vibration. -1 ~1000cm -1 A peak was confirmed. In the table, Ti indicates the amount (mmol) of Ti element per 100 g of toner base particles in the toner, and Si indicates the amount (mmol) of Si element per 100 g of toner base particles in the toner. In the table, for example, 1.0E-02 means 1.0 x 10 -2 Shows.

[0126] Example 1 Toner 1 was used to carry out various evaluations using the following evaluation machines. <Evaluation machine> The following two types of modified machines were used for evaluation. As an image forming device, a commercially available laser printer LBP-722Ci (Canon) was connected to an external high-voltage power supply and modified to provide an arbitrary potential difference between the charging blade and the developing roller, and the process speed was set to 268 mm / sec. This modified machine was used as evaluation machine 1. there was.

[0127] As an image forming device, a commercially available laser printer LBP-722Ci (manufactured by Canon) was connected to an external high-voltage power supply and modified to allow any potential difference to be set between the charging blade and the developing roller, and the modified machine with a process speed of 90 mm / sec was used as evaluation machine 2. The process cartridge used was a commercially available toner cartridge 064H (black) (manufactured by Canon).

[0128] The product toner was removed from the inside of the cartridge and cleaned with an air blower, after which 600 g of the toner to be evaluated was filled into the cartridge for evaluation machine 1 and 150 g into the cartridge for evaluation machine 2. The loading amount on the developing roller was 0.35 mg / cm 3 The position of the charging blade was adjusted so that the toner remaining amount detection mechanism was disabled, and the yellow, magenta, and cyan cartridges were inserted into each of the yellow, magenta, and cyan stations, and the product toner was removed.

[0129] <Durability evaluation in low temperature and low humidity environments> The evaluation was performed using two evaluation machines, evaluation machine 1 and 2. The main body and cartridge were left in a low temperature and low humidity environment (15.0°C / 10% RH, hereinafter referred to as LL environment) for three days. After leaving them, the following evaluation was performed. The development conditions were set to a charging blade voltage of -500 V and a developing roller voltage of -300 V. Under an LL environment, an intermittent operation in which the printer was temporarily stopped every two sheets of an image with a print rate of 1% was repeated, and a total of 40,000 sheets of output test was performed for evaluation machine 1, and 10,000 sheets of output test was performed for evaluation machine 2.

[0130] <Evaluation of image fog under low temperature and low humidity environment> The developing conditions were set as follows: the charging blade voltage was -500V, and the developing roller voltage was -300V. The following evaluations were carried out at the beginning of the durability evaluation and after the output test (after durability). The evaluation of fog was performed using LETTER size HP Color Laser Photo Paper, Glossy (HP, 220 g / m 2 The experiment was carried out using a new drum unit prepared for image fogging, a solid white image as the output image, and a new drum unit prepared for image fogging. The device was forcibly stopped during development, and the white image area latent on the drum (Dr) was taped with surface protection tape 331N (3M), and a LETTER size HP Color Laser Photo Paper, Glossy (HP, 220 g / m 2 For the non-image area, only the surface protection tape 331N (3M) was attached to the paper with the tape taped on the Dr.

[0131] To evaluate fogging, a green filter was set in a "REFLECTO METER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.) and the reflectance (%) of the tape taped over the Dr attached to the paper was measured. The reflectance obtained was subtracted from the reflectance (%) of the tape attached as the non-image area, which was measured in the same way, and the value (%) was used for evaluation. The smaller the value, the more suppressed the fogging. The evaluation criteria are as follows: (Evaluation Criteria) A: The deduction is less than 0.5% B: The deduction is between 0.5% and 1.5% C: The deduction is between 1.5% and 3.0%. D: The subtracted value is 3.0% or more.

[0132] <Evaluation of image density under low temperature and low humidity conditions> The developing conditions were set as follows: the charging blade voltage was -500V, and the developing roller voltage was -300V. The following evaluations were carried out at the beginning of the durability evaluation, after outputting 100 sheets, and after the sheet output test (after durability). The image density was evaluated using GF-600 (weight 60 g / m 2 A printer (Canon Marketing Japan Inc.) was used, and the output images were 5 cm x 5 cm solid images printed on the left, center, and right of the leading edge of the paper. The image density was measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite Corporation) to measure the image density of a solid image portion, and evaluated according to the following evaluation criteria. A: The average of the three points is 1.55 or more. B: The average of the three points is between 1.45 and 1.55. C: The average of the three points is between 1.35 and 1.45. D: The average of the three points is less than 1.35.

[0133] <Evaluation of component contamination in low temperature and low humidity environments> The charging roller (C roller) was removed from the toner cartridge that had been evaluated using the evaluation machine 1. The charging roller was removed from a new process cartridge (commercially available), and the charging roller that had been used was attached, and a halftone image was output. The uniformity of the halftone image was visually evaluated, and the contamination of the charging member was evaluated. It is known that if the charging roller is contaminated, uneven charging occurs on the photosensitive drum, resulting in uneven density in halftone images. A grade of C or higher was judged to be good. (Evaluation Criteria) A: The image density is uniform and there are no irregularities. B: Image density is slightly uneven C: Image density is uneven, but at a good level. D: The image density is uneven and the halftone image is not uniform.

[0134] <Durability evaluation under high temperature and high humidity environment> As the evaluation machine, evaluation machine 1 was used. The main body and cartridge were left in a high temperature and low humidity environment (30.0°C / 80% RH, hereinafter referred to as HH environment) for 3 days. After leaving it, the following evaluations were carried out. The development conditions were set to a charging blade voltage of -500V and a developing roller voltage of -300V. In the HH environment, images with a print rate of 5% were continuously output, and an output test of 10,000 sheets in total was carried out.

[0135] <Evaluation of fogging under high temperature and humidity conditions> The developing conditions were set as follows: the charging blade voltage was -500V, and the developing roller voltage was -300V. The following evaluations were carried out at the beginning of the durability evaluation (after leaving for 3 days and fogging), after outputting 100 sheets, and after the output test (after durability). The evaluation of fog was performed using LETTER size HP Color Laser Photo Paper, Glossy (HP, 220 g / m 2 The experiment was carried out using a new drum unit prepared for image fogging, a solid white image as the output image, and a new drum unit prepared for image fogging. The device was forcibly stopped during development, and the white image area latent on the drum was taped with surface protection tape 331N (3M), and a LETTER size HP Color Laser Photo Paper, Glossy (HP, 220 g / m 2 For the non-image area, only the surface protection tape 331N (3M) was attached to the paper with the tape taped on the Dr.

[0136] The evaluation of the fog was done using the "REFLECTO METER MODEL TC-6DS" (Tohoku) A green filter was set on a Kyodenshoku Co., Ltd. filter and the reflectance (%) of the tape taped onto the Dr. attached to the paper was measured. The reflectance obtained was subtracted from the reflectance (%) of the tape attached as the non-image area, which was measured in the same way, and the value (%) was used for evaluation. The smaller the value, the more suppressed the fogging. The evaluation criteria are as follows: (Evaluation Criteria) A: The deduction is less than 0.5% B: The deduction is between 0.5% and 1.5% C: The deduction is between 1.5% and 3.0%. D: The subtracted value is 3.0% or more.

[0137] <Durability evaluation under ultra-high temperature and high humidity conditions> As the evaluation machine, evaluation machine 1 was used. The main body and cartridge were left in an ultra-high temperature and low humidity environment (32.5°C / 80% RH, hereafter referred to as SHH environment) for 3 days. After leaving it, the following evaluations were carried out. The development conditions were set to a charging blade voltage of -500V and a developing roller voltage of -300V. In the SHH environment, images with a print rate of 5% were continuously output, and an output test of a total of 10,000 sheets was carried out.

[0138] <Evaluation of fogging under ultra-high temperature and humidity conditions> The developing conditions were set as follows: the charging blade voltage was -500V, and the developing roller voltage was -300V. The following evaluations were carried out at the beginning of the durability evaluation (after leaving for 3 days and fogging), after outputting 100 sheets, and after the output test (after durability). The evaluation of fog was performed using LETTER size HP Color Laser Photo Paper, Glossy (HP, 220 g / m 2 The experiment was carried out using a new drum unit prepared for image fogging, a solid white image as the output image, and a new drum unit prepared for image fogging. The device was forcibly stopped during development, and the white image area latent on the drum was taped with surface protection tape 331N (3M), and a LETTER size HP Color Laser Photo Paper, Glossy (HP, 220 g / m 2 For the non-image area, only the surface protection tape 331N (3M) was attached to the paper with the tape taped on the Dr.

[0139] To evaluate fogging, a green filter was set in a "REFLECTO METER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.) and the reflectance (%) of the tape taped over the Dr attached to the paper was measured. The reflectance obtained was subtracted from the reflectance (%) of the tape attached as the non-image area, which was measured in the same way, and the value (%) was used for evaluation. The smaller the value, the more suppressed the fogging. The evaluation criteria are as follows: (Evaluation Criteria) A: The deduction is less than 0.5% B: The deduction is between 0.5% and 1.5% C: The deduction is between 1.5% and 3.0%. D: The subtracted value is 3.0% or more.

[0140] As shown in Tables 3-1 and 3-2, the toner of Example 1 obtained good results in all evaluations.

[0141] (Examples 2 to 19, Comparative Examples 1 to 8) Examples 2 to 19 and Comparative Examples 1 to 8 were carried out using the toner combinations shown in Tables 3-1 and 3-2. The evaluation results are shown in Tables 3-1 and 3-2.

[0142] [Table 3-1]

[0143] [Table 3-2]

[0144] <Production Example of Toner Particle 28> Toner base particle dispersion 1 is adjusted to pH 1.5 with 1 mol / L hydrochloric acid and stirred for 1.5 hours. Thereafter, the mixture was washed with ion-exchanged water and filtered to obtain toner particles 28. The toner particles 28 had a number-average particle size (D1) of 6.2 μm and a volume-average particle size (D4) of 6.9 μm.

[0145] <Production Example of Silicon-Titanium Polymer Microparticles 1> <First step> An aqueous solution in which 1.0 part of sodium phosphate (12-hydrate) was dissolved was prepared in a reaction vessel containing 100.0 parts of ion-exchanged water, and the pH was adjusted to 3.0 with 1 mol / L HCl. While mixing the aqueous solution in the reaction vessel with a propeller agitator, 0.95 parts of a 44% aqueous solution of titanium lactate (TC-315: Matsumoto Fine Chemical Co., Ltd.) was added, and 15 minutes later, 8.34 parts of silicon compound liquid 1 was added. The temperature of the reaction vessel was then raised to 50°C, and the pH was adjusted to 8.5 over 30 minutes using 1 mol / L NaOH, followed by stirring for 2 hours.

[0146] <Second process> After 2 hours, the pH of the mixture was adjusted to 9.5 using 1 mol / L NaOH aqueous solution, and then a solution of 0.10 parts of TC-315 and 1.00 parts of silicon compound liquid was dropped into the mixture being mixed using a propeller stirring blade over 30 minutes. The mixture was then kept stirred for 3.0 hours. Next, the temperature was lowered to 25° C., and the mixture was washed with ion-exchanged water and filtered to obtain silicon-titanium composite particles 1 having a number average particle size of 45 nm. The physical properties of the obtained silicon-titanium polymer microparticles 1 are shown in Table 5.

[0147] <Production Examples of Silicon-Titanium Polymer Microparticles 2-4> Silicon-titanium polymer microparticles 2 to 4 were prepared in the same manner as in the production example of silicon-titanium polymer microparticles 1, except that the materials in each step were changed to the materials and amounts shown in Table 4. The physical properties of the obtained silicon-titanium polymers 2 to 4 are shown in Table 5.

[0148] <Production Example of Silicon-Titanium Polymer Microparticle 5> Using Clearmix, 0.045 parts of titanium oxide having a number-average particle size of 25 nm was dispersed in 100 parts of distilled water whose pH had been adjusted to 9.0 using a 1 mol / L aqueous NaOH solution, and the temperature had been adjusted to 50° C. A solution was prepared. While stirring this dispersion with a propeller impeller, 6.55 parts of silicon compound liquid 1 was added dropwise over 30 minutes, and the mixture was kept stirred at 50° C. for 5 hours, to obtain a slurry of silicon-titanium polymer microparticles 5. The temperature of the slurry was lowered to 25° C., and then the slurry was washed with ion-exchanged water and filtered to obtain silicon-titanium composite particles 5 having a number average particle size of 45 nm. The physical properties of the obtained silicon-titanium polymer microparticles 5 are shown in Table 5.

[0149] [Table 4]

[0150] <Toner 28 Manufacturing Example> Toner particles 28: 100 parts Silicon-titanium polymer particles 1: 5 parts The above materials were dry mixed for 10 minutes in a Henschel mixer (manufactured by Nippon Coke Corporation) to obtain toner 28. The physical properties of the obtained toner 28 are shown in Table 5.

[0151] <Production Example of Toner 29 to 32> Toners 29 to 32 were produced in the same manner as in Production Example of Toner 28, except that the silicon-titanium polymer fine particles 1 in Production Example of Toner 28 were changed to the fine particles shown in Table 5. The physical properties of the obtained toners 29 to 32 are shown in Table 5.

[0152] [Table 5] In toners 28-31, the results were obtained by infrared spectroscopy of fine particles of silicon-titanium polymer composite. In the spectrum obtained, the 900 cm 2 band assigned to the Ti-O-Si stretching vibration was -1 ~1000cm -1 A peak was confirmed. In the table, H is the number average particle size of the silicon-titanium polymer microparticles.

[0153] Example A The following evaluations were carried out in the same manner as in Example 1. Good results were obtained for the toner of Example A. Detailed evaluation results are shown in Tables 6-1, 6-2, and 6-3.

[0154] (Examples B to D, Comparative Example A) The following evaluations were carried out in the same manner as in Example 1. Detailed evaluation results are shown in Tables 6-1, 6-2, and 6-3.

[0155] [Table 6-1]

[0156] [Table 6-2]

[0157] [Table 6-3]

[0158] The present disclosure relates to the following configurations. (Configuration 1) A toner comprising toner particles, The toner particles are toner base particles having a binder resin and a colorant; a silicon-titanium polymer composite present on the surface of the toner base particle; The silicon-titanium polymer composite contains a silicon polymer moiety and a titanium chelate moiety; The silicon-titanium polymer composite has a 900 cm peak attributable to Ti-O-Si stretching vibration in a spectrum obtained by infrared spectroscopy. -1 ~1000cm -1 It has a peak at When the ratio of the number of titanium atoms to the sum of the numbers of carbon atoms, oxygen atoms, silicon atoms, phosphorus atoms, and titanium atoms obtained by X-ray photoelectron spectroscopy of the toner is defined as Ti-E and the ratio of the number of silicon atoms is defined as Si-E, The toner, wherein the Ti-E and the Si-E satisfy the following formulas (1) and (2): 1.0×10 -3 ≦Ti-E≦ 2.5×10 -2 (1) 1.0×10 -2 ≦Ti-E / Si-E≦ 7.0×10 -2 (2) (Configuration 2) 2. The toner according to claim 1, wherein the titanium chelate in the titanium chelate moiety comprises at least one titanium chelate selected from the group consisting of titanium phosphate chelate, titanium lactate, titanium ammonium lactate, titanium dodecylbenzenesulfonate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, and titanium octylene glycolate. (Configuration 3) 3. The toner according to claim 1 or 2, wherein the titanium chelate in the titanium chelate moiety includes at least one titanium chelate selected from the group consisting of titanium phosphate, titanium lactate, ammonium titanium lactate, and titanium dodecylbenzenesulfonate. (Configuration 4) In an EDS mapping image of constituent elements of a cross section of the toner, which is obtained by analyzing the cross section of the toner observed with a transmission electron microscope with an energy dispersive X-ray spectrometer, The toner according to any one of configurations 1 to 3, wherein MX is a ratio of the number of titanium atoms to the sum of the numbers of silicon atoms and titanium atoms in a region outside the contour of the toner base particle, and MX satisfies the following formula (3): 0.50×10 -4 ≦MX≦1.50×10 -1 (3) (Configuration 5) In the spectrum obtained by infrared spectroscopy of the silicon-titanium polymer composite, a 900 cm peak attributable to Ti-O-Si stretching vibration was observed. -1 ~1000cm -1 The maximum value of the peak is P_Ti. 1000cm attributed to Si-O-Si stretching vibration -1 ~1100cm -1 When the maximum value of the peak is P_Si, The toner according to any one of configurations 1 to 4, wherein P_Ti and P_Si satisfy the following formula (4): 0.06≦P_Ti / P_Si≦0.15 (4) (Configuration 6) the silicon-titanium polymer composite is fixed to the surface of the toner base particle in a convex shape; When the number average height of the convex portions measured by a scanning probe microscope is H, 6. The toner according to any one of configurations 1 to 5, wherein H is 25 to 100 nm. (Configuration 7) The toner according to any one of configurations 1 to 6, wherein the silicon polymer portion is a condensation polymer of an organosilicon compound. (Configuration 8) The toner according to any one of configurations 1 to 7, wherein the silicon polymer moiety has a structure represented by the following formula (5): R-SiO 3 / 2 (5) In formula (5), R is an alkyl group having 1 to 6 carbon atoms or a phenyl group. (Configuration 9) In a toner particle having a binder resin and a colorant, and a toner having fine particles of a silicon-titanium polymer composite, The silicon-titanium polymer composite contains a silicon polymer moiety and a titanium chelating moiety; The silicon-titanium polymer composite has a 900 cm peak attributable to Ti-O-Si stretching vibration in a spectrum obtained by infrared spectroscopy. -1 ~1000cm -1 It has a peak at When the ratio of the number of titanium atoms to the sum of the numbers of carbon atoms, oxygen atoms, silicon atoms, phosphorus atoms, and titanium atoms obtained by X-ray photoelectron spectroscopy of the toner is defined as Ti-E and the ratio of the number of silicon atoms is defined as Si-E, The toner, wherein the Ti-M and Si-M satisfy the following formulas (1) and (2): 1.0×10 -3 ≦Ti-E≦2.5×10 -2 (1) 1.0×10 -2 ≦Ti-E / Si-E≦ 7.0×10 -2 (2)

Claims

1. Toner containing toner particles, The toner particles are Toner matrix particles having a binder resin and a colorant, The toner matrix particles have a silicon-titanium polymer composite present on their surface, The silicon-titanium polymer composite contains a silicon polymer moiety and a titanium chelate moiety. The silicon-titanium polymer composite exhibits a 900 cm² vibration attributable to the Ti-O-Si stretching vibration in the spectrum obtained by infrared spectroscopy. －１ ~1000cm －１ It has a peak at, Ti-E is defined as the ratio of titanium atoms to the sum of the total number of carbon, oxygen, silicon, phosphorus, and titanium atoms obtained from X-ray electron spectroscopy analysis of the toner. When the ratio of silicon atoms to the sum of the total number of carbon, oxygen, silicon, phosphorus, and titanium atoms obtained from X-ray electron spectroscopy analysis of the toner is denoted as Si-E, A toner characterized in that the Ti-E and Si-E satisfy the following formulas (1) and (2). 1.0×10 －３ ≦Ti-E≦ 2.5×10 －２ ・・・(1) 1.0×10 －２ ≦Ti-E / Si-E≦ 7.0×10 －２ ・・・(2)

2. The toner according to claim 1, wherein the titanium chelate in the titanium chelate site comprises at least one titanium chelate selected from the group consisting of titanium chelate phosphate, titanium lactate, titanium lactate ammonium, titanium dodecylbenzenesulfonate, titanium acetylacetonate, titanium tetraacetylacetonate, titanium ethylacetoacetate, and titanium octylene glycolate.

3. The toner according to claim 1, wherein the titanium chelate in the titanium chelate portion comprises at least one titanium chelate selected from the group consisting of titanium phosphate, titanium lactate, titanium lactate ammonium, and titanium dodecylbenzenesulfonate.

4. In an EDS mapping image of the constituent elements of the toner cross-section obtained by analyzing the cross-section of the toner observed with a transmission electron microscope using an energy-dispersive X-ray spectrometer, The toner according to any one of claims 1 to 3, wherein when M-X is the ratio of the number of titanium atoms to the sum of the number of silicon atoms and titanium atoms in the region outside the contour of the toner matrix particles, M-X satisfies the following formula (3). 0.50×10 －４ ≦ M-X ≦ 1.50×10 －１ ・・・(3)

5. In a spectrum obtained by infrared spectroscopic analysis of the silicon-titanium polymer composite, 900 cm attributed to Ti-O-Si stretching vibration －１ to 1000 cm －１ Let the maximum value of the peak be P_Ti, 1000 cm² is attributed to Si-O-Si stretching vibration. －１ ~1100cm －１ When the maximum value of the peak is denoted as P_Si, The toner according to any one of claims 1 to 3, wherein P_Ti and P_Si satisfy the following formula (4). 0.06≦P_Ti / P_Si≦0.15...(4)

6. The silicon-titanium polymer composite is fixed in a convex shape to the surface of the toner matrix particles. When H is the average height of the protrusions measured by a scanning probe microscope, The toner according to any one of claims 1 to 3, wherein the H is 25 to 100 nm.

7. The toner according to any one of claims 1 to 3, wherein the silicon polymer portion is a condensed polymer of an organosilicon compound.

8. The toner according to any one of claims 1 to 3, wherein the silicon polymer portion has a structure represented by the following formula (5). R-SiO ３／２ ・・・(5) In formula (5), R is an alkyl group having 1 to 6 carbon atoms or a phenyl group.

9. In a toner having toner particles having a binder resin and a colorant, and fine particles of a silicon-titanium polymer composite, The silicon-titanium polymer composite contains a silicon polymer moiety and a titanium chelate moiety. The silicon-titanium polymer composite exhibits a 900 cm² vibration originating from the Ti-O-Si stretching vibration in the spectrum obtained by infrared spectroscopy. －１ ~1000cm －１ It has a peak at, Ti-E is defined as the ratio of titanium atoms to the sum of the total number of carbon, oxygen, silicon, phosphorus, and titanium atoms obtained from X-ray electron spectroscopy analysis of the toner. When the ratio of silicon atoms to the sum of the total number of carbon, oxygen, silicon, phosphorus, and titanium atoms obtained from X-ray electron spectroscopy analysis of the toner is denoted as Si-E, A toner characterized in that the Ti-E and Si-E satisfy the following formulas (1) and (2). 1.0×10 －３ ≦Ti-E≦2.5×10 －２ ・・・(1) 1.0×10 －２ ≦Ti-E / Si-E≦ 7.0×10 －２ ・・・(2)