toner

Abstract

To provide a toner with excellent hot off-set resistance and gloss uniformity on rough paper, while having better low-temperature fixability than conventional ones.SOLUTION: A toner contains toner particles containing resin A. The resin A contains 30 mass% or more of a unit (a) represented by the following formula (1). A content of the resin A based on toner mass is between 20.0 mass% and 100.0 mass%. The toner satisfies a specific relationship equation in the viscoelasticity measurement of the toner, and contains THF insoluble content. The resin A has a siloxane structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to toner used in electrophotography, electrostatic recording, magnetic recording, and the like. [Background technology]

[0002] In recent years, electrophotographic image forming devices such as laser beam printers (LBPs) and photocopiers have been increasingly required to achieve higher printing speeds and energy efficiency. Therefore, the toner, which is a developer, also needs to be addressed in the same way as above. Specifically, the importance of low-temperature fixing performance, which allows for fixing with less heat, is increasing year by year. To achieve this, the addition of plasticizers to the main binder of toner has been widely practiced. Specifically, plasticizers are crystalline molecules such as hydrocarbon waxes and crystalline resins such as crystalline polyesters. Crystalline polyesters, in particular, which have a higher molecular weight than low molecular weight plasticizers, are currently widely used because they cause fewer problems such as bleeding (Patent Document 1). However, since the toner softens after the plasticizer melts and then plasticizes the binder resin, there is a limit to the toner's melting speed, and further improvements in low-temperature fixation are desired. Therefore, methods using crystalline resins as the main binder are being considered. When considered as a binder resin, crystalline resins have the property that they hardly soften at temperatures below their melting point due to the regular arrangement of their molecular chains. Furthermore, above the melting point, the crystals melt rapidly, resulting in a rapid decrease in viscosity. For this reason, they are attracting attention as materials that exhibit excellent sharp melt properties and low-temperature fixability. However, as the amount of crystalline resin components increased in pursuit of even better low-temperature fixing performance, the deterioration of hot offset due to the low elasticity of the crystalline resin during melting, and the non-uniformity of gloss on rough paper with greater irregularities, became challenges. To address these challenges, there is a conventional method of adding and increasing the amount of polymerizable crosslinking agents to increase the amount of gel components that exhibit high elasticity (Patent Document 2).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, when the crosslinking degree of the gel is increased as in Patent Document 2 above, there arises a problem that the compatibility with other binder components decreases. For this reason, rather than separating other low-viscosity components, it becomes a direction of separation, and the effects of improving hot offset and gloss non-uniformity are limited, and there is also a problem that low-temperature fixing property is inhibited. An object of the present invention is to solve the above problems and provide a toner that exhibits better low-temperature fixing property than before and is excellent in hot offset resistance and gloss uniformity on rough paper.

Means for Solving the Problems

[0005] The present invention is a toner having toner particles containing resin A as a binder resin, wherein the resin A The structure represented by the following formula (5) has

[0006]

Chemical formula

[0007]

Chemical formula

[0008] According to the present invention, it is possible to provide a toner that exhibits superior low-temperature fixing performance compared to conventional toners, while also having excellent resistance to hot offset printing and gloss uniformity on rough paper. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic diagram of a measurement sample and jig for measuring viscoelasticity. [Modes for carrying out the invention]

[0010] In this disclosure, unless otherwise specified, the expressions "XX or greater and YY or less" or "XX to YY" that represent a numerical range mean a numerical range that includes the lower and upper limits.

[0011] (Meth)acrylic acid ester refers to acrylic acid ester and / or methacrylic acid ester.

[0012] When numerical ranges are given in stages, the upper and lower limits of each range can be combined in any way.

[0013] A "monomer unit" refers to the reacted form of monomer substances in a polymer. For example, one carbon-carbon bond in the main chain formed by the polymerization of polymerizable monomers in a polymer is considered one unit. A polymerizable monomer can be represented by the following formula (7).

[0014] [ka] [In formula (7), R A R represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), B represents any substituent.

[0015] Crystalline resins are resins that exhibit a clear endothermic peak in differential scanning calorimeter (DSC) measurements.

[0016] [Features of the present invention] The present invention relates to a toner having toner particles containing resin A as a binder resin, The aforementioned resin A is (i) Contains 30% by mass or more of unit (a) shown in the following formula (1):

[0017] [ka] [In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond, an ester bond, or an amide bond, and m represents an integer between 15 and 30.] (ii) The content, based on the mass of the toner, is 20.0% by mass or more and 100.0% by mass or less. In the viscoelasticity measurement of the toner, the storage modulus G' of the toner was 1.0 × 10⁻⁶. 7 Let T1 [°C] be the temperature at which Pa occurs, and let tanδ(T1) be the ratio of the loss modulus G'' at temperature T1 [°C] to the storage modulus G', and let tanδ(T1-10) be the ratio of tanδ at temperature T1-10 [°C]. Then, the following equations (2) to (4) are satisfied. 50.0 ≤ T1 ≤ 70.0 (2) 0.30 ≤ tanδ(T1) ≤ 1.00 (3) 1.00≦tanδ(T1) / tanδ(T1-10)≦1.90 (4) The toner contains THF-insoluble components, and the THF-insoluble components have a structure represented by the following formula (5):

[0018] [ka] In formula (5), A independently represents resin A, n is an integer between 1 and 10, and X independently represents a hydrogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group, and the mass of silicon derived from the siloxane structural site, as measured by the method described below, is 0.005% to 0.150% of the THF insoluble content. [Using a PerkinElmer TGA7 thermal analyzer, the THF-insoluble components were heated from 50°C to 900°C at a heating rate of 25°C / min, and the reduced amount of Si was considered to be the Si mass derived from the siloxane structure.]

[0019] The toner is characterized in that the resin A has a structure represented by formula (5).

[0020] According to the inventors' research, the above-mentioned toner makes it possible to provide a toner that exhibits better low-temperature fixing performance than conventional toners, while also having excellent resistance to hot offset printing and gloss uniformity on rough paper.

[0021] The details are explained below.

[0022] In order to achieve low-temperature fixation while suppressing drawbacks such as poor storage properties, it is necessary for the storage modulus to be high up to the temperature required for heat-resistant storage, and then to decrease rapidly at temperatures higher than that, in other words, to exhibit sharp melt properties.

[0023] Furthermore, generally, the ratio of the loss modulus G'' to the storage modulus G' (tanδ) represents the ease of deformation of a polymer material, indicating whether it exhibits strong elastic or viscous properties. A smaller tanδ makes it more difficult to deform, resulting in a so-called "rubber-like" material, while a larger tanδ makes it more easily deformable, resulting in a so-called "gum-like" material. Therefore, by appropriately controlling the change in tanδ in the sharp-melting temperature range, the ease of deformation of the toner during low-temperature fixing can be controlled, thereby ensuring the gloss uniformity of the toner.

[0024] However, the above configuration was insufficient when seeking lower-temperature fixing performance than conventional methods. Furthermore, as the toner becomes more prone to melting in pursuit of lower-temperature fixing, countermeasures against the resulting hot offset were essential. Therefore, the inventors discovered that the above problems could be solved by introducing a siloxane bonding site into the THF-insoluble component (gel component), which is a highly elastic part of the toner resin.

[0025] Conventionally, to improve the high-temperature elasticity of toner, the addition of crosslinking agent monomers was common. This increases the gel content, which is the highly crosslinked region, making it possible to improve the high-temperature elasticity of the toner.

[0026] However, when the gel component is highly crosslinked, it tends to separate from other resin components, and even with large amounts added, its effect tends to saturate. The presence of separated low-elasticity components ultimately causes hot offset and gloss non-uniformity. Furthermore, this method had many drawbacks, such as inhibited low-temperature fixing.

[0027] Therefore, the inventors attempted to solve the above problems by introducing siloxane bonding sites into the gel resin in order to impart high elasticity and suppress the separation of the gel component from other resin components. This creates a large-scale gel structure in which gel domains are loosely bonded together by generating affinity between siloxane bonding sites with different polarities relative to the carbon-based structure of the surrounding resin. It is believed that this can impart high elasticity to the toner without hindering low-temperature fixation, thereby improving hot offset and gloss uniformity.

[0028] The mechanism is thought to be due to the weak interaction between siloxane bond sites, which allows other resin components to be incorporated within a large gel structure. This makes it possible to impart high elasticity similar to that achieved by increasing the crosslinking density using conventional techniques, without promoting the separation of the gel from other resin components.

[0029] [Configuration of the toner of the present invention] The present invention will be described in detail below.

[0030] The toner of the present invention contains resin A, and from the viewpoint of low-temperature fixation, resin A must contain 30% by mass or more of unit (a) shown in the following formula (1). If it is less than 30% by mass, the low-temperature fixation will be insufficient.

[0031] [ka] [In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond, an ester bond, or an amide bond, and m represents an integer between 15 and 30.]

[0032] Furthermore, from the viewpoint of low-temperature fixation, the content of resin A, based on the mass of the toner, must be 20.0% by mass or more. If it is less than 20.0% by mass, the low-temperature fixation will be insufficient. Preferably, the content of resin A is between 25.0% by mass and 85.0% by mass.

[0033] In the viscoelasticity measurement of toner, the present invention relates to a storage modulus G' of 1.0 × 10⁻⁶. 7 Let T1 [°C] be the temperature at which Pa occurs, and let tanδ(T1) be the ratio (tanδ) of the loss modulus G'' at temperature T1 [°C] to the storage modulus G', and let tanδ(T1-10) be the ratio of tanδ at temperature T1-10 [°C]. Then the following equation (2) is satisfied. 50.0 ≤ T1 ≤ 70.0 (2)

[0034] Satisfying equation (2) results in good low-temperature fixing performance of the toner. If T1 is less than 50.0°C, it is advantageous for low-temperature fixing performance, but it can lead to drawbacks such as poor heat resistance of the toner during storage. Conversely, if T1 is greater than 70.0°C, low-temperature fixing performance decreases.

[0035] T1 can be controlled by the length of the long-chain alkyl group and the proportion of the long-chain alkyl group in the binder resin when the crystalline resin in the toner is a vinyl resin having a long-chain alkyl group. Furthermore, when the crystalline resin is a polyester resin, T1 can be controlled by the number of carbon atoms in the diol and dicarboxylic acid components used.

[0036] Furthermore, the present invention satisfies the following formulas (3) and (4). 0.30 ≤ tanδ(T1) ≤ 1.00 (3) 1.00≦tanδ(T1) / tanδ(T1-10)≦1.90 (4)

[0037] Since T1 is the temperature during sharp melting, if tanδ(T1) is within the range of equation (3) above, the ease of deformation of the toner during low-temperature fixing is appropriately maintained. Combined with the gel component containing siloxane bonds described later, it is possible to increase gloss on rough paper.

[0038] Furthermore, when tanδ(T1) / tanδ(T1-10) is within the range of formula (4) above, together with the gel component containing siloxane bonds described later, the ease of deformation in the convex and concave parts of the rough paper is kept within a certain range, improving gloss uniformity.

[0039] If tanδ(T1) is less than 0.30, the elastic properties become too large during low-temperature fixing, resulting in a decrease in gloss on rough paper. Conversely, if it is greater than 1.00, the viscous properties become too large during low-temperature fixing, causing the toner to soak into the paper more easily, thus worsening gloss uniformity.

[0040] tanδ(T1) can be controlled by the amount of crystalline resin added to the toner. In particular, if the crystalline resin is a vinyl resin with long-chain alkyl groups, it can be controlled by the length of the long-chain alkyl groups and the proportion of long-chain alkyl groups in the binder resin. It can also be controlled by the type and amount of crosslinking agent added during toner manufacturing.

[0041] Furthermore, if tanδ(T1) / tanδ(T1-10) is less than 1.00, deformation becomes less likely even with sharp melting, thus reducing the scratch resistance of the fixed image. If tanδ(T1) / tanδ(T1-10) is greater than 1.90, the toner rapidly changes from elastic to viscous properties near the melting start temperature, making convex areas more prone to deformation and concave areas more difficult to deform during low-temperature fixing. As a result, gloss uniformity deteriorates.

[0042] The tanδ(T1) / tanδ(T1-10) ratio can be controlled by the type and amount of amorphous resin used in the toner.

[0043] The toner of the present invention contains THF-insoluble components, and the THF-insoluble components have a structure represented by the following formula (5).

[0044] [ka]

[0045] In formula (5), A independently represents resin A, n is an integer between 1 and 10, and X independently represents a hydrogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group. Furthermore, the mass of silicon derived from the siloxane structural moiety, as measured by the method described below, is between 0.005% by mass and 0.150% by mass of the THF insoluble content.

[0046] The method for measuring the silicon mass involves using a PerkinElmer TGA7 thermal analyzer to heat the THF-insoluble portion from 50°C to 900°C at a heating rate of 25°C / min, and the amount of Si that decreases is considered to be the Si mass derived from the siloxane structure.

[0047] The THF-insoluble components have the structure of formula (5), which allows the aforementioned siloxane structural sites to exhibit affinity, forming a loose gel structure that includes non-gel components, making it possible to achieve low-temperature fixation, resistance to hot offset, and gloss uniformity on rough paper simultaneously.

[0048] If the amount of siloxane structural units is less than 0.005% by mass (calculated by silicon weight), the aforementioned loose gel structure cannot be formed due to the insufficient amount of siloxane structural units, making it difficult to achieve hot offset resistance and gloss uniformity. Conversely, if the amount is greater than 0.150% by mass, the increased amount of siloxane structural units leads to aggregation and domainization, making it difficult to form a loose gel structure.

[0049] In this invention, the resin A has a structure represented by formula (5). This suppresses the separation of the gel component from the other resin components, making it possible to achieve low-temperature fixation, resistance to hot offset, and gloss uniformity simultaneously.

[0050] The proportion of unit (a) in the resin A is preferably 50.0% by mass or more and 90.0% by mass or less, because this allows for low-temperature fixing while maintaining hot offset resistance and gloss uniformity.

[0051] In the viscoelasticity measurement of the toner of the present invention, the storage modulus G' is 3.0 × 10⁻⁶. 7 T2 [°C] is the temperature at which Pa is obtained, and the storage modulus G' is 3.0 × 10⁻⁶. 6 When the temperature at which Pa is obtained is T3 [°C], it is preferable that the following equation (6) is satisfied. |T3-T2|≦10.0 (6)

[0052] Satisfying equations (2) and (6) above is preferable because it allows for both low-temperature fixability and heat-resistant storage of the toner. |T3-T2| can be controlled by the proportion of crystalline resin in the toner, the proportion of crystalline parts in the crystalline resin, and so on.

[0053] Furthermore, in formula (5), when n=1, the dispersibility of the siloxane binding site in the toner binder is good, the mixing of the loose gel structure and non-gel components is good, and it is preferable that low-temperature fixation is achieved while maintaining hot offset resistance and gloss uniformity.

[0054] <Resin A> The resin A used in this invention will be described in detail below.

[0055] Examples of resin A include crystalline vinyl resin, polyester resin, polyurethane resin, epoxy resin, etc., but crystalline vinyl resin is preferred.

[0056] Resin A has a monomer unit (a) represented by the above formula (1). Formula (1) indicates the presence of a long-chain alkyl group, and the presence of a long-chain alkyl group makes the resin more likely to exhibit crystallinity. Furthermore, the fact that n in formula (1) is between 15 and 30 makes it easier to control the above formula (2) within a range. Preferably, n is between 17 and 29.

[0057] One method for introducing monomer unit (a) is to polymerize (meth)acrylic acid esters, such as stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosa (meth)acrylate, myricyl (meth)acrylate, dodoriaconta (meth)acrylate, and 2-decyltetradecyl (meth)acrylate.

[0058] The unit in formula (2) may be used individually or in combination of two or more types.

[0059] If resin A is a crystalline vinyl resin, it is possible to have other monomer units in addition to the monomer unit (a). One method for introducing other monomer units is to polymerize the (meth)acrylic acid ester with other vinyl monomers.

[0060] Other vinyl monomers include the following:

[0061] (Meth)acrylic acid esters such as styrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.

[0062] Monomers having a urea group: For example, monomers obtained by reacting an amine having 3 to 22 carbon atoms [primary amines (n-butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, and cycloxylamine, etc.)] with an isocyanate having 2 to 30 carbon atoms and having an ethylenically unsaturated bond, by known methods.

[0063] Monomers having a carboxyl group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylate.

[0064] Monomers having a hydroxyl group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.

[0065] Monomers having an amide group; for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by known methods.

[0066] In particular, styrene, methyl (meth)acrylate, and t-butyl (meth)acrylate are preferred.

[0067] If resin A is a polyester resin, then any crystalline polyester resin that can be obtained by the reaction of a divalent or higher polycarboxylic acid with a polyhydric alcohol can be used.

[0068] Examples of polycarboxylic acids include the following compounds: dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, and dodecenylsuccinic acid, and their anhydrides or lower alkyl esters; and aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and their anhydrides or lower alkyl esters. These may be used individually or in combination of two or more.

[0069] Examples of polyhydric alcohols include the following compounds: alkylene glycols (ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol); alkylene ether glycols (polyethylene glycol and polypropylene glycol); alicyclic diols (1,4-cyclohexanedimethanol); bisphenols (bisphenol A); and alkylene oxide (ethylene oxide and propylene oxide) adducts of alicyclic diols. The alkyl portions of alkylene glycols and alkylene ether glycols may be linear or branched. Furthermore, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol are also examples. These may be used individually or in combination of two or more.

[0070] Furthermore, monohydric acids such as acetic acid and benzoic acid, and monohydric alcohols such as cyclohexanol and benzyl alcohol may be used as needed to adjust the acid value and hydroxyl value.

[0071] The method for producing the polyester resin is not particularly limited, but for example, the transesterification method or the direct polycondensation method can be used alone or in combination.

[0072] The method for introducing the structure represented by formula (5) above into resin A is not particularly limited, but one method is to add a silane coupling agent having a vinyl polymerizable site during polymerization of the vinyl monomer, and then condense the silane coupling agent in a subsequent manufacturing process. Specific examples of polymerizable silane coupling agents having a vinyl polymerizable site include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[0073] Another method involves reacting the epoxy group of an epoxysilane compound with the carboxyl group of resin A to introduce a silanol structure, followed by condensation of a silane coupling agent in a subsequent manufacturing process. Specific examples of epoxysilane compounds include 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

[0074] Another method involves reacting the amino group of an aminosilane compound with the carboxyl group of resin A to introduce a silanol structure, followed by condensation of a silane coupling agent in a subsequent manufacturing process. Specific examples of aminosilane compounds include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-2-(aminoethyl)-3-aminopropyltrimethoxysilane.

[0075] <Other binder resins and resin components> In addition to the resin A mentioned above, the toner of the present invention may use known binder resins such as a polymer of (meth)acrylate lauryl and the vinyl monomer.

[0076] Furthermore, the toner of the present invention may contain resin components for various purposes other than the binder resin. Examples of usable resins include vinyl resins, polyesters, polyurethanes, epoxy resins, etc., which are not binder resins.

[0077] <Release agent> The toner may contain a release agent. The release agent is at least one selected from the group consisting of hydrocarbon waxes and ester waxes. Using hydrocarbon waxes and / or ester waxes makes it easier to ensure effective release properties.

[0078] There are no particular limitations on hydrocarbon waxes, but examples include the following:

[0079] Aliphatic hydrocarbon waxes: low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymers, Fischer-Tropsch waxes, or waxes obtained by oxidation or acid addition of these materials.

[0080] Ester waxes only need to have at least one ester bond in each molecule, and either natural or synthetic ester waxes may be used.

[0081] There are no particular limitations on ester waxes, but examples include the following:

[0082] Esters of monohydric alcohols and monocarboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate; Esters of divalent carboxylic acids and monoalcohols, such as dibehenyl sebacate; Esters of dihydric alcohols such as ethylene glycol distearate and hexanediol dibehenate with monocarboxylic acids; Esters of trihydric alcohols such as glycerol tribehenate and monocarboxylic acids; Esters of tetrahydric alcohols such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate with monocarboxylic acids; Esters of hexahydritol alcohols such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabéhenate with monocarboxylic acids; Esters of polyfunctional alcohols such as polyglycerin behenates and monocarboxylic acids; natural ester waxes such as carnauba wax and rice wax; Among these, esters of hexavalent alcohols and monocarboxylic acids, such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabéhenate, are preferred.

[0083] The release agent may be a hydrocarbon wax or an ester wax alone, or a combination of hydrocarbon wax and an ester wax, or a mixture of two or more types. It is particularly preferable to use a hydrocarbon wax alone or two or more types. It is even more preferable that the release agent is a hydrocarbon wax.

[0084] In toner, the content of the release agent in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, and more preferably 2.0% by mass or more and 25.0% by mass or less. Having the release agent content in the toner particles within this range makes it easier to ensure release properties during fixing.

[0085] The melting point of the release agent is preferably between 60°C and 120°C. A melting point within this range allows the release agent to melt during fixing and easily seep onto the toner particle surface, thus facilitating release properties. More preferably, the melting point is between 70°C and 100°C.

[0086] <Coloring agent> The toner may contain a colorant. Examples of colorants include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic particles. Other colorants conventionally used in toners may also be used.

[0087] Examples of yellow colorants include: condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, CI Pigment Yellows 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, and 180 are preferably used.

[0088] Examples of magenta colorants include: condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolon compounds, thioindigo compounds, and perylene compounds. Specifically, CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254 are preferably used.

[0089] Examples of cyanide colorants include: copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, CI pigment blues 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66 are preferably used.

[0090] The colorants are selected based on their hue angle, saturation, brightness, lightfastness, OHP transparency, and dispersibility in toner.

[0091] The coloring agent content is preferably 1.0 part by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of the binder resin. When magnetic particles are used as the coloring agent, their content is preferably 40.0 parts by mass or more and 150.0 parts by mass or less per 100.0 parts by mass of the binder resin.

[0092] <Charge control agent> A charge control agent may be incorporated into the toner particles as needed. Alternatively, the charge control agent may be added externally to the toner particles. By incorporating a charge control agent, the charge characteristics can be stabilized, and the optimal amount of triboelectric charge can be controlled according to the developing system.

[0093] Known charge control agents can be used, and charge control agents that have a fast charging speed and can stably maintain a constant amount of charge are particularly preferred.

[0094] Examples of charge control agents that control the toner's charge to match the load charge include the following: Organometallic compounds and chelate compounds are effective, and examples include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, and oxycarboxylic acid and dicarboxylic acid-based metal compounds.

[0095] Examples of substances that control the toner's positive charge include: nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganosucroses, guanidine compounds, and imidazole compounds.

[0096] The charge control agent content is preferably 0.01 parts by mass to 20.0 parts by mass, and more preferably 0.5 parts by mass to 10.0 parts by mass, per 100.0 parts by mass of toner particles.

[0097] <External additives> The toner particles can be used as is as toner, or, if necessary, external additives can be mixed in and attached to the surface of the toner particles to create toner.

[0098] Examples of external additives include inorganic fine particles selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, or composite oxides thereof. Examples of composite oxides include silica-aluminum fine particles and strontium titanate fine particles.

[0099] The content of the external additive is preferably 0.01 parts by mass or more and 8.0 parts by mass or less per 100 parts by mass of toner particles, and more preferably 0.1 parts by mass or more and 4.0 parts by mass or less.

[0100] <Toner manufacturing method> The toner particles of the present invention may be manufactured by any of the conventionally known methods, such as suspension polymerization, emulsification and agglutination, dissolution and suspension, or pulverization, as long as they are within the scope of the present configuration, but it is preferable that they be manufactured by suspension polymerization.

[0101] I will now describe the suspension polymerization method in detail.

[0102] For example, a pre-synthesized resin A is added to a mixture of polymerizable monomers that produce an amorphous resin. If necessary, other materials such as colorants, release agents, and charge control agents are added and uniformly dissolved or dispersed to prepare a polymerizable monomer composition.

[0103] Subsequently, the polymerizable monomer composition is dispersed in an aqueous medium using a stirrer or the like to prepare suspended particles of the polymerizable monomer composition. Then, toner particles are obtained by polymerizing the polymerizable monomers contained in the particles with an initiator or the like.

[0104] After polymerization is complete, the toner particles should be filtered, washed, and dried by known methods, and external additives may be added as needed to obtain toner.

[0105] A known polymerization initiator can be used as the polymerization initiator.

[0106] Examples of azo or diazo polymerization initiators include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile; and peroxide polymerization initiators such as benzoyl peroxide, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutylate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

[0107] In addition, known chain transfer agents and polymerization inhibitors may be used.

[0108] The aqueous medium may contain an inorganic or organic dispersion stabilizer. Known dispersion stabilizers can be used as the dispersion stabilizer.

[0109] Examples of inorganic dispersion stabilizers include phosphates such as hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; metal hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; sulfates such as calcium sulfate and barium sulfate; calcium metasilicate; bentonite; silica; and alumina.

[0110] On the other hand, examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, polyacrylic acid and its salts, and starch.

[0111] When using inorganic compounds as dispersion stabilizers, commercially available compounds may be used as is, but in order to obtain finer particles, the inorganic compounds may be generated in an aqueous medium before use.

[0112] For example, in the case of calcium phosphate such as hydroxyapatite or tricalcium phosphate, it is best to mix the phosphate aqueous solution with the calcium salt aqueous solution under high stirring.

[0113] The aqueous medium may contain a surfactant. Known surfactants can be used as the surfactant. Examples include anionic surfactants such as sodium dodecylbenzene sulfate and sodium oleate; cationic surfactants; amphoteric surfactants; and nonionic surfactants.

[0114] [Method for measuring the physical properties of the toner of the present invention] The following describes the calculation and measurement methods for various physical properties of toner and toner materials.

[0115] <Method for measuring storage modulus G' and tanδ> In this invention, the storage modulus G' and tanδ are measured using a viscoelasticity measuring device (rheometer) ARES (manufactured by Rheometrics Scientific). The general procedure for the measurement is described in the ARES operating manuals 902-30004 (August 1997 edition) and 902-00153 (July 1993 edition) published by Rheometrics Scientific, and is as follows. • Measuring jig: Torsion rectangular • Measurement sample: For the toner, a rectangular parallelepiped sample with a width of approximately 12 mm, a height of approximately 20 mm, and a thickness of approximately 2.5 mm is prepared using a pressure molding machine (maintaining 25 kN for 30 minutes at room temperature). The pressure molding machine used is the NPa Systems 100kN press NT-100H.

[0116] After leaving the jig and the sample at room temperature (23°C) for 1 hour, attach the sample to the jig. As shown in Fig. 1, fix it so that the width of the measurement part is about 12 mm, the thickness is about 2.5 mm, and the height is 10.0 mm. After adjusting the temperature to 30°C over 10 minutes, perform the measurement with the following settings. · Measurement frequency: 6.28 rad / s · Setting of measurement strain: Set the initial value to 0.1%, and perform the measurement in the automatic measurement mode. · Elongation correction of sample: Adjust in the automatic measurement mode. · Measurement temperature: Increase the temperature from 30°C to 150°C at a rate of 2°C per minute. · Measurement interval: Every 30 seconds, that is, measure the viscoelastic data every 1°C.

[0117] Transfer the data through the interface to RSI Orchesrator (control, data collection and analysis software) (manufactured by Rheometrics Scientific) operating on Windows (registered trademark) 2000 manufactured by Microsoft.

[0118] Among the measurement data, the temperature at which the storage modulus G' becomes 1.0×10 7 Pa is T1 [°C], the temperature at which the storage modulus G' becomes 3.0×10 7 Pa is T2 [°C], and the temperature at which the storage modulus G' becomes 3.0×10 6 Pa is T3 [°C]. Also, let the ratio (tanδ) of the loss modulus G'' to the storage modulus G' at the temperature T1 [°C] be tanδ(T1), and the tanδ at the temperature T1 - 10 [°C] be tanδ(T1 - 10).

[0119] <Method for Measuring the Mass of Silicon Derived from the Siloxane Structural Site of THF-Insoluble Content> The mass of silicon derived from the siloxane site in the THF-insoluble content can be measured using a thermal analyzer, TGA7, manufactured by PerkinElmer.

[0120] Heat the THF-insoluble content at a heating rate of 25°C / min from 50°C to 900°C, and take the reduced silicon mass as the Si mass derived from the siloxane structure.

[0121] The silicon content in the THF-insoluble fraction before and after the decrease is measured using X-ray fluorescence.

[0122] The measurement of X-ray fluorescence will conform to JIS K 0119-1969, specifically as follows: The measurement equipment used will be the wavelength-dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and the accompanying dedicated software "SuperQ ver.5.0L" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data.

[0123] The anode of the X-ray tube will be Rh, the measurement atmosphere will be vacuum, and the measurement diameter (collimator mask diameter) will be 27 mm. The measurement will be performed using the Omnian method to measure elements from F to U. Light elements will be detected using a proportional counter (PC), and heavy elements will be detected using a scintillation counter (SC).

[0124] Furthermore, the acceleration voltage and current values ​​of the X-ray generator are set to an output of 2.4kW (voltage 32kV, current 125mA). As the measurement sample, 4g of THF-insoluble material is placed in a dedicated aluminum ring for pressing, leveled, and then pressed at 20MPa for 60 seconds using a tablet molding compressor "BRE-32" (manufactured by Maekawa Testing Machinery Co., Ltd.) to form pellets with a thickness of 2mm and a diameter of 39mm.

[0125] The pellets formed under the above conditions are irradiated with X-rays, and the resulting characteristic X-rays (fluorescent X-rays) are spectrally analyzed using a spectrometer. Next, the intensity of the fluorescent X-rays spectrally separated at angles corresponding to the wavelengths specific to each element contained in the sample is analyzed using the FP method (fundamental parameter method). This allows the content ratio of each element in the THF insoluble matter to be obtained as an analysis result, and the content of silicon atoms in the THF insoluble matter is determined.

[0126] <Method for measuring THF-insoluble content in toner> Weigh approximately 1.5g of toner (W1g) and place it in a pre-weighed cylindrical filter paper (for example, product name No. 86R (size 28 x 100mm), manufactured by Advantec Toyo Co., Ltd.) and set it in a Soxhlet extractor. Extract using 200ml of tetrahydrofuran (THF) as the solvent for 20 hours, performing the extraction at a reflux rate such that the solvent extraction cycle occurs approximately once every 5 minutes.

[0127] After extraction is complete, the cylindrical filter paper is removed and air-dried, then vacuum-dried at 40°C for 8 hours. The mass of the cylindrical filter paper containing the extraction residue is weighed, and the mass of the extraction residue (W2g) is calculated by subtracting the mass of the cylindrical filter paper.

[0128] Next, the content of components other than resin (W3g) is determined by the following procedure. Approximately 2g of toner is weighed (Wag) into a pre-weighed 30ml magnetic crucible. The crucible is placed in an electric furnace and heated at approximately 900°C for approximately 3 hours, then allowed to cool in the electric furnace, and then allowed to cool at room temperature in a desiccator for at least 1 hour. The mass of the crucible containing the incineration residue ash is weighed, and the incineration residue ash (Wbg) is calculated by subtracting the mass of the crucible. Then, the mass of incineration residue ash in 1g of material W (W3g) is calculated using the following formula (A). W3 = W1 × (Wb / Wa) (A)

[0129] In this case, the THF-insoluble portion can be calculated using the following formula (B). THF insoluble content (mass%)={(W2-W3) / (W1-W3)}×100 (B)

[0130] <Method for verifying the structure of formula (5) in resin A> The structure of formula (5) contained in resin A is confirmed using nuclear magnetic resonance (NMR) spectroscopy.

[0131] Samples for NMR measurement are prepared as follows:

[0132] Preparation of the measurement sample: Weigh 10.0 g of resin A, place it in cylindrical filter paper (Toyo Filter Paper Co., Ltd. No. 86R), and place it in a Soxhlet extractor. Extraction is carried out for 20 hours using 200 ml of tetrahydrofuran as the solvent, and the filtered material in the cylindrical filter paper is vacuum dried at 40°C for several hours to obtain the sample for NMR measurement.

[0133] In the structure represented by equation (5), the X bonded to the silicon atom is: 13 Confirmation is performed by 13C-NMR (solid-state) measurement. The measurement conditions are shown below.

[0134] " 13 Measurement conditions for C-NMR (solid state) Equipment: JEOL RESONANCE JNM-ECX500II Sample tube: 3.2mmφ Sample: 150 mg of tetrahydrofuran-insoluble matter from toner particles for NMR measurement. Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 123.25MHz (13C) Reference substance: Adamantane (external standard: 29.5ppm) Sample rotation speed: 20kHz Contact time: 2ms Delay time: 2 seconds Total number of times: 1024

[0135] Of the structures represented by formula (5), the siloxane bond portion is as follows: 29 This was confirmed by Si-NMR (solid-state) measurement. The measurement conditions are shown below.

[0136] " 29 Measurement conditions for Si-NMR (solid state) Equipment: JEOL RESONANCE JNM-ECX500II Sample tube: 3.2mmφ Sample: 150 mg of tetrahydrofuran-insoluble matter from toner particles for NMR measurement. Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 97.38MHz ( 29 Si) Reference material: DSS (external standard: 1.534ppm) Sample rotation speed: 10kHz Contact time: 10ms Delay time: 2 seconds Cumulative number of times: 2000-8000

[0137] <Method for measuring the molecular weight of toner> The molecular weight (weight-average molecular weight Mw) of the THF-soluble component of toner is measured by gel permeation chromatography (GPC) as follows.

[0138] First, the toner is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution is then filtered through a solvent-resistant membrane filter, "Myshoridisk" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm, to obtain the sample solution. The sample solution is adjusted so that the concentration of THF-soluble components is 0.8% by mass. This sample solution is then used for measurement under the following conditions. • Equipment: HLC8120 GPC (Detector: RI) (Manufactured by Tosoh Corporation) • Columns: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko) • Eluent: Tetrahydrofuran (THF) ·Flow rate: 1.0ml / min Oven temperature: 40.0℃ • Sample injection volume: 0.10 ml

[0139] To calculate the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (for example, "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0140] <Method for separating resin A from toner> The separation of resin A from toner can be done by known methods, and one example is shown below.

[0141] Gradient LC is used as a method for separating resin components from toner. This analysis allows for separation based on the polarity of the resin in the binder resin, regardless of molecular weight.

[0142] First, the toner was dissolved in chloroform. The sample was adjusted to a sample concentration of 0.1% by mass using chloroform, and the solution was filtered through a 0.45 μm PTFE filter before being used for measurement. The measurement conditions for gradient polymer LC are shown below. Equipment: UlTIMATE3000 (manufactured by Thermo Fisher Scientific) Mobile phase: A. Chloroform (HPLC), B. Acetonitrile (HPLC) Gradient: 2 min (A / B=0 / 100) → 25 min (A / B=100 / 0) (Note that the gradient of the mobile phase change was made to be a straight line.) Flow rate: 1.0mL / min Injection: 0.1% by mass x 20μL Column: Tosoh TSKgel ODS (4.6mmφ x 150mm x 5μm) Column temperature: 40℃ Detector: Corona Charged Particle Detector (Corona-CAD) (manufactured by Thermo Fisher Scientific)

[0143] The time-intensity graph obtained from the measurement shows that the resin component can be separated into two peaks depending on its polarity. Subsequently, by repeating the above measurement and separating the samples at the time of the trough of each peak, it is possible to separate them into two types of resin. DSC measurement is performed on the separated resins, and the resin with a melting point peak is designated as resin A.

[0144] Furthermore, if the toner contains a release agent, it is necessary to separate the release agent from the toner. The release agent is separated by recycled HPLC, which separates components with a molecular weight of 2000 or less as the release agent. The measurement method is as follows. First, a chloroform solution of the toner is prepared using the method described above. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshoridisk" (manufactured by Tosoh Corporation) with a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in chloroform is 1.0 mass%. This sample solution is used for measurement under the following conditions. ·Equipment: LC-Sakura NEXT (manufactured by Nippon Analytical Industry Co., Ltd.) • Columns: JAIGEL2H, 4H (manufactured by Nippon Analytical Engineering Co., Ltd.) • Eluent: Chloroform ·Flow rate: 10.0ml / min Oven temperature: 40.0℃ • Sample injection volume: 1.0 ml

[0145] To calculate the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (for example, "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0146] From the molecular weight curve obtained in this way, components with a molecular weight of 2000 or less are repeatedly separated, and the release agent is removed from the toner.

[0147] <Method for measuring the content ratio of various monomer units in resin> The measurement of the content ratio of various monomer units in the resin is performed as follows: 1 The procedure is performed using H-NMR under the following conditions. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 Measurement temperature: 30℃ Sample: Place 50 mg of the sample to be measured into a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as a solvent, and dissolve in a constant temperature bath at 40°C to prepare the sample. 1 The H-NMR chart is analyzed to identify the structure of each monomer unit. Here, as an example, the measurement of the content of monomer unit (a) in crystalline resin A is described. 1 In the 1H-NMR chart, a peak independent of the peaks attributed to the components of monomer unit (a) is selected from among the peaks attributed to the components of the other monomer units, and the integral value S1 of this peak is calculated. The integral values ​​are calculated similarly for each of the other monomer units contained in resin A.

[0148] If the monomer units constituting resin A consist of monomer unit (a) and one other monomer unit, the content ratio of monomer unit (a) is determined as follows using the integral value S1 and the integral value S2 of the peak of the other monomer unit. Note that n1 and n2 are the number of hydrogen atoms in the constituent element to which the peak of interest belongs for each part. Percentage of monomer unit (a) (mol%) = {(S1 / n1) / ((S1 / n1)+(S2 / n2))}×100

[0149] The content ratio of monomer unit (a) can be calculated similarly even if there are two or more other monomer units.

[0150] Furthermore, if a polymerizable monomer is used in which no hydrogen atoms are present in any component other than the vinyl group, 13 The atomic nuclei to be measured using C-NMR 13 Let C be used, and the measurement will be performed in single-pulse mode. 1 The same calculation is performed using 1H-NMR. The percentage (mol%) of each monomer unit calculated by the above method is multiplied by the molecular weight of each monomer unit to convert the content of each monomer unit into mass%. [Examples]

[0151] The present invention will be described in detail below with reference to examples, but these examples are not intended to limit the present invention in any way. In the following formulations, parts are by mass unless otherwise specified.

[0152] (Preparation of resin A1) The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. • Toluene 100,000 copies • Monomer composition 100,000 parts (The monomer composition shall be a mixture of the following monomers in the proportions shown below.) Behenyl acrylate (monomer (a)) 80,000 parts • Styrene 18,000 units • Methacrylic acid 2,000 parts • 3-Methacryloxypropyltrimethoxysilane 2.036 parts • Polymerization initiator: t-butyl peroxypivalate (manufactured by NOF Corporation: perbutyl PV) 0.500 copies The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer polymer was dissolved in toluene. Subsequently, the solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain resin A1.

[0153] (Preparation of resins A2 to A14) Resins A2 to A14 were prepared in the same manner as in the preparation of resin A1, except that the amount of each component added to the monomer composition was changed to that shown in Table 1.

[0154] [Table 1]

[0155] [ka]

[0156] (Preparation of resin B1) The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. • Toluene 100.0 parts • Monomer composition 100.0 parts (The monomer composition shall be a mixture of the following monomers in the proportions shown below.) • Lauryl acrylate (monomer (b)) 25.0 parts • Styrene 75.0 parts • Polymerization initiator: t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 0.5 parts The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer polymer was dissolved in toluene. Subsequently, the solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain resin B1.

[0157] (Preparation of resins B2 to B7) Resins B2 to B7 were prepared in the same manner as resin B1, except that the amounts of each component of the monomer composition were changed as shown in Table 2. For resins B4 and B7, a predetermined amount of crosslinking agent (HDDA; 1,6-hexanediol-diacrylate) was added.

[0158] [Table 2]

[0159] <Example 1> [Toner manufacturing by suspension polymerization method] (Manufacturing of toner particles 1) • Lauryl acrylate (monomer (b)) 15.0 parts • Styrene 45.0 parts • Coloring agent: Pigment Blue 15:3 6.5 parts A mixture consisting of the above was prepared. The above mixture was placed in an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed using 5 mm diameter zirconia beads at 200 rpm for 2 hours to obtain a raw material dispersion.

[0160] Meanwhile, 735.0 parts of deionized water and 16.0 parts of trisodium phosphate (dodecahydrate) were added to a container equipped with a high-speed stirring device homomixer (Primix Corporation) and a thermometer, and the temperature was raised to 60°C while stirring at 12,000 rpm. Then, an aqueous calcium chloride solution, prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of deionized water, was added, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining the temperature at 60°C. Then, 10% hydrochloric acid was added to adjust the pH to 6.0, obtaining an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.

[0161] Next, the above raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and heated to 60°C while being stirred at 100 rpm. • Resin A1 40.0 parts ·Resin B1 60.0 parts • Release agent 1 9.0 parts (Release agent 1: DP18 (Dipentaerythritol stearate wax, melting point 79°C, manufactured by Nippon Seiro Co., Ltd.) After adding the mixture and stirring at 100 rpm for 30 minutes while maintaining a temperature of 60°C, 9.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) were added as a polymerization initiator and stirred for another minute. Subsequently, the mixture was added to an aqueous medium being stirred at 12000 rpm using the high-speed stirring device described above. Stirring was continued at 12000 rpm for 20 minutes while maintaining a temperature of 60°C using the high-speed stirring device described above to obtain a granulated liquid.

[0162] The granulated liquid described above was transferred to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube, and heated to 70°C while stirring at 150 rpm under a nitrogen atmosphere. The polymerization reaction was carried out at 150 rpm for 12 hours while maintaining the temperature at 70°C to obtain a toner particle dispersion.

[0163] The obtained toner particle dispersion was cooled to 45°C while being stirred at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. After that, while maintaining stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid components were filtered off, thoroughly washed with deionized water, and then vacuum-dried at 30°C for 24 hours to obtain toner particles 1.

[0164] (Preparation of Toner 1) For the above toner particles in a 1:98.0 ratio, silica microparticles (hydrophobized with hexamethyldisilazane, primary particle number average particle size: 10 nm, BET specific surface area: 170 m²) are used as an external additive. 2 2.0 parts of ( / g) were added and mixed for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain Toner 1. The physical properties of the obtained Toner 1 are shown in Table 4.

[0165] <Examples 2-19> In Example 1, toner particles 2 to 19 were obtained in the same manner as in Example 1, except that the types and amounts of resins A and B used were changed as shown in Table 3.

[0166] Furthermore, toners 2-19 were obtained by performing the same external additive procedure as in Example 1. The physical properties of the toners are shown in Table 4.

[0167] <Comparative Examples 1-11> Comparative toner particles 1 to 11 were obtained in the same manner as in Example 1, except that the types and amounts of resins A and B used were changed as shown in Table 3.

[0168] Furthermore, comparative toners 1 to 11 were obtained by performing the same external additive procedure as in Example 1. The physical properties of the toners are shown in Table 4.

[0169] <Comparative Example 12> In Example 1, comparative toner particles 12 were obtained in the same manner as in Example 1, except that 3-methacryloxypropyltrimethoxysilane was removed from resin A1 and added at the start of the polymerization reaction at 70°C during toner production.

[0170] Furthermore, a comparative toner 12 was obtained by performing the same external additive procedure as in Example 1. The physical properties of the toner are shown in Table 4.

[0171] <Comparative Example 13> • Bisphenol A ethylene oxide (2.2 molar adduct): 50.0 molar parts • Bisphenol A propylene oxide (2.2 molar adduct): 50.0 molar parts Terephthalic acid: 90.0 molar parts • Trimellitus anhydride: 10.0 moles 97 parts of the above monomer for forming the polyester portion and 3 parts of silicone oil (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd.) having hydroxyl groups at both ends were mixed with 500 ppm of titanium tetrabutoxide in a 5-liter autoclave.

[0172] A reflux condenser, moisture separator, N2 gas introduction tube, thermometer, and stirring device were attached to the autoclave, and a condensation polymerization reaction was carried out at 230°C while introducing N2 gas into the autoclave. The reaction time was adjusted to achieve the desired softening point, and after the reaction was complete, the material was removed from the container, cooled, and pulverized to obtain the binder resin P1. • Solvent: Toluene 100.0 parts • Monomer composition 100.0 parts (The monomer composition is a mixture of behenyl acrylate, methacrylonitrile, and styrene in the proportions shown below.) (Behenyl acrylate (first monomer) 67.0 parts (28.9 mol%)) (Methacrylonitrile (second monomer) 22.0 parts (53.8 mol%)) (Styrene (third monomer) 11.0 parts (17.3 mol%)) • Polymerization initiator t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 0.5 parts The above materials were placed in a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer composition polymer was dissolved in toluene. Subsequently, the solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain polymer A1.

[0173] • Binding resin P1 100.0 parts • Polymer A1 5.0 parts Fischer-Tropsch wax (peak temperature of maximum endothermic peak: 90°C) 6.0 parts CI Pigment Blue 15:3 9.0 parts The raw materials shown in the formula were mixed using a Henschel mixer (FM75J model, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotation speed of 20 seconds. -1 The ingredients were mixed for a rotation time of 5 minutes. The mixed raw materials were then kneaded in a twin-shaft kneader (PCM-30 model, manufactured by Ikegai Co., Ltd.) set to a temperature of 130°C and a barrel rotation speed of 200 rpm.

[0174] The resulting mixture was cooled and coarsely ground to a size of 1 mm or less using a hammer mill to obtain a coarse material. The obtained coarse material was finely ground using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain comparative toner particles 13. The weight-average particle size (D4) of the obtained comparative toner particles 13 was 6.5 μm.

[0175] For comparison, the toner particles 13:100.0 contain hydrophobic silica (BET:200m 2 Mix 2.0g of the mixture in a Henschel mixer (FM75J model, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at 30s of rotation. -1 The mixture was mixed with a rotation time of 5 minutes. The resulting mixture was passed through an ultrasonic vibrating sieve with a mesh size of 54 μm to obtain comparative example toner 13.

[0176] The physical properties of the toner are shown in Table 4.

[0177] <Comparative Example 14> Styrene 72.1 moles Butyl acrylate 19.5 moles • Silane coupling agent 0.1 mole (Manufactured by Shin-Etsu Silicone Co., Ltd., product name: KBM503) A monomer mixture consisting of the above composition was subjected to radical polymerization to produce high-molecular-weight and low-molecular-weight compounds with the following molecular weights. High molecular weight Mw=9.0×10 5 Mn = 3.9 × 10 5 Low molecular weight substance Mw=8.0×10 3 Mn = 2.7 × 10 3 Next, the obtained high molecular weight and low molecular weight materials were mixed in a ratio of low molecular weight material:high molecular weight material = 70:30 to obtain styrene-butyl acrylate-silane copolymer resin A.

[0178] The raw materials, consisting of the following composition, were mixed in a super mixer, melt-kneaded, and then pulverized and classified to obtain negatively charged toner matrix particles (comparative toner particles 14) with a weight-average particle size (D4) of 11.0 μm. 100 parts of styrene-butyl acrylate-silane copolymer resin A Carbon black (MA-100, manufactured by Mitsubishi Chemical Industries, Ltd.) 6.5 parts Chromium-containing metal dye (S-34, manufactured by Orient Chemical Industry Co., Ltd.) 2.0 parts Polypropylene 3.0 parts Subsequently, using a Henschel mixer, 0.3 parts of hydrophobic silica (R-972, manufactured by Nippon Aerosil Co., Ltd.) was applied to the surface of 100 parts of the obtained comparative toner particles 14 to obtain comparative toner 14.

[0179] The physical properties of the toner are shown in Table 4.

[0180] [Table 3]

[0181] [Table 4]

[0182] [Toner Evaluation Method] The performance evaluations for toners 1-19 related to Examples 1-19 and comparative toners 1-14 related to Comparative Examples 1-14 were performed according to the following procedures.

[0183] <1> Low-temperature fixation A process cartridge filled with toner was left at 25°C and 40% RH for 48 hours. Using an LBP-712Ci modified to operate without the fuser, an unfixed image was printed with an image pattern consisting of 10mm x 10mm squares evenly distributed at 9 points across the entire transfer paper. The amount of toner adhering to the transfer paper was 0.80 mg / cm². 2 The fixing start temperature was then evaluated. The transfer paper used was A4 paper equivalent to rough paper ("Proverbond paper": 105g / m²). 2 (Fox River Industries) was used.

[0184] For the fuser, an external fuser was used, which was created by removing the fuser unit from the LBP-712Ci and operating it outside the laser beam printer. The external fuser performed the fixing process at a process speed of 260 mm / sec, with the fixing temperature gradually increased in 5°C increments starting from 90°C.

[0185] The fixed image was visually inspected, and the lowest temperature at which no cold offset occurred was defined as the fixing start temperature. Low-temperature fixing performance was evaluated according to the following criteria. The evaluation results are shown in Table 5.

[0186] [Evaluation Criteria] A: Fixation start temperature is 100°C or lower B: Fixation start temperature is between 105°C and 110°C. C: Fixing start temperature is 115°C or higher but less than 120°C D: Fixing start temperature is 125°C or higher

[0187] <2> Evaluation of gloss and gloss unevenness In the evaluation of <1> above, the fixing image at the fixing start temperature was used. The gloss value was measured using a handy gloss meter PG-1 (manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement conditions were set such that the light projection angle and the light reception angle were each 75°, all of the 9-point arrayed image patterns were measured, and the average value thereof was evaluated. Also, the standard deviation of the measured values was used as the evaluation of gloss unevenness. The evaluation results are shown in Table 5.

[0188] [Gloss Evaluation Criteria] A: The average value of gloss is 25.0 or more B: The average value of gloss is 20.0 or more and less than 25.0 C: The average value of gloss is 15.0 or more and less than 20.0 D: The average value of gloss is less than 15.0

[0189] [Gloss Unevenness Evaluation Criteria][[ID=?]] A: The standard deviation of gloss is 1.00 or less B: The standard deviation of gloss exceeds 1.00 and is 2.00 or less C: The standard deviation of gloss exceeds 2.00 and is 3.00 or less D: The standard deviation of gloss exceeds 3.00

[0190] <3>Evaluation of Hot Offset Under the environment of normal temperature and normal humidity (25°C / 50%RH), at a process speed of 260 mm / sec, the fixing temperature was changed in increments of 10°C, and a solid image (toner loading amount: 0.9 mg / cm [[ID=?]] 2 ) was formed. The transfer paper used was ordinary paper (XEROX 4200 paper of LETTER size, manufactured by XEROX, 75 g / m [[ID=?]] 2 ). The hot offset resistance was evaluated visually. In the present invention, C or more was judged as good. The evaluation results are shown in Table 5.

[0191] [Evaluation Criteria] A: Offset occurs at 160°C or higher B: Offset occurs at 150°C or higher and less than 160°C C: Offset occurs at 140°C or higher and less than 150°C D: Offset occurs at less than 140°C It should be noted that there are some "?" in the translation where the original tags seem to be incomplete or incorrect in the provided text. Please check and correct the original text for a more accurate translation.

[0192] Table 5

Claims

1. A toner having toner particles containing resin A as a binder resin, The aforementioned resin A has a structure represented by the following formula (5): 【Chemistry 1】 In formula (5) above, n represents an integer between 1 and 10, In formula (5) above, X independently represents a hydrogen atom, a hydroxyl group, an alkoxyl group, or an alkyl group. In formula (5) above, A contains 30% by mass or more of unit (a) represented by the following formula (1), 【Chemistry 2】 R in formula (1) 1 This represents a hydrogen atom or a methyl group. L in formula (1) 1 This represents a single bond, an ester bond, or an amide bond. In formula (1) above, m represents an integer between 15 and 30, The content of resin A in the toner, based on the mass of the toner, is 20.0% by mass or more and 100.0% by mass or less. In the viscoelasticity measurement of the toner, the storage modulus G' of the toner was found to be 1.0 × 10⁻⁶. 7 Let T1 [°C] be the temperature at which Pa occurs, let tanδ(T1) be the ratio of the loss modulus G'' of the toner at temperature T1 [°C] to the storage modulus G', and let tanδ(T1-10) be the ratio of the loss modulus G'' of the toner at temperature T1-10 [°C] to the storage modulus G', then the toner satisfies the following equations (2) to (4), 50.0 ≤ T1 ≤ 70.0 (2) 0.30≦tanδ(T1)≦1.00 (3) 1.00≦tanδ(T1) / tanδ(T1-10)≦1.90 (4) The toner contains THF-insoluble components, The THF-insoluble portion includes the structure represented by formula (5) of the resin A, Using a PerkinElmer TGA7 thermal analyzer, the THF-insoluble matter was heated from 50°C to 900°C at a heating rate of 25°C / min, and the reduced mass of silicon was taken as the mass of silicon derived from the siloxane structure in the structure represented by formula (5). In this case, the mass of silicon derived from the siloxane structure was 0.005% or more and 0.150% or less of the THF-insoluble matter. A toner characterized by the following features.

2. The toner according to claim 1, wherein A in formula (5) contains 50.0% by mass or more and 90.0% by mass or less of the unit (a).

3. In the viscoelasticity measurement of the toner, the storage modulus G' of the toner is 3.0 × 10 7 Let T2 [°C] be the temperature at which it becomes Pa, and let the storage modulus G' of the toner be 3.0 × 10⁻⁶. 6 The toner according to claim 1 or 2, wherein when the temperature at which Pa is reached is T3 [°C], the toner satisfies the following formula (6). |T3-T2|≦10.0 (6)

4. The toner according to claim 1, wherein n in formula (5) is 1.

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