toner

Abstract

To provide a toner that has good low temperature fixability and hot offset resistance, and can maintain its fast fixing speed even after storage in a high temperature environment.SOLUTION: A toner contains a toner particle containing a binder resin and a mold release agent. The binder resin contains a crystalline vinyl resin. The crystalline vinyl resin contains a monomer unit (a) represented by the following formula (1) in an amount of 5.0 mass% or more with respect to the mass of the crystalline vinyl resin. In the formula (1), at least two of R1-R4 are each independently -X-COOR5, and the remainder are each independently a hydrogen atom or an alkyl group having 1-4 carbon atoms. X is a single bond or an alkylene group having 1 or 2 carbon atoms. R5 is an alkyl group having 16-30 carbon atoms. The peak molecular weight Mp of the mold release agent is 800 or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a toner used in electrophotography and electrostatic recording methods.

Background Art

[0002] Methods for visualizing image information using toner such as electrophotography are currently used in various fields, and improvements in performance such as higher image quality and energy savings are required. In electrophotography, first, an electrostatic latent image is formed on an electrophotographic photoreceptor (image holding member) by a charging and exposure process. Next, the electrostatic latent image is developed with a developer containing toner, and a visualized image (fixed image) is obtained through a transfer process and a fixing process.

[0003] Among them, the fixing process is a process that requires relatively a lot of energy, and the development of a system and materials that achieve both energy savings and higher image quality has become an important technical issue. As an approach from the material aspect, a technique of using a crystalline resin for the binder resin of the toner has been studied. Crystalline resins have excellent heat storage stability because the molecular chains are regularly arranged and hardly soften at temperatures lower than the melting point. On the other hand, when the melting point is exceeded, the crystals rapidly melt, accompanied by a rapid decrease in viscosity. Therefore, crystalline resins are attracting attention as materials with excellent sharp meltability and low-temperature fixability.

[0004] Known crystalline resins include main-chain crystalline resins in which the main chain crystallizes, typified by crystalline polyesters, and side-chain crystalline resins in which the side chains crystallize, typified by long-chain alkyl acrylate polymers. Among them, side-chain crystalline resins are known to exhibit excellent low-temperature fixability because they are easy to increase the degree of crystallinity and have been widely studied. Examples of side-chain crystalline resins include crystalline vinyl resins. Crystalline vinyl resins have a long-chain alkyl group as a side chain, and exhibit crystallinity by the orientation of the long-chain alkyl groups in the side chains.

[0005] In Patent Document 1, as a toner using a crystalline vinyl resin, a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group and an amorphous polymerizable monomer having a different SP value is used, and a release agent having a molecular weight of 1000 or more is used. By controlling the SP value, the polymerizable monomer having a long-chain alkyl group is bonded continuously to some extent, so that the crystallinity of the crystalline vinyl resin is likely to be maintained. In addition, in order to reduce the compatibility with the crystalline vinyl resin during fixing, by using a release agent having a molecular weight of 1000 or more, it is said that both low-temperature fixability, heat-resistant storage stability, durability, and releasability can be achieved.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] The technology of Patent Document 1 is an excellent technology for achieving both low-temperature fixability, heat-resistant storage stability, durability, and releasability. Furthermore, in recent years, with various usage scenarios assumed, in order to improve productivity during printer use, an improvement in the speed of the printing process is required, and in particular, the demand for improving the fixing speed is increasing. As a result of investigations by the present inventors, it has been found that since the toner of the conventional technology is excellent in low-temperature fixability, it can also cope with a fixing process set at high speed. On the other hand, regarding the toner of Patent Document 1, when the adaptability to a high-speed fixing process is confirmed after storage in a high-temperature environment, it does not fix at the same fixing speed and the fixing speed for achieving the same fixing temperature is found to decrease.

[0008] For this reason, the following speculation is made. The toner of Patent Document 1 is characterized in that the crystalline resin contains a (meth)acrylate structure having a long-chain alkyl group as a side chain. Such a crystalline resin is hard below the melting point. However, at the molecular level, molecular motion may occur in some cases. Particularly at high temperatures, molecular motion is likely to be activated. The toner of Patent Document 1 has excellent heat-resistant storage properties, and aggregation of the toners during high-temperature storage can be suppressed. However, it is considered that molecular motion inside the toner cannot be completely suppressed, and when stored in a high-temperature environment, some crystals have changed. These partial crystals cause molecular motion and form a eutectic state with a release agent having a similar crystal structure in the toner. From these points, the inventors of the present invention consider the reason for the change in the fixing property after storage compared to before storage in a high-temperature environment as follows. It is considered that the release agent and the crystalline vinyl resin in the toner easily form a eutectic, the release agent is trapped by the binder resin, and the rate of bleeding of the release agent during high-speed fixing is reduced.

[0009] The present disclosure provides a toner having excellent low-temperature fixing property and hot offset resistance (release property), and further having a fixing rate that does not change even after storage in a high-temperature environment.

Means for Solving the Problems

[0010] The toner according to the present disclosure is a toner containing toner particles containing a binder resin and a release agent, the binder resin contains a crystalline vinyl resin, the crystalline vinyl resin contains 5.0% by mass or more of a monomer unit (a) represented by the following formula (1) based on the mass of the crystalline vinyl resin,

Chemical formula

Advantages of the Invention

[0011] According to the present disclosure, it is possible to provide a toner having excellent low-temperature fixability and hot offset resistance, and further having a constant fixing speed even after storage in a high-temperature environment.

Brief Description of the Drawings

[0012]

Figure 1

Modes for Carrying Out the Invention

[0013] In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range including the lower limit and the upper limit which are the endpoints, unless otherwise specified. Further, when the numerical ranges are described stepwise, the upper limit and the lower limit of each numerical range can be arbitrarily combined. Further, in the present disclosure, for example, the description such as "selected from the group consisting of XX, YY, and ZZ at least one" means any one 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. (Meth)acrylic acid ester means acrylic acid ester and / or methacrylic acid ester.

[0014] "Monomer unit" refers to the reacted form of the monomer substance in the polymer. For example, in the main chain in which the polymerizable monomer in the polymer has polymerized, one section of the carbon-carbon bond is taken as one unit. The polymerizable monomer can be represented by the following formula (C).

Chemical Formula

[0015] <Features of the present disclosure> As a result of extensive studies by the present inventors to solve the above problems, by combining a crystalline vinyl resin having a specific monomer unit and a release agent having a peak molecular weight Mp of 800 or more as the binder resin constituting the toner particles, it has been found that a toner excellent in low-temperature fixability and hot offset resistance can be provided, and further, the fixing rate does not change even after storage in a high-temperature environment, and the toner can be fixed at a high fixing rate.

[0016] That is, the toner of the present disclosure is a toner containing toner particles containing a binder resin and a release agent. The binder resin contains a crystalline vinyl resin. The crystalline vinyl resin contains 5.0% by mass or more of a monomer unit (a) represented by the following formula (1) based on the mass of the crystalline vinyl resin. [Chemical formula] In the formula (1), at least two of R 1 to R 4 are each independently -X-COOR 5 and the rest are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is a single bond or an alkylene group having 1 or 2 carbon atoms, and R 5 is an alkyl group having 16 to 30 carbon atoms. The peak molecular weight Mp of the release agent is 800 or more.

[0017] The present inventors consider the mechanism by which such a configuration can solve the above problems to be as follows. As described above, in the toner of the prior art, the crystalline resin that constitutes the binder resin contains a (meth)acrylate structure having a long-chain alkyl group as a side chain. In this case, storing the toner in a high-temperature environment tends to form a eutectic between the crystalline resin and the release agent. Although the binder resin contained in the toner particles is hard below its melting point or glass transition point, it is not completely immobile at the molecular level, and molecular motion can occur. This molecular motion continues at room temperature. The higher the degree, the more active it is. According to the inventor's research, when the toner is stored in a high-temperature environment, the molecular chains of both the crystalline resin and the release agent move, and a eutectic in which both are stable with each other is easily formed. As a result, the release agent is trapped in the binder resin, and it is believed that the release agent does not ooze out sufficiently during high-speed fixing.

[0018] In contrast, the toner of the present disclosure has the above-mentioned configuration. As described later, the use of a release agent having a high peak molecular weight reduces the compatibility between the crystalline vinyl resin and the release agent during fixing, thereby ensuring excellent hot offset resistance. On the other hand, crystalline vinyl resins exhibit excellent low-temperature fixability that is unique to crystalline resins. Furthermore, when the crystalline vinyl resin contains a certain amount of the monomer unit (a) represented by the above formula (1), the long-chain alkyl groups that contribute to crystallinity are close to each other. Therefore, it is considered that the crystal density is high, the degree of freedom of the molecules is reduced, and the mobility of the molecules is reduced.

[0019] Therefore, even in the case of a toner exposed to a high temperature environment, it is believed that the unintended formation of a eutectic between the crystalline vinyl resin and the release agent with a high peak molecular weight is suppressed, and the release agent and the binder resin are maintained in a phase-separated state. In such a toner with little eutectic, the release agent exists in a phase-separated state from the binder resin during fixing, and quickly seeps out onto the toner surface when melted. Therefore, it is believed that the release property is maintained even at high fixing speeds. Thus, attempts have not been made to maintain fixability even after storage in a high-temperature environment in a high-speed fixing system by controlling the crystal density based on the distance between linear alkyl groups as side chains. Based on the above mechanism, it is considered that the toner of the present disclosure can provide a toner having excellent low-temperature fixability and hot offset resistance, and further having a constant fixing speed even after storage in a high-temperature environment.

[0020] Hereinafter, the toner will be described in detail. The toner contains toner particles. The toner particles may be used as the toner as they are, or may be used as the toner by mixing external additives or the like and attaching them to the surface of the toner particles as necessary.

[0021] <Toner particles> The toner particles will be described. The toner particles contain a binder resin and a release agent. The toner particles may contain a colorant, a charge control agent, etc. in addition to the binder resin.

[0022] (Binder resin) The binder resin contains a crystalline vinyl resin, and the crystalline vinyl resin contains 5.0 mass% or more of the monomer unit (a) represented by the above formula (1) based on the mass of the crystalline vinyl resin. That is, the content ratio of the monomer unit (a) is 5.0 mass% or more based on the mass of the crystalline vinyl resin. When the content ratio (hereinafter also referred to as ratio J) of the monomer unit (a) represented by the above formula (1) based on the mass of the crystalline vinyl resin is less than 5.0 mass%, a fast fixing speed cannot be maintained after storage in a high-temperature environment.

[0023] From the viewpoint of reducing the change in the fixing speed even after storage in a high-temperature environment in a high-speed fixing system, the ratio J is preferably 30.0 mass% or more, and more preferably 45.0 mass% or more. For example, the ratio J is preferably 5.0 to 100.0 mass%, more preferably 5.0 to 90.0 mass%, still more preferably 30.0 to 90.0 mass%, and particularly preferably 45.0 to 85.0 mass%. Furthermore, from the viewpoint of reducing the change in the fixing rate even after storage in a high-temperature environment in the high-speed fixing system, the ratio J is preferably 0.7 mol% or more. For example, the ratio J is preferably 0.7 to 40.0 mol% in terms of molar ratio, more preferably 4.0 to 40.0 mol% and even more preferably 20.0 to 35.0 mol%. The method of introducing the monomer unit (a) into the crystalline vinyl resin will be described later. The ratio J can be controlled by the charged amount of raw materials during the synthesis of the crystalline vinyl resin, etc.

[0024] The crystalline vinyl resin contains the monomer unit (a) represented by the above formula (1). In the formula (1), R 1 ~R 4 Among them, at least two are each independently -X-COOR 5 (X is a single bond or an alkylene group having 1 or 2 carbon atoms, R 5 is an alkyl group having 16 to 30 carbon atoms), and the rest are each independently hydrogen or an alkyl group having 1 to 4 (preferably 1 to 2) carbon atoms.

[0025] When such a structure is satisfied, it is excellent in low-temperature fixability and hot offset resistance, and the change in the fixing rate can be reduced even after storage in a high-temperature environment in the high-speed fixing system. R 1 ~R 4 Among them, when there is one part satisfying -X-COOR 5 and the rest are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, the high fixing rate may not be maintained after storage in a high-temperature environment in the high-speed fixing system.

[0026] As a preferable substituent structure, two of R 1 ~R 4 (more preferably one of R 1 and R 2 , and one of R 3 and R 4 ) are each independently -X-COOR 5 (X is a single bond or an alkylene group having 1 or 2 carbon atoms, R5 is an alkyl group having 16 to 30 carbon atoms), and the rest are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Further, R 1 ~R 4 Among two of them (more preferably one of R 1 and R 2 and one of R 3 and R 4 ), each is independently -X-COOR 5 (X is a single bond or an alkylene group having 1 or 2 carbon atoms, and R 5 is an alkyl group having 16 to 30 carbon atoms), and the rest are more preferably a hydrogen atom or a methyl group. Also, X is preferably a single bond.

[0027] R 5 is an alkyl group having 16 to 30 carbon atoms. When R 5 is an alkyl group having 16 to 30 carbon atoms, the crystalline vinyl resin is likely to exhibit crystallinity, and a toner excellent in low-temperature fixing property can be obtained. Also, a fast fixing speed can be maintained after storage in a high-temperature environment. When R 5 has less than 16 carbon atoms, the fixing speed is likely to decrease after storage in a high-temperature environment, and when R 5 has more than 30 carbon atoms, the low-temperature fixing property is likely to decrease. R 5 is preferably an alkyl group having 18 to 28 carbon atoms, and more preferably an alkyl group having 20 to 24 carbon atoms. The alkyl group of R 5 is preferably linear.

[0028] The binder resin preferably contains 20.0% by mass or more of a crystalline vinyl resin based on the mass of the binder resin (the content ratio of the crystalline vinyl resin based on the mass of the binder resin is hereinafter also referred to as ratio I). When ratio I is 20% by mass or more, it becomes easier to achieve both low-temperature fixing properties and the effect of maintaining a fast fixing speed even after storage in a high-temperature environment. The upper limit of ratio I is not particularly limited, but for example, it is preferably 20.0 to 100.0% by mass, more preferably 20.0 to 70.0% by mass, and even more preferably 40.0 to 60.0% by mass. Ratio I can be controlled by the charged amount of the crystalline vinyl resin during toner particle production and the charged amounts of other materials.

[0029] In addition, the crystalline vinyl resin may or may not contain a monomer unit having an alkyl group with 16 to 30 carbon atoms different from monomer unit (a) in addition to monomer unit (a). In the crystalline vinyl resin, among the monomer units having an alkyl group with 16 to 30 carbon atoms including monomer unit (a), the content ratio of monomer unit (a) (hereinafter also referred to as ratio K) is preferably 50.0 to 100% by mass, more preferably 75.0 to 100.0% by mass, and even more preferably 90.0 to 100.0% by mass.

[0030] The fact that ratio K is within the above range indicates that there are many sites with a high side-chain density. Therefore, the movement of resin molecules is restricted and it becomes difficult to form a eutectic, and the change in the fixing speed can be reduced even after storage in a high-temperature environment in a high-speed fixing system.

[0031] As a method for introducing monomer unit (a) represented by formula (1) into the crystalline vinyl resin, there is a method of using a polymerizable ester, which is a condensate of a polyvalent carboxylic acid having 4 to 6 carbon atoms with a carbon-carbon double bond and a monoalcohol having a chain hydrocarbon group with 16 to 30 carbon atoms, as a polymerizable monomer. Monomer unit (a) represented by formula (1) may be used alone or in combination of two or more.

[0032] Examples of the polyvalent carboxylic acid having 4 to 6 carbon atoms and a carbon-carbon double bond include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, glutaconic acid, trans-aconitic acid, and cis-aconitic acid. Further, acid anhydrides and lower alkyl (1 to 4 carbon atoms) esters (for example, methyl ester, ethyl ester, and isopropyl ester, etc.) of these polyvalent carboxylic acids may be used. The polyvalent carboxylic acid may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of maleic acid, fumaric acid, itaconic acid, and their acid anhydrides is preferable. More preferably, it is at least one selected from the group consisting of maleic acid, fumaric acid, and their acid anhydrides.

[0033] Examples of the monoalcohol having 16 to 30 carbon atoms and a chain hydrocarbon group include alcohols having a linear alkyl group (alkyl group having 16 to 30 carbon atoms) (such as cetanol, stearyl alcohol, 1-eicosanol, behenyl alcohol, 1-tetracosanol, and 1-triacontanol) and alcohols having a branched alkyl group (alkyl group having 16 to 30 carbon atoms) (such as 2-decyl-1-tetradecanol). Among these, from the viewpoint of crystallinity, an alcohol having a linear alkyl group (alkyl group having 16 to 30 carbon atoms) is preferable. More preferably, it is an alcohol having a linear alkyl group (alkyl group having 18 to 28 carbon atoms), and still more preferably, it is an alcohol having a linear alkyl group (alkyl group having 20 to 24 carbon atoms).

[0034] The method for producing the polymerizable ester is not particularly limited except for condensing a polyvalent carboxylic acid having 4 to 6 carbon atoms and a carbon-carbon double bond with a monoalcohol having 16 to 30 carbon atoms and a chain hydrocarbon group. In order to perform the condensation reaction reliably and prevent the reaction of the carbon-carbon double bond during the production of the polymerizable ester, it is preferable to use an esterification catalyst and a stabilizer (polymerization inhibitor).

[0035] The crystalline vinyl resin preferably has an acid value of 3.0 mgKOH / g or less from the viewpoint of further improving the low-temperature fixability and reducing the change in the fixing rate even after storage in a high-temperature environment in a high-speed fixing system. The acid value of the crystalline vinyl resin is preferably 0.0 to 3.0 mgKOH / g, more preferably 0.0 to 1.0 mgKOH / g, and even more preferably 0.2 to 1.0 mgKOH / g. The fact that the acid value is 3.0 mgKOH / g or less indicates that there are few unreacted sites when synthesizing the crystalline vinyl resin. Therefore, it is considered that crystallinity is preferably expressed and the crystal density is higher. In order to control the acid value within the above range, methods such as changing the ratio of carboxylic acid and alcohol when synthesizing the crystalline vinyl resin can be mentioned.

[0036] In addition to the monomer unit (a) represented by the formula (1), the crystalline vinyl resin may contain other monomer units. The crystalline vinyl resin may contain a plurality of other monomer units. As a method for introducing other monomer units, there is a method of polymerizing the above polymerizable ester and other vinyl monomers. The crystalline vinyl resin is preferably a polymer of the above polymerizable ester and other vinyl monomers.

[0037] Examples of other vinyl monomers include the following. Styrene, α-methylstyrene, (meth)acrylic acid methyl esters such as (meth)acrylic acid methyl, (meth)acrylic acid ethyl, (meth)acrylic acid -n-butyl, (meth)acrylic acid -t-butyl, (meth)acrylic acid -2-ethylhexyl. Monomers having a urea group: For example, amines having 3 to 22 carbon atoms [primary amines (such as normal butylamine, t-butylamine, propylamine and isopropylamine, etc.), secondary amines (such as di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline and cyclohexylamine, etc.] and ethylenically unsaturated isocyanates having 2 to 30 carbon atoms are reacted by a known method, and monomers and the like. Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate, etc. Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. 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 a known method. Monomers having a lactam structure; for example, N-vinyl-2-pyrrolidone.

[0038] Among them, it is preferable that the crystalline vinyl resin contains, in addition to the monomer unit (a), a monomer unit (b) different from the monomer unit (a). And, when the SP value of the monomer unit (a) is SPa (J / cm 3 ) 0.5 and the SP value of the monomer unit (b) is SPb (J / cm 3 ) 0.5 it is preferable that SPa and SPb satisfy the following formula (3). However, when there are two or more other monomer units used in addition to the monomer unit (a) represented by the formula (1), among these, the one having the largest difference from the SP value of the monomer unit (a) is defined as the monomer unit (b). 3.0 ≦ |SPb - SPa| ≦ 21.0 (3)

[0039] When the relationship between the SP value SPa of the monomer unit (a) and the SP value SPb of the monomer unit (b) is within the above range, the crystalline sites and the amorphous sites in the crystalline vinyl resin are likely to form a distinct phase separation state. Therefore, the crystallinity does not decrease, and the low-temperature fixability is easily enhanced. The value of |SPb - SPa| can be controlled by the type and addition amount of the polymerizable monomer when preparing the crystalline vinyl resin. Furthermore, it is more preferable that the relationship between SPa and SPb satisfies the following formula (3-1). 7.0 ≦ |SPb - SPa| ≦ 12.0 (3-1)

[0040] The crystalline vinyl resin preferably contains a monomer unit corresponding to methacrylonitrile. The crystalline vinyl resin preferably contains 1.0 to 25.0% by mass of the monomer unit corresponding to methacrylonitrile, more preferably 10.0 to 20.0% by mass. Further, the crystalline vinyl resin preferably contains a monomer unit corresponding to styrene. The crystalline vinyl resin preferably contains 1.0 to 81.0% by mass of the monomer unit corresponding to styrene, more preferably 1.0 to 60.0% by mass, and even more preferably 4.0 to 10.0% by mass.

[0041] The crystalline vinyl resin may be produced by any conventionally known method as long as it is within the scope of the present configuration. However, it is preferably produced by polymerizing a composition of polymerizable monomers containing the above polymerizable ester with an initiator or the like.

[0042] (Release agent) The toner contains a release agent having a peak molecular weight Mp of 800 or more. When the peak molecular weight is 800 or more, the compatibility during fixing with the crystalline vinyl resin decreases. Therefore, the release agent oozes out to the toner surface during fixing, and the hot offset resistance is improved. When the peak molecular weight of the release agent is less than 800, it easily becomes compatible with the crystalline vinyl resin in the toner during fixing, and it becomes difficult to ooze out, thereby reducing the hot offset resistance. Here, the peak molecular weight (Mp) of the release agent refers to the peak molecular weight in gel permeation chromatography (GPC) measurement. The measurement method will be described later.

[0043] The release agent is not particularly limited as long as its peak molecular weight Mp is 800 or more. The release agent preferably contains at least one selected from the group consisting of ester wax and hydrocarbon wax, more preferably contains ester wax. Further, the release agent is preferably at least one selected from the group consisting of ester wax and hydrocarbon wax, more preferably is ester wax. Since the release agent contains an ester wax, the release agents in the toner exist in a united state. As a result, it is difficult to form a eutectic with the crystalline vinyl resin after storage in a high-temperature environment, and it is easy to reduce the change in the fixing speed even after storage in a high-temperature environment in a high-speed fixing system. The ester wax only needs to have at least one ester bond in one molecule, and either natural ester wax or synthetic ester wax may be used.

[0044] Although there is no particular limitation on the ester wax, for example, the following may be mentioned. Esters of monohydric alcohols and monocarboxylic acids such as behenyl behenate, stearyl stearate, and palmitoyl palmitate; Esters of dicarboxylic acids and monohydric alcohols such as dibehenyl sebacate; Esters of dihydric alcohols and monocarboxylic acids such as ethylene glycol distearate and hexanediol dibehenate; Esters of trihydric alcohols and monocarboxylic acids such as glycerin tribehenate; Esters of tetrahydric alcohols and monocarboxylic acids such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate; Esters of hexahydric alcohols and monocarboxylic acids such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabehenate; Esters of polyfunctional alcohols and monocarboxylic acids such as polyglycerin behenate; natural ester waxes such as carnauba wax and rice wax.

[0045] Among them, it is preferable that the release agent contains an ester wax which is an ester of an alcohol having 4 to 8 valences and an aliphatic monocarboxylic acid, or an ester wax which is an ester of a carboxylic acid having 4 to 8 valences and an aliphatic monoalcohol. Further, it is more preferable that the release agent is an ester wax which is an ester of an alcohol having 4 to 8 valences and an aliphatic monocarboxylic acid, or an ester wax which is an ester of a carboxylic acid having 4 to 8 valences and an aliphatic monoalcohol. When these ester waxes are included, in addition to the effects of the above ester waxes, it is easy to control the molecular weight, and by reducing the compatibility with the crystalline vinyl resin during fixing, it is easy to enhance the hot offset resistance.

[0046] In addition, esters of hexavalent alcohols such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, dipentaerythritol hexabehenate and monocarboxylic acids, and esters of octavalent alcohols such as tripentaerythritol octastearate, tripentaerythritol octapalmitate, tripentaerythritol octabehenate and monocarboxylic acids are more preferable.

[0047] The hydrocarbon wax is not particularly limited. For example, it is preferable that the release agent contains an aliphatic hydrocarbon wax. Further, it is more preferable that the release agent is an aliphatic hydrocarbon wax. When the release agent contains an aliphatic hydrocarbon wax, it is easy to create a polarity difference with the crystalline vinyl resin, thereby reducing the compatibility with the crystalline vinyl resin during fixing and improving the hot offset resistance. Examples of the aliphatic hydrocarbon wax include the following. Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, Fischer-Tropsch wax, polyalphaolefin wax, or waxes obtained by oxidizing or adding acid to these.

[0048] Aliphatic hydrocarbon waxes are more preferably those having monomer units represented by the following formula (15) corresponding to polyα-olefins. By having the monomer units represented by the following formula (15), in addition to the effects of the aliphatic hydrocarbon wax, due to the high crystallinity of the release agent and the release agents in the toner existing in a aggregated state, it is difficult to form a eutectic with the crystalline vinyl resin after storage in a high-temperature environment, and it is easy to reduce the change in the fixing speed even after storage in a high-temperature environment in a high-speed fixing system. Examples of the aliphatic hydrocarbon wax having monomer units represented by the following formula (15) include copolymers of alkenes having 16 to 37 carbon atoms. The alkenes having 16 to 37 carbon atoms are not particularly limited, but 1-triacontene is preferred. [Chemical formula] [In formula (15), R 6 represents a hydrogen atom or a methyl group, and R 7 represents a linear alkyl group having 14 to 34 (preferably 20 to 32, more preferably 25 to 30) carbon atoms, and X 1 represents a methylene group.]

[0049] The peak molecular weight of the release agent is preferably 1000 to 5000, and more preferably 1200 to 4600. When the peak molecular weight is 1000 or more, it becomes difficult for the crystalline vinyl resin and the release agent to be compatible during fixing, and it is easy to improve the hot offset resistance. When the peak molecular weight is 5000 or less, the molecular mobility is high, and it is easier to bleed out earlier during fixing after storage in a high-temperature environment, and it is easy to improve the fixing speed after storage in a high-temperature environment. The peak molecular weight of the release agent can be adjusted according to the type of the release agent. The method for measuring the peak molecular weight of the release agent will be described later.

[0050] In the molecular weight distribution measured by gel permeation chromatography of the o-dichlorobenzene-soluble component of the release agent, in the differential molecular weight distribution curve where the horizontal axis is log M, which is the logarithmic value of the molecular weight, when RI detection is performed, and the vertical axis is the value [dW / d(log M)] obtained by differentiating the concentration fraction with respect to the logarithmic value of the molecular weight, it is preferable that the ratio (hereinafter referred to as ratio H) of the peak area in the region of molecular weight 700 to 1,000,000 to the total peak area in the region of molecular weight 1,000,000 or less is 90.0% or more. When ratio H is 90% or more, the compatibility between the crystalline vinyl resin and the release agent becomes poor, and it becomes easier to improve the hot offset resistance. Ratio H is more preferably 95.0% or more, and even more preferably 98.0% or more. The upper limit is not particularly limited, but for example, preferably 90.0 to 100.0%, 95.0 to 100.0%, 98.0 to 100.0%. Ratio H can be adjusted according to the type of the release agent. The measurement method of ratio H will be described later.

[0051] Based on the mass of the crystalline vinyl resin, the content ratio of the release agent (hereinafter also referred to as ratio L) is preferably 2.0 to 80.0% by mass. When ratio L is 2.0% by mass or more, the release action of the release agent becomes sufficient, and it becomes easier to improve the hot offset resistance. When it is 80.0% by mass or less, it becomes difficult to form a eutectic between the release agent and the crystalline vinyl resin during storage in a high-temperature environment, and it becomes easier to improve the fixing rate after storage in a high-temperature environment. Ratio L is preferably 5.0 to 75.0% by mass, and more preferably 10.0 to 65.0% by mass.

[0052] The release agent preferably has a melting point of 60 to 120°C. When the melting point of the release agent is within the above range, it is likely to melt during fixing and seep out onto the toner surface, making it easier to exhibit release properties. The melting point is more preferably 70 to 100°C. If the melting point is lower than 60°C, it is likely to form a eutectic of the release agent and the crystalline vinyl resin during storage in a high-temperature environment, making it difficult to improve the fixing speed after storage in a high-temperature environment. On the other hand, if the melting point is higher than 120°C, it is difficult for the release agent to melt appropriately during fixing, and the low-temperature fixability and offset resistance are likely to decrease.

[0053] Let the SP value of the crystalline vinyl resin be SP(A) (J / cm 3 ) 0.5 and the SP value of the release agent be SP(W) (J / cm 3 ) 0.5 When this is the case, it is preferable that SP(A) and SP(W) satisfy the following formula (2). (SP(A) - SP(W)) ≧ 0.4 (2) When SP(A) and SP(W) satisfy formula (2), the crystalline vinyl resin and the release agent are likely to phase-separate in the toner. Also, the release agent has a lower polarity than the crystalline vinyl resin. As a result, the release agent is effectively likely to seep out onto the toner surface during fixing, and the hot offset resistance is likely to improve. The upper limit of the value of SP(A) - SP(W) is not particularly limited, but for example, the value of SP(A) - SP(W) can be 0.4 to 3.0, 0.8 to 2.4. SP(A) and SP(W) can be controlled by the types and addition amounts of polymerizable monomers when preparing the crystalline vinyl resin and the release agent. The calculation methods of SP(A) and SP(W) will be described later.

[0054] In the viscoelasticity measurement of the toner, when the storage elastic modulus G' of the toner becomes 1.0×10 7 Pa, the temperature is T1 (°C), and it is preferable that T1 satisfies the following formula (4). 50.0 ≦ T1 ≦ 70.0 (4) When T1 is 50.0 °C or higher, it becomes easier to improve the fixing speed after storage in a high-temperature environment. On the other hand, when T1 is 70.0 °C or lower, it becomes easier to improve the low-temperature fixability. Further, it is more preferable that T1 satisfies the following formula (4-1). 50.0 ≦ T1 ≦ 65.0 (4-1) T1 can be controlled by the length of the long-chain alkyl group of the crystalline vinyl resin, the ratio of the long-chain alkyl group in the binder resin, and the like.

[0055] Also, in the viscoelasticity measurement of the toner, when the ratio of the loss elastic modulus G” of the toner at the above T1 (°C) to the storage elastic modulus G’ is defined as tanδ(T1), and the ratio of the loss elastic modulus G” of the toner at the temperature T1 - 10 (°C) to the storage elastic modulus G’ is defined as tanδ(T1 - 10), it is preferable that tanδ(T1) and tanδ(T1 - 10) satisfy the following formulas (5) and (6). 0.30 ≦ tanδ(T1) ≦ 1.00 (5) 1.00 ≦ tanδ(T1) / tanδ(T1 - 10) ≦ 1.90 (6)

[0056] T1 is the temperature at the time when the toner is melting. And tanδ represents the ratio of the loss elastic modulus G” of the toner to the storage elastic modulus G’. For example, whether the toner strongly exhibits elastic properties or strongly exhibits viscous properties, which represents the ease of deformation of the toner. Therefore, by satisfying formula (5) for tanδ(T1), the ease of deformation during low-temperature fixing is appropriately maintained, and even when the transfer material is rough like rough paper, it becomes easier to maintain a high gloss on the rough paper.

[0057] It is more preferable that the lower limit of tanδ(T1) is 0.40 or higher. Also, the upper limit of tanδ(T1) is more preferably 0.90 or lower, and even more preferably 0.80 or lower. That is, it is also one of the preferable embodiments that tanδ(T1) satisfies the following formula (5-1), (5-2) or (5-3). 0.40 ≦ tanδ(T1) ≦ 1.00 (5-1) 0.40 ≦ tanδ(T1) ≦ 0.90 (5-2) 0.40 ≤ tanδ(T1) ≤ 0.80 (5-3)

[0058] tanδ(T1) can be controlled by the amount of resin added to the toner, etc. It can also be controlled by the length of the long-chain alkyl group of the crystalline vinyl resin, the proportion of the long-chain alkyl group in the binder resin, etc. Furthermore, it can be controlled by the type and amount of cross-linking agent during toner production. The method for measuring tanδ(T1) will be described later.

[0059] Also, the fact that tanδ(T1) / tanδ(T1-10) is within the range of formula (6) indicates that the ease of deformation of the toner during fixing is within a certain range, showing that the toner can be deformed gently. As a result, the ease of deformation at the convex and concave portions on rough paper is within a certain range, and the gloss uniformity is likely to be improved.

[0060] The lower limit of tanδ(T1) / tanδ(T1-10) is more preferably 1.10 or more, and even more preferably 1.20 or more. The upper limit is more preferably 1.80 or less. That is, it is also one of the preferred embodiments that tanδ(T1) and tanδ(T1-10) satisfy the following formula (6-1), (6-2), or (6-3). 1.10 ≤ tanδ(T1) / tanδ(T1-10) ≤ 1.90 (6-1) 1.20 ≤ tanδ(T1) / tanδ(T1-10) ≤ 1.90 (6-2) 1.20 ≤ tanδ(T1) / tanδ(T1-10) ≤ 1.80 (6-3)

[0061] tanδ(T1) / tanδ(T1-10) can be controlled by the type and amount of polymerizable monomer used in the toner, etc. The method for measuring tanδ(T1-10) will be described later.

[0062] (Amorphous resin) The binder resin may contain an amorphous resin. The amorphous resin is not particularly limited, but an amorphous vinyl resin is preferred. As the polymerizable monomer used for the amorphous vinyl resin, the vinyl monomers that can be used for the crystalline vinyl resin described above can be used. Among them, the amorphous resin preferably contains a monomer unit corresponding to styrene. Further, it preferably contains a monomer unit corresponding to (meth)acrylate. The monomer units may be used alone or in combination of two or more. It is more preferable to contain both a monomer unit corresponding to styrene and a monomer unit corresponding to (meth)acrylate. That is, the amorphous vinyl resin is more preferably a polymer of a monomer mixture containing styrene and (meth)acrylate. The amorphous vinyl resin preferably does not contain the monomer unit (a) represented by the formula (1). The content ratio of the amorphous vinyl resin based on the mass of the binder resin is preferably 10.0 to 90.0% by mass, more preferably 10.0 to 80.0% by mass.

[0063] <Colorant> The toner may contain a colorant. Examples of the colorant include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic particles. Examples of the colorant for yellow include the following. Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds. Specifically, C.I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180 are preferably used.

[0064] Examples of the coloring agent for magenta include the following: condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specifically, C.I. 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, 254 are preferably used. Examples of the coloring agent for cyan include the following: copper phthalocyanine compounds and their derivatives, anthraquinone compounds, basic dye lake compounds. Specifically, C.I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, 66 are preferably used.

[0065] The coloring agent is selected from the viewpoints of hue angle, chroma, lightness, lightfastness, and dispersibility in the toner. The content of the coloring agent is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin. When magnetic particles are used as the coloring agent, the content is preferably 40.0 parts by mass or more and 150.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

[0066] <Charge control agent> The toner particles may contain a charge control agent as necessary. Also, the charge control agent may be externally added to the toner particles. By blending the charge control agent, the charge characteristics can be stabilized and the optimum triboelectric charge amount can be controlled according to the developing system. As the charge control agent, known ones can be used, and in particular, a charge control agent with a fast charging speed and the ability to stably maintain a certain charge amount is preferred.

[0067] Examples of the charge control agent for controlling the toner to be negatively chargeable 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, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Examples of those for controlling the toner to be positively charged include the following. Examples include nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganotin borates, guanidine compounds, and imidazole compounds. The content of the charge control agent is preferably 0.01 part by mass or more and 20.0 parts by mass or less, more preferably 0.5 part by mass or more and 10.0 parts by mass or less, based on 100.0 parts by mass of the toner particles.

[0068] <External additive> The toner particles may be used as the toner as they are, or may be used as the toner by mixing an external additive or the like and attaching it to the surface of the toner particles as necessary. Examples of the external additive 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 the composite oxide include , silica-aluminum fine particles, strontium titanate fine particles, and the like. The content of the external additive is preferably 0.01 part by mass or more and 8.0 parts by mass or less, more preferably 0.1 part by mass or more and 4.0 parts by mass or less, based on 100 parts by mass of the toner particles.

[0069] <Method for producing toner> The method for producing the toner particles is not particularly limited. The toner particles may be produced by any known method such as suspension polymerization method, emulsion aggregation method, dissolution suspension method, and pulverization method, but the toner particles are preferably produced by the suspension polymerization method. The toner particles are preferably suspension polymerization toner particles. The suspension polymerization method will be described in detail.

[0070] For example, a previously synthesized crystalline vinyl resin is added to a mixture of each polymerizable monomer that forms an amorphous resin, together with a release agent. If necessary, other materials such as a colorant and a charge control agent are added and uniformly dissolved or dispersed to prepare a polymerizable monomer composition. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium using a stirrer or the like to prepare suspension particles of the polymerizable monomer composition. Thereafter, the polymerizable monomer contained in the particles is polymerized by an initiator or the like to obtain toner particles. The toner particles may be filtered, washed, and dried by a known method. Further, an external additive may be added if necessary to obtain a toner.

[0071] As the polymerization initiator, a known polymerization initiator can be used. For example, azo-based or diazo-based polymerization initiators such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; peroxide-based polymerization initiators such as benzoyl peroxide, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy pivalate, t-butyl peroxy isobutyrate, t-butyl peroxy neodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide. Also, known chain transfer agents and polymerization inhibitors may be used.

[0072] The aqueous medium may contain an inorganic or organic dispersion stabilizer. As the dispersion stabilizer, a known dispersion stabilizer can be used. 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.

[0073] On the other hand, examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium carboxymethylcellulose, polyacrylic acid and its salts, and starch.

[0074] When using an inorganic compound as the dispersion stabilizer, a commercially available product may be used as it is, or the inorganic compound may be generated in an aqueous medium and used to obtain finer particles. For example, in the case of calcium phosphate such as hydroxyapatite or tricalcium phosphate, it is advisable to mix an aqueous phosphate solution and an aqueous calcium salt solution under high agitation.

[0075] The aqueous medium may contain a surfactant. As the surfactant, known surfactants can be used. Examples include anionic surfactants such as sodium dodecylbenzenesulfate and sodium oleate; cationic surfactants; amphoteric surfactants; and nonionic surfactants.

[0076] [Measurement methods for various physical property values] The calculation methods and measurement methods for various physical properties of the toner and toner materials are described below. <Method for separating toner particles from toner> When analyzing toner particles, if the surface of the toner particles is treated with an external additive or the like, the external additive is separated by the following method to obtain toner particles. Add 160 g of sucrose (manufactured by Kinoshita Chemical Co., Ltd.) to 100 mL of ion-exchanged water, and dissolve it while stirring with hot water to prepare a thick sucrose solution. Put 31 g of the above thick sucrose solution and 6 mL of Contaminon N (a 10% by mass aqueous solution of a neutral detergent for precision measuring instrument cleaning with pH 7, composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) into a centrifuge tube to prepare a dispersion. Add 1.0 g of toner to this dispersion, and loosen the toner lumps with a spatula or the like. Shake the centrifuge tube with a shaker (sold by AS ONE Corporation) at 350 spm (strokes per min) for 20 min. After shaking, transfer the solution to a glass tube (50 mL) for a swinging rotor, and centrifuge it (H-9R manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 min. By this operation, the toner particles and the detached external additives are separated. Visually confirm that the toner particles and the aqueous solution are sufficiently separated, and collect the separated toner particles in the uppermost layer with a spatula or the like. After filtering the collected toner with a vacuum filter, dry it with a dryer for 1 hour or more to obtain toner particles. Repeat this operation multiple times to ensure the required amount.

[0077] <Method for Separating Tetrahydrofuran (THF) - Insoluble Component> When separating the THF-insoluble component from the toner particles, perform the separation according to the following procedure. Precisely weigh 1.5 g of toner particles from which the THF-insoluble component is to be separated (W [g]), put it into a pre-precise weighed cylindrical filter paper (product name: No. 86R, size 28×100 mm, manufactured by Advantec Toyo Co., Ltd.), and set it in a Soxhlet extractor. Extract with 200 mL of tetrahydrofuran (THF) as a solvent for 18 hours, and perform the extraction at a reflux rate such that the extraction cycle of the solvent is about once every 5 minutes. After the extraction is completed, take out the cylindrical filter paper, air-dry it, and then vacuum-dry it at 40 °C for 8 hours to obtain the obtained extraction residue as the THF-insoluble component. On the other hand, obtain the THF-soluble component by sufficiently distilling off THF from the THF solution after the above extraction with an evaporator. For the recovered THF-insoluble matter, if there is no melting point peak in the DSC measurement, it can be determined that the THF-insoluble matter is an amorphous resin. Furthermore, by combining known methods such as Fourier transform infrared spectroscopy and pyrolysis gas chromatography for the THF-insoluble matter, the constituent components of the THF-insoluble matter can be analyzed.

[0078] <Method for Separating Crystalline Vinyl Resin, Amorphous Vinyl Resin, and Release Agent from Toner Particles> Separation of the crystalline vinyl resin and the amorphous vinyl resin from the toner particles is possible by known methods, and an example is shown below. As a method for separating the resin component from the toner particles, gradient LC is used. In this analysis, separation can be performed according to the polarity of the resin in the binder resin regardless of the molecular weight. According to the aforementioned <Method for Separating Tetrahydrofuran (THF)-Insoluble Matter>, the toner particles are separated into THF-insoluble matter and THF-soluble matter.

[0079] Next, the THF-soluble matter is dissolved in chloroform. The sample was adjusted to a sample concentration of 0.1% by mass with chloroform, and the solution filtered through a 0.45 μm PTFE filter was used for measurement. The gradient polymer LC measurement conditions are shown below. Apparatus: 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 change in the mobile phase was made linear.) Flow rate: 1.0 mL / min Injection: 0.1% by mass × 20 μL Column: Tosoh TSKgel ODS (4.6 mm φ x 150 mm x 5 μm) Column temperature: 40°C Detector: Corona charged particle detector (Corona-CAD) (manufactured by Thermo Fisher Scientific) Regarding the time-intensity graph obtained by measurement, the resin components can be separated into two peaks according to polarity. Then, the above measurement is performed again, and by fractionating at the time corresponding to the valley of each peak, it is possible to separate into two types of resins. For the separated resins, DSC measurement is performed, and the resin without a melting point peak is defined as an amorphous vinyl resin (mass W12 [g]).

[0080] Since the resin with a melting point peak contains a crystalline vinyl resin and a release agent, it needs to be separated. Put 200 mL of normal hexane into the resin with a melting point peak and dissolve it in normal hexane at room temperature over 24 hours. Filter the normal hexane solution, take out the filtrate, remove the solvent with an evaporator, and vacuum dry at 40 °C for 8 hours to obtain the normal hexane soluble fraction. Also, here, the residue of the normal hexane solution filtration is the normal hexane insoluble fraction.

[0081] Next, fractionation of the normal hexane soluble fraction is performed by GPC (recycling HPLC) to separate the components with a molecular weight of 10,000 or less as the release agent. The fractionation method is shown below. Prepare a chloroform solution of the normal hexane soluble fraction. Then, filter the obtained solution through a solvent-resistant membrane filter "Micron Disc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of the components soluble in chloroform is 1.0 mass%. Using this sample solution, fractionation is performed by GPC (recycling HPLC) under the following conditions. The obtained fractionated solution is vacuum dried to obtain the release agent (mass W3 [g]). · Apparatus: LC-Sakura NEXT (manufactured by Japan Analytical Industry Co., Ltd.) · Column: JAIGEL2H, 4H (manufactured by Japan Analytical Industry Co., Ltd.) · Eluent: Chloroform · Flow rate: 10.0 ml / min · Oven temperature: 40.0 °C · Sample injection volume: 1.0 mL · Fractionation condition: Fractionate after the elution time corresponding to a molecular weight of 10,000 in the molecular weight calibration curve In the fractionation condition, a molecular weight calibration curve prepared using a standard polystyrene resin (trade names “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.

[0082] Also, in the above operation, the components with a molecular weight exceeding 10,000 in the normal hexane-insoluble matter and the normal hexane-soluble matter are crystalline vinyl resins (mass W11 [g]). Normal hexane The method for fractionating the components with a molecular weight exceeding 10,000 in the normal hexane-soluble matter is the same as the method for fractionating the release agent, except that in the fractionation condition in the molecular weight calibration curve, “fractionation is performed before the elution time corresponding to a molecular weight of 10,000”. The obtained fractionated solution is vacuum-dried to obtain a crystalline vinyl resin. The total mass of the crystalline vinyl resin obtained by vacuum-drying the normal hexane-insoluble matter and the crystalline vinyl resin obtained by vacuum-drying the fractionated solution is defined as mass W11 [g].

[0083] <Measurement of the content ratio of each component in toner particles> From each mass described in <Method for Separating Crystalline Vinyl Resin, Amorphous Vinyl Resin, and Release Agent from Toner Particles> mentioned above, the content ratio of each component in the toner particles is calculated as follows in formulas (7) and (8). 〔Content ratio of crystalline vinyl resin based on the mass of the binder resin: Ratio I (unit: mass %)) I = (W11 / (W11 + W12)) × 100 (7) 〔Content ratio of release agent based on the mass of the crystalline vinyl resin: Ratio L (unit: mass %)) L = (W3 / W11) × 100 (8)

[0084] <Method for Measuring the Molecular Weight of the Release Agent> The molecular weight distribution of the release agent is measured by gel permeation chromatography (GPC) as follows. Add special grade 2,6-di-t-butyl-4-methylphenol (BHT) to o-dichlorobenzene for gel chromatography so that the concentration is 1.0 g / L, and dissolve it at room temperature. Put the mold release agent and the o-dichlorobenzene added with the above BHT into the sample vial, heat it on a hot plate set at 150 °C to dissolve the mold release agent. Once the mold release agent has melted, put it into a pre-heated filter unit and install it on the GPC apparatus main body. Use the material that has passed through the filter unit as the GPC sample. Adjust the sample solution so that the concentration is about 0.15% by mass. Measure under the following conditions using this sample solution. Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation) Detector: RI for high temperature Column: TSKgel GMHHR-H HT twin columns (manufactured by Tosoh Corporation) Temperature: 135.0 °C Solvent: o-dichlorobenzene for gel chromatography (added with 1.0 g / L BHT) Flow rate: 1.0 mL / min Injection volume: 0.4 mL When calculating the molecular weight of the mold release agent, use the molecular weight calibration curve prepared using a standard polystyrene resin (for example, trade names "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).

[0085] In the measured molecular weight distribution, in the differential molecular weight distribution curve where the horizontal axis is log M, the logarithm of the molecular weight, and the vertical axis is the value [dW / d(log M)] obtained by differentiating the concentration fraction with respect to the logarithm of the molecular weight, the molecular weight at the peak position is defined as the peak molecular weight Mp. Also, the ratio of the area of the peak in the region where the molecular weight is 700 to 1,000,000 to the total area of the peaks in the region where the molecular weight is 1,000,000 or less in the differential molecular weight distribution curve is defined as the ratio H.

[0086] <Method for measuring the content ratio of various monomer units such as monomer unit (a) in the resin and the number of carbon atoms of the alkyl group> The content ratio of various monomer units such as the monomer unit (a) in the resin and the number of carbon atoms in the alkyl group are measured 1 by 1H-NMR under the following conditions. The measurement sample can be the crystalline vinyl resin fractionated by the above method Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.) Measuring frequency: 400 MHz Pulse condition: 5.0 μs Frequency range: 10500 Hz Number of integrations: 64 times Measuring temperature: 30 °C Sample: 50 mg of the measurement sample is placed in a sample tube with an inner diameter of 5 mm, and deuterated chloroform (CDCl3) is added as a solvent, and this is dissolved in a constant temperature bath at 40 °C for preparation. The obtained 1 1H-NMR chart is analyzed to identify the structure of each monomer unit. Here, as an example, the measurement of the content ratio of the monomer unit (a) and the number of carbon atoms in the alkyl group in the crystalline vinyl resin will be described. The obtained 1 In the 1H-NMR chart, from the peaks attributed to the components of the monomer unit (a), a peak independent of the peaks attributed to the components of the other monomer units is selected, and the integral value S1 of this peak is calculated. For the other monomer units contained in the crystalline vinyl resin, the integral values are calculated in the same manner

[0087] For example, when the monomer units constituting the crystalline vinyl resin are the monomer unit (a) and one other monomer unit, the content ratio of the monomer unit (a) is obtained as follows using the above integral value S1 and the integral value S2 of the peak of the other monomer unit. Here, n1 and n2 are the numbers of hydrogens in the components to which the peaks focused on each site are attributed Content ratio of monomer unit (a) (mol%) = {(S1 / n1) / ((S1 / n1)+(S2 / n2))}×100 ​Even when there are two or more other monomer units (using S3···Sx, n3···nx), the content ratio of monomer unit (a) can be calculated. Also, the number of carbon atoms in the alkyl group 1 can be calculated from the integration ratio of proton peaks in the H-NMR chart.

[0088] When a polymerizable monomer containing no hydrogen atom in components other than the vinyl group is used, 13 using C-NMR, the measurement nucleus 13 is set to C, and the measurement is performed in the single pulse mode, 1 and it is calculated in the same manner as in H-NMR.

[0089] Multiply the ratio (mol%) of each monomer unit calculated by the above method by the molecular weight of each monomer unit to convert the content ratio of each monomer unit to mass%. Thereby, based on the mass of the crystalline vinyl resin, the ratio J of the monomer unit (a) represented by the above formula (1) is calculated using the following formula (9). 〔Content ratio of monomer unit (a) based on the mass of the crystalline vinyl resin: ratio J (unit: mass%)〕 J={(S1 / n1)×M1 / ((S1 / n1)×M1+(S2 / n2)×M2)}×100 (9)

[0090] When a monomer unit having an alkyl group with 16 to 30 carbon atoms exists in addition to the monomer unit (a) represented by the formula (1), among the monomer units having an alkyl group with 16 to 30 carbon atoms including the monomer unit (a), the content ratio (ratio K) of the monomer unit (a) is calculated as follows. For example, when the unit having an alkyl group with 16 to 30 carbon atoms is the monomer unit (a) and one other monomer unit, it is calculated using the following formula (10) with the above integration value S1 and the integration value S3 of the peak of the other monomer unit. 〔Mass ratio of monomer unit (a) in the monomer unit having an alkyl group with 16 to 30 carbon atoms : ratio K (unit: mass%)〕 K = { (S1 / n1) × M1 / ((S1 / n1) × M1 + (S3 / n3) × M3)} × 100 (10) However, M1 and M3 are the molecular weights of each monomer unit. The same method is used for measurement even in the case of an amorphous vinyl resin.

[0091] <Calculation method of solubility parameter (SP value)> The SP value of the resin is determined as follows according to the calculation method proposed by Fedors. First, the SP values of the monomer units constituting the resin are determined as follows. Here, the monomer unit constituting the resin means the molecular structure in a state where the double bond of the monomer used when obtaining the resin by polymerization is cleaved by polymerization. For example, when calculating the SP value (σm) (J / cm 3 ) 0.5 of the monomer unit, for the atoms or atomic groups in the molecular structure of the monomer unit, the evaporation energy (Δei) (J / mol) and the molar volume (Δvi) (cm 3 / mol) are obtained from the table described in "Polym. Eng. Sci., 14(2), 147 - 154(1974)" and calculated from the following formula (11). σm = (ΣΔei / ΣΔvi) 0.5 (11)

[0092] The SP value of the resin is obtained by determining the evaporation energy (Δei) and the molar volume (Δvi) of the monomer units constituting the resin for each monomer unit. Then, the products with the molar ratio (j) of each monomer unit in the resin are calculated respectively, and the sum of the evaporation energies of each monomer unit is divided by the sum of the molar volumes, and calculated from the following formula (12). σp = { (Σj × ΣΔei) / (Σj × ΣΔvi)} 0.5 (12) For example, when assuming that the resin is composed of two types of monomer units, X and Y, if the composition ratios of each monomer unit are Wx and Wy (mass %), the molecular weights are Mx and My, the evaporation energies are Δei(X) and Δei(Y), and the molar volumes are Δvi(X) and Δvi(Y), then the molar ratios (j) of each monomer unit are Wx / Mx and Wy / My, respectively, and the SP value (σp) of this resin is as shown in the following formula (13). σp=[{(Wx / Mx)×Δei(X)+Wy / My×Δei(Y)} / {(Wx / Mx)×Δvi(X)+Wy / My×Δvi(Y)}] 0.5 (13) Furthermore, when two or more types of resins are mixed, the SP value (σM) of the mixture is calculated as the product of the mass composition ratio (Wi) of the mixture and the SP value (σi) of each resin, and is as shown in the following formula (14). σM=Σ(Wi×σi) (14) Also, the SP value of the mold release agent can be determined in the same manner as the SP value of the above resin.

[0093] <Method for Measuring Acid Value> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the resin is measured in accordance with JIS K 0070-1992. Specifically, it is measured according to the following procedure. (1) Preparation of Reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add ion-exchanged water to make 100 mL, and obtain a phenolphthalein solution. Dissolve 7 g of special grade potassium hydroxide in 5 mL of water, add ethyl alcohol (95% by volume) to make 1 L. Place it in an alkali-resistant container so as not to come into contact with carbon dioxide gas, etc., leave it for 3 days, and then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by taking 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask and adding the phenolphth Add several drops of the thallium solution and titrate with the potassium hydroxide solution. Determine it from the amount of the potassium hydroxide solution required for neutralization. Use the 0.1 mol / L hydrochloric acid prepared in accordance with JIS K 8001-1998.

[0094] (2) Procedure (A) This test Precisely weigh 2.0 g of the sample (for example, crystalline vinyl resin) into a 200 mL Erlenmeyer flask, add 100 mL of a mixed solution of toluene / ethanol (2:1), and dissolve it over 5 hours. Next, add several drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of the titration is when the faint red color of the indicator persists for 30 seconds. (B) Blank test Conduct titration in the same manner as the above operation except that no sample is used (that is, only the mixed solution of toluene / ethanol (2:1) is used). (3) Substitute the obtained results into the following formula to calculate the acid value. A = [(C - B) × f × 5.61] / S Here, A: acid value (mgKOH / g), B: amount of potassium hydroxide solution added in the blank test (mL), C: amount of potassium hydroxide solution added in this test (mL), f: factor of the potassium hydroxide solution, S: mass of the sample (g).

[0095] ><Measurement method of peak temperature of endothermic peak> The peak temperature of the endothermic peak is measured under the following conditions using DSC Q2000 (manufactured by TA Instruments). Temperature rising rate: 10 °C / min Measurement start temperature: 20 °C Measurement end temperature: 180 °C For temperature correction of the device detection part, use the melting points of indium and zinc, and for heat quantity correction, use the heat of fusion of indium. Specifically, 5 mg of the sample is precisely weighed, placed in an aluminum pan, and differential scanning calorimetry is performed. An empty aluminum pan is used as the reference. As the temperature rising process, the temperature is raised to 180 °C at a rate of 10 °C / min. Then, the peak temperature is calculated from each peak, and the peak temperature is taken as the melting point of the mold release agent.

[0096] <Measurement method of viscoelasticity> <Measurement method of storage modulus G' and tanδ> The storage modulus G' and tanδ are measured using a viscoelasticity measuring device (rheometer) ARES (manufactured by Rheometrics Scientific). The general outline of the measurement is described in the ARES operation manual 902-30004 (August 1997 edition), 902-00153 (July 1993 edition) issued by Rheometrics Scientific, and is as follows. · Measuring jig: torsion rectangular · Measurement sample: For the toner, a rectangular parallelepiped sample with a width of 12 mm, a height of 20 mm, and a thickness of 2.5 mm is prepared using a compression molding machine (maintaining 25 kN for 30 minutes at room temperature). The compression molding machine used is the 100 kN press NT-100H manufactured by NPa Systems.

[0097] After leaving the jig and the sample at room temperature (23 °C) for 1 hour, the sample is attached to the jig. Refer to Figure 1. As shown in the figure, it is fixed so that the width of the measurement part is 12 mm, the thickness is 2.5 mm, and the height is 10 mm. After temperature adjustment to the measurement start temperature of 30 °C over 10 minutes, the measurement is performed with the following settings. · Measurement frequency: 6.28 rad / s · Setting of measurement strain: The initial value is set to 0.1%, and the measurement is performed in the automatic measurement mode. · Elongation correction of the sample: Adjustment is performed in the automatic measurement mode. · Measurement temperature: The temperature is raised from 30 °C to 150 °C at a rate of 2 °C per minute. · Measurement interval: Every 30 seconds, that is, viscoelasticity data is measured every 1 °C. Transfer data through an interface to the RSI Orchesrator (control, data collection, and analysis software) (manufactured by Rheometrics Scientific) that operates on Microsoft Windows (registered trademark) 2000. Among the measurement data, the temperature at which the storage modulus G’ is 1.0×10 7 Pa is designated as T1 [°C]. Also, the ratio (tanδ) of the loss modulus G” to the storage modulus G’ at temperature T1 [°C] is designated as tanδ(T1), and the ratio of the loss modulus G” to the storage modulus G’ at temperature T1 - 10 [°C] is designated as tanδ(T1 - 10).

Example

[0098] Hereinafter, the present disclosure will be specifically described by way of examples, but these do not limit the present disclosure in any way. In the following formulations, parts are based on mass unless otherwise specified.

[0099] (Preparation of polymerizable monomer (a-1)) Into a pressurized reaction vessel equipped with a stirrer, a temperature control device, a thermometer, an air inlet tube, a pressure reduction device, and a water reduction device, 727.3 parts of cetanol, 174.1 parts of fumaric acid, 2.5 parts of dibutyltin oxide, and 1 part of 2,6-di-tert-butyl-p-cresol were charged, and the mixture was stirred at 120 °C for homogenization. Then, the temperature was raised to 165 °C, and esterification under reduced pressure was carried out while removing the distillate water at 21 kPa for 3 hours. After confirming that the acid value was less than 30.0 mgKOH / g, esterification under reduced pressure was carried out while removing the distillate water at 3 kPa or less for 12 hours. This was taken out to obtain the polymerizable monomer (a-1).

[0100] (Preparation of polymerizable monomers (a-2) to (a-12)) Polymerizable monomers (a-2) to (a-12) were produced in the same manner as in the preparation of the polymerizable monomer (a-1), except that the types and amounts of the raw materials were changed as shown in Table 1. The compositions of the polymerizable monomers (a-2) to (a-12) are shown in Table 1.

Table 1

[0101] (Preparation of Crystalline Vinyl Resin (A1)) 120.0 parts of xylene and 80.0 parts of polymerizable monomer (a-1) were charged into an autoclave, and the temperature was raised to 135°C in a sealed state with stirring, and then the pressure was released, and the temperature was raised to 155°C in a sealed state with stirring. A mixed solution of 1.6 parts of di-t-butyl peroxide and 60.0 parts of xylene was added dropwise over 3 hours while controlling the temperature inside the autoclave to 155°C, and polymerization was carried out. After the addition, the dropping line was washed with 20.0 parts of xylene. After maintaining the temperature at the same temperature for 2.2 hours, it was cooled to 70°C, and then 12.8 parts of di-t-butyl peroxide was added and reacted. After that, the solvent was removed at 170°C for 3 hours under reduced pressure of 0.5 to 2.5 kPa, and a crystalline vinyl resin (A-1) was obtained. It was confirmed that the crystalline vinyl resin (A1) was a crystalline resin that showed a clear endothermic peak in differential scanning calorimeter (DSC) measurement.

[0102] (Preparation of Crystalline Vinyl Resins (A2) to (A25)) Crystalline vinyl resins (A2) to (A25) were produced in the same manner as in the production of crystalline vinyl resin (A1), except that the types and amounts of raw materials added were changed as shown in Table 2. It was confirmed that the crystalline vinyl resins (A2) to (A25) were crystalline resins that showed clear endothermic peaks in differential scanning calorimetry (DSC) measurements. The compositions and physical properties of the crystalline vinyl resins (A2) to (A25) are shown in Table 2. [Table 2] In the table, the ratio J indicates the content (mass %) of the monomer unit (a) represented by formula (1) based on the mass of the crystalline vinyl resin. The ratio K is the ratio of the number of carbon atoms of 16 to 16, including the monomer unit (a), in the crystalline vinyl resin. The content (mass%) of monomer unit (a) among 30 alkyl group-containing monomer units is shown. The unit of acid value is mgKOH / g.

[0103] (Preparation of Amorphous Resin B1) In a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, the following materials were charged under a nitrogen atmosphere. · 100.0 parts by mass of toluene · 100.0 parts by mass of monomer composition (The monomer composition is a mixture of the following monomers in the following proportions) (25.0 parts by mass of butyl acrylate) (75.0 parts by mass of styrene) · 0.5 parts by mass of polymerization initiator t-butyl peroxy pivalate (manufactured by NOF Corporation: Perbutyl PV) While stirring the inside of the above reaction vessel at 200 rpm, it was heated to 70 °C and subjected to a polymerization reaction for 12 hours to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after cooling the above solution to 25 °C, the above solution was charged into 1000.0 parts by mass of methanol while stirring to precipitate the methanol-insoluble matter. The obtained methanol-insoluble matter was filtered off, washed further with methanol, and then vacuum dried at 40 °C for 24 hours to obtain amorphous resin B1.

[0104] (Preparation of Release Agent 10) · Solvent: 100.0 parts by mass of toluene · 100.0 parts by mass of 1-triacontene Into a heat-dried autoclave, under a hydrogen atmosphere, the above materials and the following materials were added and polymerized at 160 °C for 130 minutes. · 0.5 mmol of triisobutylaluminum · 2 μmol of (1,2’-dimethylsilylene)(2,1’-dimethylsilylene)bis(3-trimethylsilylmethylindenyl)zirconium dichloride · 8 μmol of dimethylanilinium tetrakispentafluorophenylborate After completion of the polymerization reaction, the precipitated reaction product was separated at 25 °C, washed with acetone, and then dried under heating and reduced pressure to obtain release agent 10 which is a poly-α-olefin wax. The peak molecular weight Mp of release agent 10 was 1900, and the peak top temperature of the temperature-endotherm curve was 70 °C.

[0105] <Example 1> [Manufacture of toner by suspension polymerization method] (Manufacture of toner particles 1) · 16.2 parts by mass of n-butyl acrylate · 48.8 parts by mass of styrene · 6.5 parts by mass of colorant Pigment Blue 15:3 A mixture consisting of the above materials was prepared. The above mixture was put into an attritor (manufactured by Nippon Coke Co., Ltd.), and using zirconia beads with a diameter of 5 mm, it was dispersed at 200 rpm for 2 hours to obtain a raw material dispersion liquid.

[0106] On the other hand, 735.0 parts by mass of ion-exchanged water and 16.0 parts by mass of trisodium phosphate (dodecahydrate) were added to a container equipped with a high-speed stirring device homomixer (manufactured by Primix Co., Ltd.) and a thermometer, and the temperature was raised to 60 °C while stirring at 12,000 rpm. An aqueous calcium chloride solution in which 9.0 parts by mass of calcium chloride (dihydrate) was dissolved in 65.0 parts by mass of ion-exchanged water was added thereto, and it was stirred at 12,000 rpm for 30 minutes while maintaining 60 °C. 10% hydrochloric acid was added thereto to adjust the pH to 6.0, and an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water to obtain an aqueous medium. to obtain an aqueous medium in which it was dispersed.

[0107] Subsequently, the above raw material dispersion liquid was transferred to a container equipped with a stirring device and a thermometer, and the temperature was raised to 60 °C while stirring at 100 rpm. · 35.0 parts by mass of crystalline vinyl resin (A3) · 9.0 parts by mass of release agent 1 (dipentaerythritol stearic acid ester wax, manufactured by Nisshin Oillio Group, Ltd.) The above materials were added thereto, and after stirring at 100 rpm for 30 minutes while maintaining 60 °C, 5.0 parts by mass of t-butyl peroxy pivalate (manufactured by NOF Corporation: Perbutyl PV) was added as a polymerization initiator, and after further stirring for 1 minute, it was put into the aqueous medium being stirred at 12,000 rpm by the above high-speed stirring device. Stirring was continued at 12,000 rpm for 20 minutes by the above high-speed stirring device while maintaining 60 °C to obtain a granulation liquid.

[0108] The above granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, and heated to 70°C while stirring at 150 rpm under a nitrogen atmosphere. A polymerization reaction was carried out at 150 rpm for 12 hours while maintaining the temperature at 70°C to obtain a toner particle dispersion liquid. The obtained toner particle dispersion liquid was cooled to 45°C while stirring at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. Thereafter, dilute hydrochloric acid was added until the pH reached 1.5 while stirring to dissolve the dispersion stabilizer. The solid content was filtered off, washed thoroughly with ion-exchanged water, and then vacuum-dried at 30°C for 24 hours to obtain toner particles 1.

[0109] (Preparation of Toner 1) With respect to 100.0 parts by mass of the above toner particles 1, 2.0 parts by mass of silica fine particles (hydrophobically treated with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m 2 / g) was added and mixed at 3000 rpm for 15 minutes using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain toner 1. The evaluation of the obtained toner 1 was carried out by the method shown below. The physical properties of the obtained toner 1 are shown in Tables 5-1 and 5-2, and the evaluation results are shown in Table 6.

[0110] <Examples 2 to 47> In Example 1, toner particles 2 to 47 were obtained in the same manner except that the type and addition amount of the crystalline vinyl resin used, the type and addition amount of the polymerizable monomer, the type and addition amount of the release agent, and the addition amount of the crosslinking agent were changed as shown in Tables 3-1 and 3-2. The types and physical properties of the release agents are shown in Table 4. Furthermore, the same external addition as in Example 1 was carried out to obtain toners 2 to 47. The evaluation of the obtained toners 2 to 47 was carried out by the method shown below. The physical properties of the toners are shown in Tables 5-1 and 5-2, and the evaluation results are shown in Table 6.

Table 3-1

Table 3-2

[0111] In the table, HDDA represents 1,6 - hexanediol diacrylate, St represents styrene, and BA represents butyl acrylate.

Table 4

[0112] In the table, release agents 3 - 4 are manufactured by Nisshin Oillio Group, Ltd., release agents 5 - 8 are manufactured by Mitsui Chemicals, Inc., release agents 9 and 11 are manufactured by Sasol, and release agents 2 and 12 are manufactured by Nippon Seiro Co., Ltd. Also, the molecular weight indicates the peak molecular weight.

Table 5 - 1

[0113] In the table, ratio J represents the content ratio (mass%) of monomer unit (a) represented by formula (1) based on the mass of the crystalline vinyl resin. Ratio K represents the content ratio (mass%) of monomer unit (a) among the monomer units having an alkyl group with 16 - 30 carbon atoms including monomer unit (a) in the crystalline vinyl resin. Ratio H represents the ratio of the peak area in the region of molecular weight 700 - 1,000,000 to the total peak area in the region where the molecular weight at the molecular weight peak of the release agent is 1,000,000 or less. The unit of acid value is mgKOH / g.

Table 5 - 2

[0114] In the table, ratio I represents the content ratio (mass%) of the crystalline vinyl resin based on the mass of the binder resin. Ratio L represents the content ratio (mass%) of the release agent based on the mass of the crystalline vinyl resin.

[0115] <Example 48> [Preparation of Toner by Grinding Method] · 35.0 parts by mass of crystalline vinyl resin (A3) · 65.0 parts by mass of amorphous resin B1 · 6.5 parts by mass of C.I. Pigment Blue 15:3 · 9.0 parts by mass of release agent 1 The above materials were premixed with an FM mixer (manufactured by Nippon Coke & Engineering Co., Ltd.), and then melt-kneaded with a twin-screw extrusion extruder (PCM-30 type manufactured by Ikegai Iron Works Co., Ltd.). The obtained kneaded product was cooled and roughly pulverized with a hammer mill, then pulverized with a mechanical pulverizer (T-250 manufactured by Turbo Industry Co., Ltd.), and the obtained finely pulverized powder was classified using a multi-stage classifier utilizing the Coandă effect to obtain toner particles 48. External addition similar to Example 1 was performed on the toner particles 48 to obtain toner 48. The evaluation of the obtained toner 48 was carried out by the method shown below. The physical properties of toner 48 are shown in Tables 5-1 and 5-2, and the evaluation results are shown in Table 6.

[0116] <Example 49> [Manufacture of toner by emulsion aggregation method] (Preparation of crystalline resin dispersion) · 300.0 parts by mass of toluene · 100.0 parts by mass of crystalline vinyl resin (A3) The above materials were weighed and mixed, and dissolved at 90 °C to obtain a toluene solution. Separately, 5.0 parts by mass of sodium dodecylbenzenesulfonate and 10.0 parts by mass of sodium laurate were added to 700.0 parts by mass of ion-exchanged water and heated and dissolved at 90 °C to obtain an aqueous solution. Then, the above toluene solution and aqueous solution were mixed and stirred at 7000 rpm using an ultra-high-speed stirrer T.K. Robomix (manufactured by Primix). Further, it was emulsified at a pressure of 200 MPa using a high-pressure impact type disperser Nanomizer (manufactured by Yoshida Kikai Kogyo). Then, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain a crystalline resin dispersion having a concentration of 20% by mass of crystalline resin A3 fine particles. When the 50% particle size (D50) based on the volume distribution of the crystalline resin A3 fine particles was measured using a dynamic light scattering particle size distribution analyzer NanoTrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.), it was 0.41 μm.

[0117] (Preparation of amorphous resin dispersion) · 300.0 parts by mass of toluene · 100.0 parts by mass of amorphous resin B1 The above materials were weighed and mixed, and dissolved at 90 °C to obtain a toluene solution. Separately, 5.0 parts by mass of sodium dodecylbenzenesulfonate and 10.0 parts by mass of sodium laurate were added to 700.0 parts by mass of ion-exchanged water, and heated and dissolved at 90 °C to obtain an aqueous solution. Then, the above toluene solution and the aqueous solution were mixed, and stirred at 7000 rpm using a high-speed stirrer T.K. Robomix (manufactured by Primix Corporation). Further, it was emulsified at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Thereafter, toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an amorphous resin dispersion having a concentration of 20% by mass of amorphous resin fine particles. When the 50% particle size (D50) based on the volume distribution of the amorphous resin fine particles was measured using a dynamic light scattering particle size distribution analyzer NanoTrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.), it was 0.39 μm.

[0118] (Preparation of release agent dispersion) · 100.0 parts by mass of release agent 1 · 5.0 parts by mass of anionic surfactant Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) · 395.0 parts by mass of ion-exchanged water The above materials were weighed and put into a mixing container equipped with a stirrer. After heating to 90 °C, it was circulated through a Clearmix W motion (manufactured by M Technique) for 60 minutes for dispersion treatment. The conditions for the dispersion treatment were as follows. · Outer diameter of rotor: 3 cm · Clearance: 0.3 mm · Rotor rotation speed: 19000 r / min · Screen rotation speed: 19000 r / min

[0119] After dispersion treatment, the mixture was cooled to 40 °C under the cooling treatment conditions of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10 °C / min, to obtain a mold release agent dispersion liquid with a mold release agent fine particle concentration of 20% by mass. When the 50% particle size (D50) based on the volume distribution of the mold release agent fine particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), it was 0.14 μm.

[0120] (Preparation of colorant dispersion liquid) · 50.0 parts by mass of C.I. Pigment Blue 15:3 · 7.5 parts by mass of anionic surfactant Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) · 442.5 parts by mass of ion-exchanged water The above materials were weighed, mixed, dissolved, and dispersed for 1 hour using a high-pressure impact type disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain a colorant dispersion liquid with a colorant fine particle concentration of 10% by mass in which the colorant was dispersed. When the 50% particle size (D50) based on the volume distribution of the colorant fine particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), it was 0.20 μm.

[0121] (Manufacture of toner 49) · 200.0 parts by mass of crystalline resin dispersion liquid · 300.0 parts by mass of amorphous resin dispersion liquid · 45.0 parts by mass of mold release agent dispersion liquid · 65.0 parts by mass of colorant dispersion liquid · 160.0 parts by mass of ion-exchanged water Each of the above materials was put into a round stainless steel flask and mixed. Subsequently, it was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). After adding a 1.0% nitric acid aqueous solution and adjusting the pH to 3.0, it was heated to 58 °C in a water bath for heating while appropriately adjusting the rotation speed such that the mixed solution was stirred using a stirring blade. The volume average particle size of the formed aggregated particles was appropriately confirmed using a Coulter Multisizer III. When aggregated particles with a weight average particle size (D4) of 6.83 μm were formed, the pH was adjusted to 9.0 using a 5% sodium hydroxide aqueous solution. Thereafter, while continuing stirring, it was heated to 75 °C. Then, the aggregated particles were fused by holding at 75 °C for 1 hour.

[0122] Thereafter, it was cooled to 45 °C and heat-treated for 5 hours. Thereafter, it was cooled to 25 °C, filtered and solid-liquid separated, and then washed with ion-exchanged water. After completion of washing, it was dried using a vacuum dryer to obtain toner particles 49. External addition similar to Example 1 was performed on the toner particles 49 to obtain toner 49. The evaluation of the obtained toner 49 was carried out by the method shown below. The physical properties of toner 49 are shown in Tables 5-1 and 5-2, and the evaluation results are shown in Table 6.

[0123] <Comparative Examples 1 to 3, 5 to 6> In Example 1, except that the types and addition amounts of the crystalline vinyl resin, polymerizable monomer, release agent, and crosslinking agent used were changed as shown in Tables 3-1 and 3-2, everything else was the same to obtain comparative toner particles 1 to 3, 5 to 6. Furthermore, external addition similar to Example 1 was performed to obtain comparative toners 1 to 3, 5 to 6. The evaluation of the obtained comparative toners 1 to 3, 5 to 6 was carried out by the method shown below. The physical properties of the toner are shown in Tables 5-1 and 5-2, and the evaluation results are shown in Table 6.

[0124] <Comparative Example 4> (Production of Comparative Toner Particles 4) · 100.0 parts by mass of a monomer composition (the monomer composition is a mixture of behenyl acrylate, methacrylonitrile, and styrene in the following ratios) (Behenyl acrylate (first polymerizable monomer), 67.0 parts by mass (28.9 mol%)) (Methacrylonitrile (second polymerizable monomer), 22.0 parts by mass (53.9 mol%)) (Styrene (third polymerizable monomer), 11.0 parts by mass (17.2 mol%)) · Pigment Blue 15:3, 6.5 parts by mass · Aluminum di-t-butyl salicylate, 1.0 part by mass · Release agent 1, 9.0 parts by mass (Dipentaerythritol stearate wax, manufactured by Nisshin Oillio Group, Ltd.) · Toluene, 100.0 parts by mass A mixture consisting of the above materials was prepared. The above mixture was put into an attritor (manufactured by Nippon Coke Co., Ltd.), and using zirconia beads with a diameter of 5 mm, it was dispersed at 200 rpm for 2 hours to obtain a raw material dispersion.

[0125] On the other hand, into a container equipped with a high-speed stirring device homomixer (manufactured by Primix Co., Ltd.) and a thermometer, 735.0 parts by mass of ion-exchanged water and 16.0 parts by mass of trisodium phosphate (dodecahydrate) were added, and the temperature was raised to 60 °C while stirring at 12000 rpm. Thereto, an aqueous calcium chloride solution in which 9.0 parts by mass of calcium chloride (dihydrate) was dissolved in 65.0 parts by mass of ion-exchanged water was added, and it was stirred at 12000 rpm for 30 minutes while maintaining 60 °C. 10% hydrochloric acid was added thereto to adjust the pH to 6.0, and an aqueous medium containing an inorganic dispersion stabilizer containing hydroxyapatite was obtained.

[0126] Subsequently, the above raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and the temperature was raised to 60 °C while stirring at 100 rpm. Thereto, 8.0 parts by mass of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) as a polymerization initiator was added, and it was stirred at 100 rpm for 5 minutes while maintaining 60 °C, and then it was put into the aqueous medium being stirred at 12000 rpm by the above high-speed stirring device. Stirring was continued at 12000 rpm for 20 minutes by the above high-speed stirring device while maintaining 60 °C to obtain a granulation liquid. The above granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, and heated to 70°C while stirring at 150 rpm under a nitrogen atmosphere. A polymerization reaction was carried out at 150 rpm for 10 hours while maintaining the temperature at 70°C. Then, the reflux condenser was removed from the reaction vessel, and the reaction solution was heated to 95°C. Thereafter, toluene was removed by stirring at 150 rpm for 5 hours while maintaining the temperature at 95°C to obtain a toner particle dispersion. After the obtained toner particle dispersion was cooled to 20°C while stirring at 150 rpm, dilute hydrochloric acid was added until the pH reached 1.5 while maintaining the stirring to dissolve the dispersion stabilizer. The solid content was filtered off, washed thoroughly with ion-exchanged water, and then vacuum-dried at 40°C for 24 hours to obtain comparative toner particles 4. Furthermore, external addition was performed in the same manner as in Example 1 to obtain comparative toner 4. The evaluation of the obtained comparative toner 4 was carried out by the method shown below. The physical properties of the toner are shown in Tables 5-1 and 5-2, and the evaluation results are shown in Table 6.

Table 6

[0127] <Toner Evaluation Method> The following evaluations were performed on each of the obtained toners. <1> Low-temperature Fixing Property The process cartridge filled with toner was stored at 25°C and 40% relative humidity for 48 hours. Using an LBP-712Ci (manufactured by Canon Inc.) modified to operate even without the fixing unit, an unfixed image of an image pattern in which 9-point square images of 30 mm × 30 mm were evenly arranged over the entire transfer paper was output. The toner loading amount on the transfer paper was 0.80 mg / cm 2 and the fixing start temperature was evaluated. The transfer paper used was A4 paper with a rough texture (「Prover Bond Paper」: 105 g / m 2 , manufactured by Fox River). As the fixing unit, the fixing unit of the LBP-712Ci was removed externally, and an external fixing unit modified to operate outside the laser beam printer was used. The external fixing unit increased the fixing temperature in 5°C increments from 90°C and fixing was carried out under the condition of a process speed of 400 mm / sec. The fixed image was visually confirmed, and the lowest temperature at which cold offset did not occur was taken as the fixing start temperature for evaluation. The evaluation results are shown in Table 6.

[0128] <2>Hot offset resistance Under the same conditions as the low-temperature fixability, the highest temperature at which no hot offset was observed was taken as the maximum fixing temperature, and the difference between the maximum fixing temperature and the minimum fixing temperature was evaluated as the fixable region. The evaluation results are shown in Table 6.

[0129] <3>Fixable speed after storage in a high-temperature environment The process cartridge evaluated for low-temperature fixability was left standing in an environment of 50°C and 40% relative humidity for 3 days, and then left standing at 25°C and 40% relative humidity for 48 hours. After that, an unfixed image was output under the same conditions as the evaluation of <1> low-temperature fixability, and the same external fixing device was used. In the evaluation of <1> low-temperature fixability, the temperature was set to the lowest temperature at which cold offset did not occur, and the fixing evaluation was carried out by decreasing the speed in 10 mm / sec increments from a process speed of 400 mm / sec. The fixed image was visually confirmed, and the process speed at which no offset occurred was evaluated. Among the process speeds at which no offset occurred, the highest speed was taken as the fixable speed. The evaluation results are shown in Table 6.

[0130] <4>Evaluation of gloss and gloss unevenness The fixed image at the fixing start temperature output in the evaluation of <1> above 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 such that the projection angle and the light-receiving angle were each adjusted to 75°, and all the image patterns arranged in a 9-point array were measured, and the average value of the gloss and the standard deviation of the gloss were evaluated as gloss unevenness (gloss uniformity). The evaluation results are shown in Table 6.

[0131] The present disclosure relates to the following configuration. (Configuration 1) A toner containing toner particles containing a binder resin and a release agent, The binder resin contains a crystalline vinyl resin, The crystalline vinyl resin contains 5.0% by mass or more of a monomer unit (a) represented by the following formula (1) based on the mass of the crystalline vinyl resin. TIFF2025094906000013.tif28170 In the formula (1), R 1 ~R 4 Among them, at least two are each independently -X-COOR 5 , and the rest are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X is a single bond or an alkylene group having 1 or 2 carbon atoms, and R 5 is an alkyl group having 16 to 30 carbon atoms. A toner characterized in that the peak molecular weight Mp of the release agent is 800 or more. (Constitution 2) In the molecular weight distribution measured by gel permeation chromatography of the o-dichlorobenzene-soluble component of the release agent, when RI detection is performed, the horizontal axis is log M which is the logarithmic value of the molecular weight, and the vertical axis is the value [dW / d(log M)] obtained by differentiating the concentration fraction with respect to the logarithmic value of the molecular weight in the differential molecular weight distribution curve, in the total area of the peaks in the region where the molecular weight is 1,000,000 or less, the ratio of the area of the peak in the region where the molecular weight is 700 to 1,000,000 is 90.0% or more The toner according to Constitution 1. (Constitution 3) The toner according to Constitution 1 or 2, wherein the binder resin contains 20.0 to 100.0% by mass of the crystalline vinyl resin based on the mass of the binder resin. (Constitution 4) The toner according to any one of Constitutions 1 to 3, wherein the crystalline vinyl resin contains 30.0% by mass or more of the monomer unit (a) based on the mass of the crystalline vinyl resin. (Constitution 5) In the crystalline vinyl resin, among the monomer units having an alkyl group with 16 to 30 carbon atoms including the monomer unit (a), the content ratio of the monomer unit (a) is 50.0 to 100.0% by mass, and the toner according to any one of Configurations 1 to 4. (Configuration 6) The acid value of the crystalline vinyl resin is 3.0 mgKOH / g or less, and the toner according to any one of Configurations 1 to 5. (Configuration 7) The content ratio of the release agent is 2.0 to 80.0% by mass based on the mass of the crystalline vinyl resin, and the toner according to any one of Configurations 1 to 6. (Configuration 8) The peak molecular weight Mp of the release agent is 1000 to 5000, and the toner according to any one of Configurations 1 to 7. (Configuration 9) The melting point of the release agent is 60 to 120 °C, and the toner according to any one of Configurations 1 to 8. (Configuration 10) Let the SP value of the crystalline vinyl resin be SP(A) (J / cm 3 ) 0.5 and the SP value of the release agent be SP(W) (J / cm 3 ) 0.5 When this is the case, the toner according to any one of Configurations 1 to 9, where the SP(A) and the SP(W) satisfy the following formula (2). (SP(A) - SP(W)) ≧ 0.4 (2) (Configuration 11) The crystalline vinyl resin contains, in addition to the monomer unit (a), a monomer unit (b) different from the monomer unit (a), Let the SP value of the monomer unit (a) be SPa (J / cm 3 ) 0.5 and the SP value of the monomer unit (b) be SPb (J / cm 3 ) 0.5 When this is the case, the toner according to any one of Configurations 1 to 10, where the SPa and the SPb satisfy the following formula (3). 3.0 ≦ |SPb - SPa| ≦ 21.0 (3) (Configuration 12) The toner according to any one of Constitutions 1 to 11, wherein the release agent contains an ester wax. (Constitution 13) The toner according to Constitution 12, wherein the release agent is an ester wax which is an ester of an alcohol having a valence of 4 or more and 8 or less and an aliphatic monocarboxylic acid, or the toner according to Constitution 12, which contains an ester wax which is an ester of a carboxylic acid having a valence of 4 or more and 8 or less and an aliphatic monoalcohol. (Constitution 14) The toner according to any one of Constitutions 1 to 13, wherein the release agent contains an aliphatic hydrocarbon wax. (Constitution 15) The toner according to Constitution 14, wherein the release agent contains a poly-α-olefin wax. (Constitution 16) In the viscoelasticity measurement of the toner, when the temperature at which the storage elastic modulus G' of the toner becomes 1.0×10 7 Pa is defined as T1 (°C), T1 satisfies the following formula (4), 50.0 ≦ T1 ≦ 70.0 (4) In the viscoelasticity measurement of the toner, when the ratio of the loss elastic modulus G'' of the toner at the temperature T1 (°C) to the storage elastic modulus G' is defined as tanδ(T1), and the ratio of the loss elastic modulus G'' of the toner at the temperature T1 - 10 (°C) to the storage elastic modulus G' is defined as tanδ(T1 - 10), tanδ(T1) and tanδ(T1 - 10) satisfy the following formulas (5) and (6) 0.30 ≦ tanδ(T1) ≦ 1.00 (5) 1.00 ≦ tanδ(T1) / tanδ(T1 - 10) ≦ 1.90 (6) The toner according to any one of Constitutions 1 to 15, which satisfies the above.

Claims

1. A toner containing toner particles containing a binder resin and a release agent, The binder resin contains a crystalline vinyl resin, The crystalline vinyl resin contains a monomer unit (a) represented by the following formula (1) in an amount of 5.0 mass% or more based on the mass of the crystalline vinyl resin: In the formula (1), R １ ~R ４ At least two of the groups are independently -X-COOR ５ the remainders are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is a single bond or an alkylene group having 1 or 2 carbon atoms, R ５ is an alkyl group having 16 to 30 carbon atoms, The toner is characterized in that the peak molecular weight Mp of the releasing agent is 800 or more.

2. The molecular weight distribution of the o-dichlorobenzene soluble portion of the release agent measured by gel permeation chromatography is as follows: In a differential molecular weight distribution curve obtained by RI detection, the horizontal axis represents the logarithmic value of the molecular weight, log M, and the vertical axis represents the value obtained by differentiating the concentration fraction by the logarithmic value of the molecular weight [dW / d(log M)]. In the total area of ​​the peaks in the region having a molecular weight of 1,000,000 or less, The ratio of the peak area in the molecular weight range of 700 to 1,000,000 is 90.0% or more. The toner according to claim 1 ,

3. 3. The toner according to claim 1, wherein the binder resin contains the crystalline vinyl resin in an amount of 20.0 to 100.0% by mass based on the mass of the binder resin.

4. 3. The toner according to claim 1, wherein the crystalline vinyl resin contains the monomer unit (a) in an amount of 30.0% by mass or more based on the mass of the crystalline vinyl resin.

5. 3. The toner according to claim 1, wherein in the crystalline vinyl resin, a content ratio of the monomer unit (a) among monomer units having an alkyl group having 16 to 30 carbon atoms, including the monomer unit (a), is 50.0 to 100.0 mass %.

6. 3. The toner according to claim 1, wherein the crystalline vinyl resin has an acid value of 3.0 mgKOH / g or less.

7. 3. The toner according to claim 1, wherein the content of the release agent is 2.0 to 80.0% by mass based on the mass of the crystalline vinyl resin.

8. 3. The toner according to claim 1, wherein the peak molecular weight Mp of the release agent is 1,000 to 5,000.

9. 3. The toner according to claim 1, wherein the release agent has a melting point of 60 to 120°C.

10. The SP value of the crystalline vinyl resin is SP (A) (J / cm ３ ) ０．５ The release agent The SP value is expressed as SP (W) (J / cm ３ ) ０．５ The toner according to claim 1 or 2, wherein, when the SP(A) and the SP(W) satisfy the following formula (2): (SP(A)-SP(W)) ≧ 0.4 (2)

11. the crystalline vinyl resin contains, in addition to the monomer unit (a), a monomer unit (b) different from the monomer unit (a); The SP value of the monomer unit (a) is SPa (J / cm ３ ) ０．５ The SP value of the monomer unit (b) is SPb (J / cm ３ ) ０．５ The toner according to claim 1 or 2, wherein, when the SPa and the SPb satisfy the following formula (3): 3.0≦|SPb-SPa|≦21.0 (3)

12. The toner according to claim 1 or 2, wherein the release agent comprises an ester wax.

13. The release agent is an ester wax which is an ester of a tetrahydric or more and an octahydric or less alcohol and an aliphatic monocarboxylic acid, or The toner according to claim 12, comprising an ester wax which is an ester of a 4- to 8-valent carboxylic acid and an aliphatic monoalcohol.

14. The toner of claim 1 or 2, wherein the release agent comprises an aliphatic hydrocarbon wax.

15. The toner of claim 14 , wherein the release agent comprises a polyalphaolefin wax.

16. In the viscoelasticity measurement of the toner, the storage elastic modulus G′ of the toner is 1.0×10 ７ When the temperature at which the temperature becomes Pa is T1 (°C), T1 satisfies the following formula (4), 50.0≦T1≦70.0 (4) In the viscoelasticity measurement of the toner, when the ratio of the loss elastic modulus G″ of the toner to the storage elastic modulus G′ at the temperature T1 (° C.) is defined as tan δ(T1), and the ratio of the loss elastic modulus G″ of the toner to the storage elastic modulus G′ at the temperature T1-10 (° C.) is defined as tan δ(T1-10), the tan δ(T1) and the tan δ(T1-10) are expressed by the following formulas (5) and (6): 0.30≦tanδ(T1)≦1.00 (5) 1.00≦tanδ(T1) / tanδ(T1-10)≦1.90 (6) The toner according to claim 1 or 2, which satisfies the above condition.

Images