toner

Abstract

This toner solves the problems of low-temperature fixing, hot offset resistance, and gloss stability within the same image during continuous printing on small-sized paper, while also offering excellent resistance to bending and heat storage. [Solution] A toner having toner particles, wherein the toner particles contain a binder resin and an aliphatic alcohol, the binder resin contains a crystalline vinyl resin and an amorphous vinyl resin, the crystalline vinyl resin contains a monomer unit (a) of a specific structure, the amorphous vinyl resin contains a monomer unit (b) of a specific structure, the aliphatic alcohol is a compound of a specific structure, and the toner particles contain the aliphatic alcohol in an amount of 100 to 10000 ppm based on the mass of the binder resin.

Description

[Technical Field]

[0001] This disclosure relates to toner. [Background technology]

[0002] Traditionally, energy conservation has been considered a major technical challenge in electrophotographic equipment, and significant reductions in the amount of heat required for the fuser have been explored. In toner, there is a growing need for so-called "low-temperature fixing," which enables fixing with low energy consumption. To enable fixing at low temperatures, a method using crystalline resin as the binder resin is being considered. Amorphous resins, commonly used as binder resins for toner, do not show a clear endothermic peak in differential scanning calorimeter (DSC) measurements. However, when the toner contains crystalline resin components, an endothermic peak (melting point) appears in DSC measurements.

[0003] Crystalline resins have the property of hardly softening at temperatures below their melting point due to the regular arrangement of their molecular chains. Furthermore, above the melting point, the crystals melt rapidly, resulting in a sharp decrease in viscosity. Because of these excellent sharp-melt properties, crystalline resins are attracting attention as useful materials for improving the low-temperature fixation of toners.

[0004] Examples of crystalline resins include toners using crystalline vinyl resins that have long-chain alkyl groups in their side chains. Typically, crystalline vinyl resins have a structure in which long-chain alkyl groups are bonded as side chains to the main chain. The long-chain alkyl groups in the side chains crystallize together, and the molecules form a lamellar structure in which they are regularly arranged, thus becoming a crystalline resin.

[0005] While crystalline resins are excellent in low-temperature fixing properties, their viscosity drops excessively when the melting point is exceeded. Therefore, the molten binder resin during fixing cannot be released from the fixing member, resulting in separation within the toner and so-called hot offset, where images are formed after the second pass of the fixing roller. There is also an issue that even when hot offset does not occur, due to excessive viscosity drop during melting, the binder resin is stretched, causing minute irregularities on the fixed image and potentially reducing the gloss of the image.

[0006] In Patent Document 1, for the purpose of achieving both abrasion resistance and charge stability while exhibiting excellent low-temperature fixing properties by having a crystalline resin, a toner is disclosed in which the ratio of components such as a long-chain alkyl group with low polarity and a highly polar component in the crystalline resin is controlled.

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0008] The toner of Patent Document 1 contains a highly polar amorphous portion that does not contribute to crystallization in a part of the crystalline resin. However, since it contains a crystalline part and an amorphous part within the same molecule, it cannot suppress the rapid viscosity drop associated with the melting of the crystalline part, and the problems of hot offset and gloss reduction remain. On the other hand, Patent Document 2 discloses a toner in which an amorphous resin is added to a toner using a crystalline resin to control the ratio of the loss elastic modulus G” to the storage elastic modulus G’ at a specific temperature. In this toner, a crystalline resin and an amorphous resin that can maintain a certain viscosity after melting of the crystalline resin are used in combination. Therefore, hot offset and the binder after melting This method can suppress the reduction in gloss uniformity of the fixed image caused by resin separation or stretching of the resin during melting.

[0009] However, it was found that with the toner described in Patent Document 2, when printing small-sized paper continuously, the minute irregularities in the image at both the left and right edges of the paper increased as the number of printed sheets increased, and the uniformity of gloss within the same image decreased (decreased gloss stability). This is thought to be because, when printing small-sized paper continuously, the temperature does not decrease due to paper feeding in the non-feeding parts of the fixing member, so the temperature at both edges of the paper rises excessively as the number of printed sheets increases.

[0010] This disclosure provides a toner that solves the problems of low-temperature fixing, hot offset resistance, and gloss stability within the same image during continuous printing of small-sized paper, while also being excellent in terms of bend resistance and heat storage resistance. [Means for solving the problem]

[0011] This disclosure relates to a toner having toner particles, The toner particles contain a binder resin and an aliphatic alcohol, The binder resin contains crystalline vinyl resin and amorphous vinyl resin, The crystalline vinyl resin contains a monomer unit (a) represented by the following formula (1), The amorphous vinyl resin contains a monomer unit (b) represented by the following formula (2), The aliphatic alcohol is a compound represented by the following formula (3): The present invention relates to a toner in which the toner particles contain 100 to 10,000 ppm of the aliphatic alcohol based on the mass of the binder resin. [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond, an ester bond, or an amide bond, and m1 represents an integer from 15 to 29.) In formula (2), R2 represents a hydrogen atom or a methyl group, L2 represents a single bond, an ester bond, or an amide bond, and m2 represents an integer from 0 to 13. In equation (3), m3 represents an integer between 15 and 29. [Effects of the Invention]

[0012] According to this disclosure, it is possible to provide a toner that solves the problems of low-temperature fixing, hot offset resistance, and gloss stability within the same image during continuous printing of small-sized paper, while also being excellent in terms of bend resistance and heat storage resistance. [Modes for carrying out the invention]

[0013] In this disclosure, descriptions of numerical ranges such as "XX or greater and YY or less" or "XX to YY" mean a numerical range that includes the lower and upper limits, unless otherwise specified. When numerical ranges are described in steps, the upper and lower limits of each numerical range can be any combination. In this disclosure, for example, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ. Note that if XX is a group, multiple values ​​may be selected from XX, and the same applies to YY and ZZ.

[0014] "(Meth)acrylic acid ester" means acrylic acid ester and / or methacrylic acid ester. A "monomer unit" refers to the reacted form of monomer substances in a polymer. For example, one carbon-carbon bond in the main chain formed by the polymerization of polymerizable monomers in a polymer is considered one unit. A polymerizable monomer can be represented, for example, by the following formula (C). [ka] In the above formula (C), R A R represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), B This represents a monovalent group.

[0015] "Crystalline resin" refers to a resin that exhibits a clear endothermic peak in differential scanning calorimeter (DSC) measurements. An "endothermic peak" refers to a peak with a local minimum in the differential curve of the DSC endothermic curve during temperature increase in differential scanning calorimetry.

[0016] Regarding the minute irregularities in the image at both the left and right edges of the paper mentioned above, the following factors are considered to be at play. In the toner described in Patent Document 2, the bonding between the crystalline resin and the amorphous resin is insufficient, resulting in low-viscosity areas within the fixed image caused by the crystalline resin. This leads to insufficient release from the fixing material, and the fixed image may be stretched upward. Subsequently, during cooling, the amorphous resin, which solidifies slowly, is gradually absorbed into the fixed image surface while maintaining its flexibility, while the crystalline resin, which solidifies quickly, immediately loses its fluidity above the lifted fixed image and is left behind as a convex portion. As a result, minute irregularities are thought to be formed.

[0017] The inventors investigated how to enhance the bonding between crystalline resin and amorphous resin, thereby suppressing the formation of areas within the binder resin during fixing where the solidification rate originates from the crystalline resin and is particularly fast. The inventors discovered that in a toner containing crystalline vinyl resin and amorphous vinyl resin, an aliphatic alcohol can rapidly bond a portion of the crystalline resin and amorphous resin during fixing. As a result, the formation of image protrusions caused by the rapid solidification rate of the crystalline resin during fixing can be suppressed.

[0018] This disclosure relates to a toner having toner particles, The toner particles contain a binder resin and an aliphatic alcohol, The binder resin contains crystalline vinyl resin and amorphous vinyl resin, The crystalline vinyl resin contains a monomer unit (a) represented by the following formula (1), The amorphous vinyl resin contains a monomer unit (b) represented by the following formula (2), The aliphatic alcohol is a compound represented by the following formula (3): The present invention relates to a toner in which the toner particles contain 100 to 10,000 ppm of the aliphatic alcohol based on the mass of the binder resin. [ka] (In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond, an ester bond, or an amide bond, and m1 represents an integer from 15 to 29.) In formula (2), R2 represents a hydrogen atom or a methyl group, L2 represents a single bond, an ester bond, or an amide bond, and m2 represents an integer from 0 to 13. In equation (3), m3 represents an integer between 15 and 29.

[0019] The toner relating to this disclosure has toner particles containing a binder resin. The binder resin contains a crystalline vinyl resin and an amorphous vinyl resin. Because the toner particles contain crystalline vinyl resin as a binder, a rapid decrease in viscosity occurs during melting, resulting in sharp melt properties and good low-temperature fixation. Furthermore, because the toner particles contain amorphous vinyl resin, excessive viscosity reduction during melting is suppressed, preventing the molten resin from separating and adhering to the fixation material, thus improving hot offset resistance.

[0020] Furthermore, the toner according to this disclosure contains monomer unit (a) represented by formula (1) in the crystalline vinyl resin and monomer unit (b) represented by formula (2) in the amorphous vinyl resin. In addition, the toner particles contain an aliphatic alcohol. This configuration results in good gloss stability during continuous printing of small-sized paper. The inventors hypothesize the following reasons for this mechanism.

[0021] When the crystalline vinyl resin melts during fixing, the crystalline vinyl resin contains monomer units (a), and the long chain alkyl groups and aliphatic alcohols in the monomer units (a) Alkyl groups are attracted by van der Waals forces, allowing the crystalline vinyl resin and aliphatic alcohol to interact appropriately. Furthermore, because the amorphous vinyl resin contains monomer unit (b) represented by formula (2), the alkyl group in monomer unit (b) and the long-chain alkyl group of the aliphatic alcohol are attracted by van der Waals forces, allowing the amorphous vinyl resin and aliphatic alcohol to interact appropriately as well.

[0022] Furthermore, because aliphatic alcohols have a hydroxyl group in their molecule, they exhibit weak hydrogen bonding between two molecules. As a result, weak hydrogen bonds are formed between an aliphatic alcohol that interacts with the crystalline vinyl resin and another aliphatic alcohol that interacts with the amorphous vinyl resin. Consequently, a structure is formed in which the crystalline vinyl resin and the amorphous vinyl resin are moderately bound together by two molecules of aliphatic alcohol. When such a structure is adopted, after the binder resin melts during fixing, and then solidifies, the crystalline vinyl resin bonds with the amorphous vinyl resin, which solidifies more slowly and retains its fluidity, with moderate force at the molecular level.

[0023] As a result, it is presumed that the resin, which is pulled up towards the fixing member during melting, is prevented from rapidly solidifying in the pulled-up state and forming protrusions during cooling, due to the rapid solidification rate of the crystalline vinyl resin. Consequently, even when the fixing roller end becomes particularly hot during continuous feeding of small-sized paper such as A5, and the paper edge near the hot fixing roller end becomes particularly hot, causing a significant decrease in the viscosity of the binding resin, the occurrence of irregularities at the paper edge can be suppressed. As a result, gloss stability can be improved.

[0024] The effects described above are particularly pronounced when using aliphatic alcohols, which are compounds that have long-chain alkyl groups and exhibit hydrogen bonding. This is because, for example, when using fatty acids, the hydrogen bonds of fatty acids are very strong compared to the hydrogen bonds of alcohols, making it easy for fatty acids to form dimers on their own and for fatty acids to aggregate. Therefore, it is thought that they do not move quickly between crystalline vinyl resin and amorphous vinyl resin during melting, and the effects described above cannot be obtained. Furthermore, in the case of ester waxes, the cohesive force between the waxes is high, so, similar to fatty acids, they do not easily move to the site of action. In addition, during fixing, they move to the image surface and act as a release agent, so it is thought that the effects seen with aliphatic alcohols cannot be obtained.

[0025] In the toner relating to this disclosure, the crystalline vinyl resin contains a monomer unit (a) represented by the following formula (1). [ka]

[0026] In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond, an ester bond, or an amide bond, and m1 represents an integer from 15 to 29. L1 is preferably an ester bond, and in the ester bond, the carbonyl is preferably bonded to the carbon atom to which R1 is bonded. When m1 is 15 or higher, the effect of gross stability is obtained, the melting point of the crystal is raised, and the heat resistance to storage is improved. Also, when m1 is 29 or lower, the viscosity during melting does not increase easily, and low-temperature fixing properties are good. m1 is preferably 17 to 29, more preferably 19 to It is 24.

[0027] If the amorphous vinyl resin contains multiple monomer units (a) represented by formula (1), the value of m1 is determined by a weighted average weighted by the mass proportion of each monomer unit. If the value of m1 is not an integer, the value is rounded to the first decimal place.

[0028] Furthermore, the amorphous vinyl resin contains monomer units (b) represented by the following formula (2). The improved rigidity derived from the amorphous vinyl resin enhances its resistance to bending.

[0029] [ka]

[0030] In formula (2), R2 represents a hydrogen atom or a methyl group, and L2 represents a single bond, an ester bond, or an amide bond. m2 represents an integer from 0 to 13. m2 is preferably an integer from 3 to 13, more preferably from 3 to 12. L2 is preferably an ester bond, and in the ester bond, the carbonyl is preferably bonded to the carbon atom to which R2 is bonded.

[0031] When m2 is 0 or greater, the alkyl group interacts with the aliphatic alcohol, improving gross stability. When m2 is 3 or greater, the interaction between the alkyl group and the aliphatic alcohol becomes stronger, resulting in a greater improvement in gross stability. However, when m2 exceeds 13, the interaction between the alkyl group and the aliphatic alcohol becomes excessively strong, which can prevent the aliphatic alcohol from moving to the site where it contributes to gross stability, potentially leading to a decrease in gross stability.

[0032] If the amorphous vinyl resin contains multiple monomer units (b) represented by formula (2), the value of m2 is determined by a weighted average weighted by the mass proportion of each unit. If the value of m2 is not an integer, the value is rounded to the first decimal place.

[0033] Toner particles contain aliphatic alcohols. Aliphatic alcohols are compounds represented by the following formula (3). [ka]

[0034] In equation (3), m3 represents an integer between 15 and 29. When m3 is 15 or higher, the interaction between aliphatic alcohols and crystalline and amorphous vinyl resins becomes sufficiently large, improving gloss stability. When m3 is 29 or lower, the van der Waals force interaction between aliphatic alcohols does not become too strong, suppressing aggregation among aliphatic alcohols, and allowing them to quickly move to the desired location as anchors. Therefore, an effect of improving gloss stability is obtained. m3 is preferably 17 to 26, more preferably 19 to 24.

[0035] If the toner particles contain multiple aliphatic alcohols represented by formula (3), the mass ratio of each is as follows: The value of m3 is determined by a weighted average. If the value of m3 is not an integer, the value is rounded to the first decimal place.

[0036] Examples of aliphatic alcohols represented by formula (3) include cetanol, octadecanol, 1-icosanol, behenyl alcohol, 1-tetracosanol, 1-hexacosanol, and myricyl alcohol.

[0037] With respect to m1 in equation (1) and m3 in equation (3), the values ​​of |m1-m3| can be, for example, 0 to 8 and 0 to 4. It is preferable that m1 in equation (1) and m3 in equation (3) satisfy the following equation (4). |m1-m3|≦2 ···(4) When m1 and m3 satisfy equation (4), the carbon chain lengths of the crystalline vinyl resin and the aliphatic alcohol become sufficiently close, resulting in a strong interaction. Therefore, the gross stability is further improved. The value of |m1-m3| is more preferably between 0 and 1, and even more preferably 0.

[0038] With respect to m2 in equation (2) and m3 in equation (3), the value of |m2-m3| is, for example, between 4 and 26. It is preferable that m2 in equation (2) and m3 in equation (3) satisfy the following equation (5). |m2-m3|≧6 ···(5) When m2 and m3 satisfy equation (5), the carbon chain lengths of the amorphous vinyl resin and the aliphatic alcohol do not become too close, resulting in an interaction of moderate strength. Therefore, the bond between the amorphous vinyl resin, which has high melt viscosity and is not very mobile, and the alcohol does not become too strong, allowing the alcohol to easily move to the area where it interacts with the crystalline vinyl resin, thus improving gloss stability. The value of |m2-m3| is preferably between 6 and 26, and more preferably between 6 and 20.

[0039] Furthermore, the toner particles contain 100 to 10,000 ppm of aliphatic alcohol based on the mass of the binder resin. Including 100 ppm or more of aliphatic alcohol ensures a sufficient amount of aliphatic alcohol to bind the crystalline vinyl resin and amorphous vinyl resin, improving gloss stability. Additionally, while high concentrations of aliphatic alcohol tend to attract alkyl groups and form polymers, keeping the aliphatic alcohol content below 10,000 ppm suppresses the aggregation of alcohols, further improving gloss stability.

[0040] The toner particles contain, based on the mass of the binder resin, an aliphatic alcohol, preferably 100 to 6000 ppm, more preferably 1000 to 6000 ppm, and even more preferably 3000 to 6000 ppm.

[0041] Including 1000 ppm or more of aliphatic alcohols provides a more sufficient amount of aliphatic alcohol to bind the crystalline vinyl resin and amorphous vinyl resin, thereby further improving gloss stability. Furthermore, including 3000 ppm or more of aliphatic alcohols provides an even more sufficient amount of aliphatic alcohol to bind the crystalline vinyl resin and amorphous vinyl resin, further improving gloss stability. By keeping the aliphatic alcohol content below 6000 ppm, the aggregation of alcohols can be further suppressed, resulting in improved gross stability.

[0042] The crystalline vinyl resin related to this disclosure will be described below. The content of crystalline vinyl resin, based on the mass of the binder resin, is, for example, 1.0 to 80.0% by mass, preferably 5.0 to 75.0% by mass, and more preferably 10.0 to 55.0% by mass.

[0043] When the crystalline vinyl resin content is 5.0% by mass or more, it contains a sufficient amount of crystalline components, resulting in a pronounced sharp melt property characteristic of crystalline resins. Therefore, low-temperature fixing properties are excellent. Furthermore, because the crystalline vinyl resin content is 75.0% by mass or less, there is no excess amount of crystalline components, which reduces the likelihood of resin stretching and excessive viscosity reduction, resulting in improved gloss stability and resistance to hot offset.

[0044] When the crystalline vinyl resin content is 10.0% by mass or more, the sharp melt properties characteristic of crystalline resins become more pronounced because a sufficient amount of crystalline components is also included. Furthermore, when the crystalline vinyl resin content is 55.0% by mass or less, the resin is less prone to stretching and excessive viscosity reduction, resulting in improved gloss stability and hot offset.

[0045] Crystalline vinyl resin has monomer units (a) represented by the following formula (1). [ka]

[0046] In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond, an ester bond, or an amide bond, and m1 represents an integer from 15 to 29. When L1 is an ester bond, monomer unit (a) can be incorporated as a monomer unit of crystalline vinyl resin by vinyl polymerization using an alkyl (meth)acrylate ester having an alkyl group with 16 to 30 carbon atoms as a polymerizable monomer.

[0047] Examples of alkyl (meth)acrylate esters having an alkyl group with 16 to 30 carbon atoms include cetyl (meth)acrylate, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myricyl (meth)acrylate, and the like.

[0048] Of these, from the viewpoint of low-temperature fixation and heat-resistant storage of the toner, it is preferably at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group with 18 to 30 carbon atoms, and more preferably at least one selected from the group consisting of linear (meth)acrylic acid stearyl and (meth)acrylic acid behenyl. That is, in formula (1) above, m1 is preferably 17 to 29, more preferably 19 to 24, and even more preferably 17 or 21. Also, it is preferable that R1 is a hydrogen atom.

[0049] The crystalline vinyl resin may have only one monomer unit (a) or two or more monomer units (a). One method for introducing monomer units (a) into crystalline vinyl resin is to polymerize (meth)acrylic acid esters such as the following: For example, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myricyl (meth)acrylate, etc.

[0050] The content of monomer unit (a) represented by formula (1) in crystalline vinyl resin is: For example, it is 3.0 to 100.0% by mass, preferably 5.0 to 100.0% by mass, and more preferably 50.0 to 100.0% by mass. Furthermore, the content of monomer unit (a) is the sum of the content of all monomer units shown in formula (1) above, and the same applies when there are multiple types of monomer unit (a).

[0051] When the monomer unit (a) content is 5.0% by mass or more, the amount of crystalline portion within the crystalline vinyl resin becomes sufficiently large, and the sharp melt properties characteristic of crystalline resins are significantly exhibited. As a result, low-temperature fixability is further improved. Furthermore, when the monomer unit (a) content is 50.0% by mass or more, the amount of crystalline portion within the crystalline vinyl resin becomes even more sufficient, and the sharp melt properties characteristic of crystalline resins are even more significantly exhibited. As a result, low-temperature fixability is further improved.

[0052] Crystalline vinyl resin may have monomer units other than monomer unit (a) in addition to monomer unit (a). One method for introducing other monomer units into crystalline vinyl resin is to polymerize a (meth)acrylic acid ester that forms monomer unit (a) with another vinyl monomer.

[0053] Other vinyl monomers include, for example, the following: (Meth)acrylic acid esters such as styrene, α-methylstyrene, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Monomers having a urea group: For example, monomers obtained by reacting a carbon 3-22 amine [primary amines (n-butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, and cycloxylamine, etc.)] with a carbon 2-30 isocyanate having an ethylenically unsaturated bond by known methods. Monomers having a carboxyl group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylate. Monomers having a hydroxyl 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 known methods. Monomers having a lactam structure; for example, N-vinyl-2-pyrrolidone.

[0054] Furthermore, the crystalline vinyl resin may contain monomer units made of styrene. The crystalline vinyl resin preferably contains 0.0 to 95.0% by mass of monomer units made of styrene, and more preferably contains 0.0 to 45.0% by mass. Furthermore, the crystalline vinyl resin may contain monomer units of (meth)acrylonitrile. The crystalline vinyl resin preferably contains 0.0 to 15.0% by mass of monomer units of (meth)acrylonitrile, and more preferably contains 0.0 to 12.0% by mass.

[0055] The crystalline vinyl resin preferably has a weight-average molecular weight (Mw) of tetrahydrofuran (THF) soluble content measured by gel permeation chromatography (GPC) between 30,000 and 200,000. Having Mw within this range makes it easier to adjust the melting point of the crystalline vinyl resin to an appropriate range for exhibiting low-temperature fixability. The preferred range for Mw is between 40,000 and 180,000, and more preferably between 60,000 and 150,000.

[0056] The binder resin contains an amorphous vinyl resin containing monomer units (b) represented by the following formula (2). [ka]

[0057] In formula (2), R2 represents a hydrogen atom or a methyl group, L2 represents a single bond, an ester bond, or an amide bond, and m2 represents an integer from 0 to 13. The monomer unit (b) can be incorporated as a monomer unit in amorphous vinyl resin by vinyl polymerization of an alkyl (meth)acrylate having an alkyl group with 1 to 14 carbon atoms as a polymerizable monomer.

[0058] Examples of alkyl (meth)acrylates having an alkyl group with 1 to 14 carbon atoms include: Examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, dodecyl (meth)acrylate, and tetradecyl (meth)acrylate.

[0059] The content of amorphous vinyl resin, based on the mass of the binder resin, is, for example, 20.0 to 96.0% by mass, preferably 25.0 to 95.0% by mass, and more preferably 40.0 to 90.0% by mass.

[0060] When the amorphous vinyl resin content is 25.0% by mass or more, the number of alkyl groups that interact with the crystalline vinyl resin via aliphatic alcohols becomes sufficient, resulting in improved gloss stability. Furthermore, excessive reduction in melt viscosity can be more effectively suppressed. When the amorphous vinyl resin content is 95.0% by mass or less, the rapid decrease in viscosity during melting is not hindered, resulting in better low-temperature fixability.

[0061] Furthermore, when the amorphous vinyl resin content is 40.0% by mass or more, the number of alkyl groups that interact with the crystalline vinyl resin via aliphatic alcohols becomes more sufficient, thus further improving gloss stability. In addition, excessive reduction in melt viscosity can be further suppressed. When the amorphous vinyl resin content is 90.0% by mass or less, the rapid decrease in viscosity during melting is further inhibited, resulting in even better low-temperature fixability.

[0062] The content of monomer units (b) in amorphous vinyl resin is, for example, 10.0 to 85.0% by mass, preferably 18.0 to 80.0% by mass, more preferably 20.0 to 40.0% by mass, and even more preferably 22.0 to 40.0% by mass.

[0063] The amorphous vinyl resin may have monomer units other than monomer unit (b) in addition to monomer unit (b). A method for introducing other monomer units into the amorphous vinyl resin is, for example, to polymerize an alkyl (meth)acrylate that forms monomer unit (b) with another vinyl monomer. Other vinyl monomers that can be used include, for example, vinyl monomers that can be used in crystalline vinyl resins. These vinyl monomers can be used within the range in which the amorphous resin does not exhibit crystallinity.

[0064] As other vinyl monomers, it is preferable to use styrene, which has high amorphousness. Based on the mass of the amorphous vinyl resin, the amorphous vinyl resin contains, for example, 15.0 to 90.0% by mass of monomer units made of styrene, preferably 20.0 to 90.0% by mass, more preferably 60.0 to 85.0% by mass, and even more preferably 60.0 to 80.0% by mass.

[0065] Including 20.0% by mass or more of styrene units increases amorphousness, and even when crystalline resin is used to improve low-temperature fixability, the effect of increased rigidity derived from the amorphous resin becomes greater. Furthermore, because styrene units have aromatic rings within them, the formation of π-π interactions between units further enhances the effect of increased rigidity. As a result, bending resistance is improved. Furthermore, when the styrene unit content is 90.0% by mass or less, there is a sufficient amount of monomer units (b) that interact with alcohol in the amorphous resin, and the monomer units (b) are uniformly distributed throughout the fixed image, thus further improving gloss stability.

[0066] In addition, so-called crosslinking agents, which have multiple vinyl groups per monomer, can also be used. Examples of crosslinking agents include: diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis(4-(acryloxydiethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis(4-(methacryloxydiethoxy)phenyl)propane, 2,2'-bis(4-(methacryloxypolyethoxy)phenyl)propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether, 4,4'-divinylbiphenyl.

[0067] The binder resin may contain amorphous vinyl resin as well as other amorphous resins other than amorphous vinyl resin. Examples of other amorphous resins include polyester resin, polyurethane resin, epoxy resin, and the like.

[0068] When the amorphous resin is a polyester resin, a polyester resin that is a reaction product of a divalent or higher polycarboxylic acid and a polyhydric alcohol can be used.

[0069] Examples of polycarboxylic acids include: dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, and dodecenylsuccinic acid, and their anhydrides or lower alkyl esters; and aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and their anhydrides or lower alkyl esters. These may be used individually or in combination of two or more.

[0070] Examples of polyhydric alcohols include the following: alkylene glycols (ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol) ); Alkylene ether glycols (polyethylene glycol and polypropylene glycol); Alicyclic diols (1,4-cyclohexanedimethanol); Bisphenols (bisphenol A); Alkylene oxide (ethylene oxide and propylene oxide) adducts of alicyclic diols. The alkyl portions of alkylene glycols and alkylene ether glycols may be linear or branched. Furthermore, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol, etc. These may be used individually or in combination of two or more.

[0071] Furthermore, monohydric acids such as acetic acid and benzoic acid, and monohydric alcohols such as cyclohexanol and benzyl alcohol may be used as needed to adjust the acid value and hydroxyl value. For example, the transesterification method and the direct polycondensation method can be used individually or in combination as methods for producing polyester resin.

[0072] The toner particles preferably have a core-shell structure toner particle having a core particle and a shell formed on the surface of the core particle. By providing the shell, the adhesion to the fixing roller can be reduced, so that the resin can be prevented from being stretched upward during fixing, and the gloss stability is further improved.

[0073] In addition, since the aliphatic alcohol has a hydroxyl group, when the aliphatic alcohol is present on the surface of the toner, moisture in the air may be adsorbed. From the viewpoint of improving charge stability and suppressing fogging, it is preferable that the toner particles have a shell. When the core is covered with the shell, the exposure of the alcohol can be suppressed, so that fogging is easily suppressed. In addition, since the low molecular weight component inside the core can be suppressed from being exposed by storage in a high temperature and high humidity environment, the heat-resistant storage property is further improved.

[0074] Furthermore, the shell is preferably an amorphous resin. When the shell is an amorphous resin, excessive viscosity reduction on the toner surface during fixing is less likely to occur, so that the melted resin is less likely to be stretched upward, and the gloss stability is further improved.

[0075] Furthermore, the SP value of the amorphous resin of the shell is SP S (J / cm 3 ) 0.5 and the SP value of the crystalline vinyl resin is SP A (J / cm 3 ) 0.5 At this time, SP S -SP A is, for example, 0 to 5.5. It is preferable that SP S and SP A satisfy the following formula (6). SP S -SP A ≦5.0 ···(6)

[0076] SP S (J / cm 3 ) 0.5 and SP A (J / cm 3 ) 0.5The fact that equation (6) is satisfied indicates that the amorphous resin of the shell and the crystalline vinyl resin have a high affinity. In this case, the interface between the core particles and the shell is easily stabilized, and the effects of coating the core with the shell as described above are easily obtained. As a result, gloss stability, electrostatic stability, and heat resistance are further improved. SP S -SP A It is more preferably 0 to 2.0, and even more preferably 0 to 1.0.

[0077] SP S (J / cm 3 ) 0.5 and SP A (J / cm 3 ) 0.5 This can be adjusted by changing the types of polymerizable monomers, polycarboxylic acids, and polyhydric alcohols used to obtain the resin used for the shell and core particles.

[0078] From the viewpoint of electrostatic stability, the amorphous resin in the shell is preferably a vinyl resin or a polyester resin. More preferably, it is an amorphous polyester resin. As the vinyl resin and polyester resin constituting the shell, the vinyl resins and polyester resins that can be used for the crystalline vinyl resins and amorphous resins described above can be used.

[0079] The shell does not necessarily need to cover the entire core particle; there may be parts of the core that are exposed. For example, the shell only needs to cover the core particle to the extent that it can suppress moisture adsorption by aliphatic alcohols. The shell content in the toner particles is preferably 1.0 to 8.0% by mass, more preferably 2.0 to 6.0% by mass, and even more preferably 3.0 to 5.0% by mass.

[0080] The toner particles may contain wax. The wax is at least one selected from the group consisting of hydrocarbon waxes and ester waxes. Using hydrocarbon waxes and / or ester waxes makes it easier to ensure effective release properties.

[0081] Examples of hydrocarbon waxes include the following: Aliphatic hydrocarbon waxes: low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, Fischer-Tropsch wax, or waxes obtained by oxidation or acid addition of these.

[0082] Ester waxes only need to have at least one ester bond in each molecule, and either natural or synthetic ester waxes may be used. Examples of ester waxes include the following: Esters of monohydric alcohols and monocarboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate; Esters of divalent carboxylic acids and monoalcohols, such as dibehenyl sebacate; Esters of dihydric alcohols such as ethylene glycol distearate and hexanediol dibehenate with monocarboxylic acids; Esters of trihydric alcohols such as glycerol tribehenate and monocarboxylic acids; Esters of tetrahydric alcohols such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate with monocarboxylic acids; Esters of hexahydritol alcohols such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabéhenate with monocarboxylic acids; Esters of polyfunctional alcohols such as polyglycerin behenates and monocarboxylic acids; natural ester waxes such as carnauba wax and rice wax;

[0083] Among these, ester waxes with two or more functionalities are preferred. In particular, ester waxes that are esters of an alcohol with a tetravalent to an octavalent alcohol and an aliphatic monocarboxylic acid, or ester waxes that are esters of a carboxylic acid with a tetravalent to an octavalent carboxylic acid and an aliphatic monoalcohol are more preferred. Including these waxes reduces compatibility with crystalline vinyl resin during fixing, which improves release properties during low-temperature fixing and enhances low-temperature fixing performance.

[0084] Furthermore, esters of tetrahydric alcohols such as pentaerythritol tetrastearate, pentaerythritol tetrapalmitate, and pentaerythritol tetrabehenate with monocarboxylic acids, esters of hexahydric alcohols such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabehenate with monocarboxylic acids, and esters of octahydric alcohols such as tripentaerythritol octastearate, tripentaerythritol octapalmitate, and tripentaerythritol octabehenate with monocarboxylic acids are even more preferred.

[0085] The wax content in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, more preferably 2.0% by mass or more and 25.0% by mass or less. Having the content within the aforementioned range makes it easier to ensure release properties during fixation.

[0086] The melting point of the wax is preferably between 60°C and 120°C. A melting point within this range allows the wax to melt during fixing and easily seep onto the toner particle surface, thus facilitating the wax's release properties. More preferably, the melting point is between 70°C and 100°C.

[0087] Toner particles may contain colorants. Examples of colorants include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic particles. Other colorants conventionally used in toners may also be used.

[0088] Examples of yellow colorants include: condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Among these, CI Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, and 180 are preferred.

[0089] Examples of magenta colorants include: condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolon compounds, thioindigo compounds, and perylene compounds. Among these, CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254 are preferably used.

[0090] Examples of cyanide colorants include: copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Among these, CI pigment blues 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66 are preferably used.

[0091] The colorants are selected based on their hue angle, saturation, brightness, lightfastness, OHP transparency, and dispersibility in toner. The colorant content in the toner particles is preferably 1.0 part by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of the binder resin. When magnetic particles are used as the colorant, their content is preferably 40.0 parts by mass or more and 150.0 parts by mass or less per 100.0 parts by mass of the binder resin.

[0092] The toner particles may contain a charge control agent. Alternatively, the charge control agent may be added externally to the toner particles. By using a charge control agent, the charge characteristics can be stabilized, and the optimal amount of triboelectric charge can be controlled according to the developing system. As a charge control agent, one that has a fast charging speed and can stably maintain a constant amount of charge is preferred.

[0093] Examples of charge control agents that control the toner's charge properties 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.

[0094] Examples of substances that control the toner's positive charge include: nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganostin borates, guanidine compounds, and imidazole compounds. The charge control agent content in the toner particles is preferably 0.01 parts by mass to 20.0 parts by mass, and more preferably 0.5 parts by mass to 10.0 parts by mass, per 100.0 parts by mass of toner particles.

[0095] The toner particles can be used as is as toner, or, if necessary, external additives can be mixed in and attached to the surface of the toner particles to create toner. Examples of external additives include inorganic fine particles selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, or composite oxides thereof. Examples of composite oxides include silica-aluminum fine particles and strontium titanate fine particles. The content of the external additive is preferably 0.01 parts by mass or more and 8.0 parts by mass or less per 100 parts by mass of toner particles, and more preferably 0.1 parts by mass or more and 4.0 parts by mass or less.

[0096] Toner particles can be manufactured by methods such as suspension polymerization, emulsification and agglutination, dissolution and suspension, and pulverization. Suspension polymerization is preferred. The toner particles are preferably suspension polymerized toner particles.

[0097] I will now describe the suspension polymerization method in detail. For example, a polymerizable monomer composition can be prepared by mixing a polymerizable monomer that forms an amorphous vinyl resin, a pre-synthesized crystalline vinyl resin, and an aliphatic alcohol. If necessary, other materials such as colorants, waxes, and charge control agents may be added and uniformly dissolved or dispersed to prepare the polymerizable monomer composition.

[0098] Subsequently, the polymerizable monomer composition is dispersed in an aqueous medium using a stirrer or the like to prepare suspended particles of the polymerizable monomer composition. Then, the polymerizable monomers contained in the particles are polymerized with an initiator or the like, and the resulting toner particle dispersion is cooled to obtain a toner particle dispersion.

[0099] After cooling, the toner particle dispersion may undergo an annealing process to maintain a constant temperature, if necessary. After polymerization is complete, the toner particles are filtered, washed, and dried, and external additives are added as needed to obtain the toner. If a shell is to be formed, for example, a resin for the shell with higher polarity than crystalline vinyl resin and amorphous vinyl resin can be selected and incorporated into the polymerizable monomer composition to form the shell.

[0100] Examples of polymerization initiators include azo or diazo polymerization initiators such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile; and peroxide polymerization initiators such as benzoyl peroxide, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyoctoate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

[0101] Peroxide-based polymerization initiators are preferred as polymerization initiators that readily undergo hydrogen abstraction reactions. Among these, initiators such as t-butyl peroxy 2-ethyl hexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyoctoate, and t-butyl peroxyneodecanoate are more preferably used. In addition, chain transfer agents and / or polymerization inhibitors may be used.

[0102] The aqueous medium may contain inorganic and / or organic dispersion stabilizers. 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.

[0103] Examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, polyacrylic acid and its salts, and starch.

[0104] When using an inorganic compound as a dispersion stabilizer, commercially available products may be used as is, but in order to obtain finer particles, the inorganic compound may be generated in an aqueous medium before use. For example, in the case of calcium phosphate such as hydroxyapatite or tricalcium phosphate, it is best to mix the phosphate aqueous solution with the calcium salt aqueous solution under high stirring.

[0105] The aqueous medium may contain surfactants. Examples of surfactants include anionic surfactants such as sodium dodecylbenzene sulfate and sodium oleate; cationic surfactants; amphoteric surfactants; and nonionic surfactants.

[0106] The following describes the methods for calculating and measuring various physical properties of toner, toner particles, and toner materials. <Separation of toner particles from toner> The toner particles obtained by separating them from the external additive using the following method can be used for each analysis. Add 160g of sucrose (manufactured by Kishida Chemical Co., Ltd.) to 100mL of deionized water and dissolve it in a water bath to prepare a sucrose aqueous solution. Place 31g of the sucrose aqueous solution and 6mL of Contaminon N (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) into a centrifuge tube to prepare a dispersion. Add 1g of toner to this dispersion and break up any clumps of toner with a spatula or similar tool.

[0107] The centrifugation tube is placed in an Iwaki Sangyo Co., Ltd. "KM Shaker" (model: V.SX) and shaken for 20 minutes at a rate of 350 strokes per minute. After shaking, the solution is transferred to a 50 mL glass tube for the swing rotor and centrifuged in a centrifuge (H-9R, manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 minutes. In the glass tube after centrifugation, toner particles are present in the uppermost layer, while external additives such as silica microparticles are present in the lower aqueous solution layer. The toner particles from the upper layer are collected, filtered, and washed with 2 liters of deionized water heated to 40°C. The washed toner particles are then removed.

[0108] <Measurement method for differential scanning calorimetry (DSC)> The presence or absence of crystalline and amorphous resins in toner and toner particles is measured using a differential scanning calorimetry analyzer "Q2000" (TA Instruments) in accordance with ASTM D3418-82. The temperature correction for the instrument's detection unit uses the melting points of indium and zinc, and the heat of fusion of indium is used for heat quantity correction. To measure the toner, first weigh out 10 mg of toner and place it in an aluminum pan. An empty aluminum pan is used as a reference. In the first heating process, measurements are taken while the sample is heated from 20°C to 180°C at a rate of 10°C / min to obtain differential scanning calorimetry curve A. After holding at 180°C for 10 minutes, measurements are taken while cooling from 180°C to 10°C at a rate of 10°C / min to obtain differential scanning calorimetry curve B. Furthermore, after holding at 10°C for 10 minutes, in the second heating process, measurements are taken again while heating from 10°C to 180°C at a rate of 10°C / min to obtain differential scanning calorimetry curve C. The presence or absence of crystalline resin is confirmed by checking the melting point peak that appears in the obtained differential scanning calorimetry curve C. In addition, by checking the glass transition point originating from amorphous resin in differential scanning calorimetry curve C, it is determined that amorphous resin is contained in the toner.

[0109] <Method for separating crystalline vinyl resin, amorphous vinyl resin, and other resins such as shell resin from toner particles> Separation of crystalline vinyl resin, amorphous vinyl resin, and other resins such as shell resin from toner is possible by known methods, one example of which is shown below. Gradient polymer LC is used as a method for separating resin components from toner. This analysis allows for separation based on the polarity of the resin in the binder resin, regardless of molecular weight. First, the toner is dissolved in chloroform. The sample was adjusted to a sample concentration of 0.1% by mass with chloroform, and the solution was filtered through a 0.45 μm PTFE filter and used for measurement.

[0110] The measurement conditions for gradient polymer LC are shown below. Equipment: UlTIMATE3000 (manufactured by Thermo Fisher Scientific) Mobile phase: A. Chloroform (HPLC), B. Acetonitrile (HPLC) Gradient: 2 min (A / B=0 / 100) → 25 min (A / B=100 / 0) (Note that the gradient of the mobile phase change was made to be a straight line.) Flow rate: 1.0mL / min Injection: 0.1 mass% x 20 μL Column: Tosoh TSKgel ODS (4.6mmφ x 150mm x 5μm) Column temperature: 40℃ Detector: Corona Charged Particle Detector (Corona-CAD) (manufactured by Thermo Fisher Scientific) The time-intensity graph obtained from the measurement shows that the resin component can be separated into two peaks depending on its polarity. Subsequently, by repeating the above measurement and sampling at the time of the trough of each peak, it is possible to separate the two types of resin.

[0111] DSC analysis is performed on the separated resins. Resins exhibiting a melting point peak are classified as crystalline vinyl resins, while those without a melting point peak are classified as amorphous vinyl resins. If the toner contains wax, it is necessary to separate the wax from the toner. Wax separation is performed by recycling HPLC, separating components with a molecular weight of 2000 or less as wax.

[0112] The measurement method is as follows. First, a chloroform solution of toner is prepared using the method described above. Then, the obtained solution is filtered through a solvent-resistant membrane filter, "Myshori Disc" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm, to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in chloroform is 1.0% by mass. This sample solution is then measured under the following conditions. ·Equipment: LC-Sakura NEXT (manufactured by Nippon Analytical Industry Co., Ltd.) • Columns: JAIGEL2H, 4H (manufactured by Nippon Analytical Engineering Co., Ltd.) • Eluent: Chloroform ·Flow rate: 10.0ml / min Oven temperature: 40.0℃ • Sample injection volume: 1.0 ml To calculate the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (for example, "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used. From the molecular weight curve obtained in this way, components with a molecular weight of 2000 or less are repeatedly separated, and the wax is removed from the toner.

[0113] <Identification of the structure of monomer units in crystalline vinyl resins, amorphous vinyl resins, and other resins such as shell resins, and a method for measuring the chain length of alkyl groups> Identifying the structure of monomer units in crystalline vinyl resins and amorphous vinyl resins, as well as other resins such as shell resins, and measuring their chain lengths, 1The procedure is performed by 1H-NMR under the following conditions. The sample to be measured can be crystalline vinyl resin and amorphous vinyl resin separated by the method described above, as well as other resins such as shell resin. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 Measurement temperature: 30℃ Sample: Place 50 mg of the sample to be measured into a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as a solvent, and dissolve in a constant temperature bath at 40°C to prepare the sample.

[0114] obtained 1 The H-NMR chart is analyzed to identify the structure of each monomer unit. The chain length of the alkyl group is: 1 It can be calculated from the integral ratio of proton peaks in the H-NMR chart. Furthermore, if a polymerizable monomer is used in which no hydrogen atoms are present in any component other than the vinyl group, 13 The atomic nuclei to be measured using C-NMR 13 Let C be used, and the measurement will be performed in single-pulse mode. 1 The same calculation is performed using 1H-NMR. In addition, infrared absorption spectroscopy (IR) and gas chromatography-mass spectrometry (GC-MS) results may be used as needed.

[0115] <Method for measuring the content ratio of crystalline vinyl resin and amorphous vinyl resin in the binder resin> In the method described above for separating crystalline vinyl resin, amorphous vinyl resin, and other resins such as shell resin from toner particles, the proportion of crystalline vinyl resin and amorphous vinyl resin in the binder resin is calculated based on the mass of the toner before dissolution in chloroform and the mass of the binder resin containing the crystalline vinyl resin, amorphous vinyl resin, and other resins such as shell resin separated from the toner particles.

[0116] <Method for measuring the content ratio of monomer units (a) in crystalline vinyl resin and monomer units (b) in amorphous vinyl resin> The measurement of the monomer unit content in resins, such as the content ratio of monomer units (a) in crystalline vinyl resin and monomer units (b) in amorphous vinyl resin, is performed by: 1 The procedure is performed using H-NMR under the following conditions. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 Measurement temperature: 30℃ Sample: Prepared as follows Place 50 mg of the sample into a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as a solvent, and dissolve it in a constant temperature bath at 40°C to prepare the sample.

[0117] obtained 1 The H-NMR chart is analyzed to identify the structure of each unit. obtained 1 In the H-NMR chart, a peak independent of the peaks attributed to the components of monomer unit (a) is selected from among the peaks attributed to the components of the other units, and the integral value S1 of this peak is calculated. The integral values ​​are calculated similarly for the other monomer units contained in the resin.

[0118] When the resin component consists of monomer unit (a) and one other monomer unit, the content ratio of monomer unit (a) is determined as follows using the integral value S1 and the integral value S2 of the peak of the other monomer unit. Note that n1 and n2 are the number of hydrogen atoms in the constituent element to which the peak of interest is assigned for each part.

[0119] The content of monomer unit (a) (mol %) = {(S1 / n1) / ((S1 / n1)+(S2 / n2))} × 100 Similarly, even if there are two or more other monomer units, the content ratio of monomer unit (a) can be calculated (using S3···Sx and n3···nx).

[0120] If monomers are used in which the components other than the vinyl group do not contain hydrogen atoms, 13 The atomic nuclei to be measured using C-NMR 13 Let C be used, and the measurement will be performed in single-pulse mode. 1 The same calculation can be performed using 1H-NMR. The percentage (mol%) of each monomer unit calculated by the above method is multiplied by the molecular weight of each monomer unit to convert the content of each monomer unit into mass%.

[0121] <Identification of the structure of aliphatic alcohols in toner> Using the same method as described above for identifying the structure of monomer units in crystalline vinyl resins and amorphous vinyl resins, toner was used as a sample. 1 1H-NMR can be used to identify the structure of aliphatic alcohols in toner.

[0122] <Method for measuring the aliphatic alcohol content in toner> The aliphatic alcohol content in the toner is measured using gas chromatography-mass spectrometry and a calibration curve method. Sample preparation will be carried out using the following method. Add 1 mL of chloroform to 10 mg of toner and irradiate with ultrasound for 1 minute to completely dissolve the toner. Next, methanol is added to reprecipitate the resin components. At this time, the dilution ratio with methanol should be adjusted appropriately to ensure linearity in the calibration curve preparation described later and to obtain sufficient detection accuracy in gas chromatography-mass spectrometry. After standing for 1 hour, the supernatant is filtered through a PTFE filter with a mesh size of 0.45 μm and used for measurement.

[0123] The aliphatic alcohol solution for the calibration curve is prepared using the following method. Weigh out 10 mg of aliphatic alcohol and dissolve it in 10 mL of methanol while heating and stirring at 100°C. Dilute the solution with methanol 10 to 1000 times so that the aliphatic alcohol concentration is between 1 ppm and 100 ppm, and prepare at least 5 calibration curve samples.

[0124] The sample obtained by the method described above and the aliphatic alcohol solution for the calibration curve The coal content is measured using gas chromatography-mass spectrometry under the following conditions. The liquid introduction conditions are as follows: Injection volume: 1μl Solvent: methanol Solvent cut: 2.5 min The conditions for gas chromatography-mass spectrometry are as follows: Ion source temperature: 250℃ Scan mode: m / z = 46-400 SIM mode: m / z=83 Inlet temperature: 300℃ Split setting: 50:1 Column: DB35-MS (30m, inner diameter 0.25mm, film thickness 0.25μm) Column pressure: Constant flow Emission current: 30 μA Column heating conditions: (40°C (hold for 3 min), 300°C (10°C / min), 300°C (hold for 3 min)) The mass percentage of aliphatic alcohol in the sample can be calculated using a calibration curve obtained by measuring an aliphatic alcohol solution for calibration. Based on the obtained mass percentage and the amount of binder resin in the toner as described above in the method for measuring the content ratio of crystalline vinyl resin and amorphous vinyl resin in the binder resin, the amount of aliphatic alcohol is calculated based on the mass of the binder resin.

[0125] <How to check your shell> The presence of the toner shell can be confirmed by measuring the morphology of the toner's cross-section. The specific method for measuring the morphology of the toner's cross-section is as follows: First, the toner is sufficiently dispersed in a photocurable epoxy resin, and then the epoxy resin is cured by irradiation with ultraviolet light. The resulting cured material is cut using a microtome equipped with a diamond blade to prepare a 100 nm thick thin sample. After staining the sample with ruthenium tetroxide, a transmission electron microscope (TEM) (product name: Electron microscope Tecnai TF20XT, manufactured by FEI) is used to observe the cross-section of the toner under conditions of an acceleration voltage of 120 kV to obtain a TEM image. In this case, the cross-section of the toner is selected to have a major axis diameter that is 0.9 to 1.1 times the number-average particle size (D1) of the toner measured according to the measurement method for the number-average particle size (D1) of the toner described later.

[0126] In the observation method described above, the amorphous resin in the toner particles is strongly stained by ruthenium tetroxide. As a result, the shell portion, which is mainly composed of amorphous resin, is stained, and the core portion, which contains unstained crystalline resin, becomes visible as a contrast. The observation magnification is 20,000 times. This measurement is performed on 100 toner particles, and if a shell can be confirmed in 80 or more of them, the toner is judged to have a shell.

[0127] <Method for calculating solubility parameters (SP values)> The SP value was calculated according to the method proposed by Fedors, as follows: First, the SP values ​​of the monomer units constituting the resin are determined as follows. Here, the monomer units constituting the resin refer to the molecular structure in which the double bonds of the monomers used to obtain the resin by polymerization have been cleaved by polymerization.

[0128] For example, the SP value (σm) (J / cm) of a monomer unit. 3 ) 0.5 When calculating this, for each atom or group of atoms in the molecular structure of the monomer unit, the evaporation energy (Δei) (J / mol) and molar volume (Δvi) (cm³) are taken from the table in "Polym.Eng.Sci.,14(2),147-154(1974)". 3 Determine the value of (per mole) and calculate it using the following formula. σm = (ΣΔei / ΣΔvi) 0.5 The SP value of a resin is calculated by determining the evaporation energy (Δei) and molar volume (Δvi) of each monomer unit that makes up the resin. Then, the product of the product of each monomer unit and its molar ratio (j) in the resin is calculated, and the sum of the evaporation energies of each monomer unit is divided by the sum of the molar volumes to obtain the SP value, which is then calculated using the following formula. σp={(Σj×ΣΔei) / (Σj×ΣΔvi)} 0.5

[0129] For example, assuming that the resin is composed of two types of monomer units, X and Y, and that the composition ratio of each monomer unit is 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 ratio (j) of each monomer unit will be Wx / Mx and Wy / My, respectively, and the SP value (σp) of this resin will be given by the following formula. σp=[{(Wx / Mx)×Δei(X)+Wy / My×Δei(Y)} / {(Wx / Mx)×Δvi(X)+Wy / My×Δvi(Y)}] 0.5

[0130] 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, as shown in the following formula. σM = Σ(Wi × σi)

[0131] <Method for measuring the number-average particle size (D1) of toner cartridges> The volume-average particle size (Dv) and number-average particle size (D1) of toner are calculated as follows. The particle counting analyzer "CDA-1000X" (manufactured by Sysmex Corporation), which uses the pore electrical resistance method and is equipped with a 100 μm aperture tube, is used as the measuring device. The included dedicated software "CDA-1000X" (manufactured by Sysmex Corporation) is used to set the measurement conditions and analyze the measurement data. For the electrolytic aqueous solution used in the measurement, for example, "Cellpack" (manufactured by Sysmex Corporation) can be used. Before performing the measurements and analysis, the following settings were configured for the dedicated software. In the "Measurement Condition Settings" screen of the dedicated software, set the total count to 50,000, the number of repeated measurements to 1, and the measurement mode to total count (unlimited).

[0132] The specific measurement method is as follows: (1) Place approximately 150 ml of the electrolytic solution into a dedicated glass round-bottom beaker, set it on the sample stage, and stir with the stirring propeller at 500 rpm. Then, click "Blank Check Measurement" in the dedicated software to start the measurement and confirm that the count is less than 100. If the count is 100 or more, repeat the washing of the beaker and aperture. (2) Place 30 ml of the electrolytic aqueous solution into a 100 ml flat-bottomed glass beaker. Add 0.3 ml of a diluted solution of "Contaminon N" (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted three times by mass with deionized water as a dispersant. (3) Prepare an "Ultrasonic Dispension System Tetra150" (manufactured by Nikko Bios Co., Ltd.) ultrasonic disperser with an electrical output of 120W, which incorporates two oscillators with an oscillation frequency of 50kHz with a phase difference of 180 degrees. Add 3.3L of deionized water to the water tank of the ultrasonic disperser, and add 2ml of Contaminon N to this water tank. (4) Place the beaker from (2) into the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution inside the beaker is maximized. (5) With the electrolytic aqueous solution in the beaker in (4) irradiated with ultrasound, 10 mg of toner Add the mixture in small amounts and disperse it. Then, continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank to be between 10°C and 40°C as appropriate. (6) Using a pipette, the electrolytic aqueous solution (5) containing the dispersed toner is dropped into the round-bottom beaker (1) placed in the sample stand, and the concentration is adjusted to 6%. The measurement is then continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software attached to the device to calculate the volume-average particle size (Dv) and the number-average particle size (D1). [Examples]

[0133] The following will provide a detailed explanation with reference to examples, but this disclosure is not limited to the following examples. In the following formulations, "parts" refers to "parts by mass" unless otherwise specified.

[0134] (Preparation of resin A1) The following materials were added to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. • Toluene 100.0 parts • Monomer composition 100.0 parts (The monomer composition shall be a mixture of the following monomers in the proportions shown below.) (Behenyl acrylate 60.0 parts) (Styrene 30.0 parts) (Methacrylonitrile 10.0 parts) • Polymerization initiator: t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 2.0 parts The materials were heated to 70°C in a reaction vessel while being stirred at 200 rpm, and a polymerization reaction was carried out for 12 hours to obtain a solution in which the polymer in the monomer composition was dissolved in toluene. Subsequently, the solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain resin A1 (crystalline vinyl resin). When resin A1 was analyzed by NMR and converted from mol% to mass%, it was found to contain 60.0 mass% of monomer units polymerized from behenyl acrylate, 30.0 mass% of monomer units polymerized from styrene, and 10.0 mass% of monomer units polymerized from methacrylonitrile.

[0135] (Preparation of resins A2 to A10) Crystalline resins A2 to A10 (crystalline vinyl resins) were prepared in the same manner as resin A1, except that the type and amount of monomers used were changed to those listed in Table 1. NMR analysis of resins A2 to A10 revealed that the monomer units polymerized from each monomer were present in the same proportions as the monomers used.

[0136] (Preparation of resin A11) Crystalline resin A11 (crystalline vinyl resin) was prepared in the same manner as resin A1, except that the type and amount of monomers and initiators used were changed as described below. NMR analysis of A11 revealed that monomer units polymerized from each monomer were present in the same proportions as the monomers used. Behenyl acrylate 80.0 parts • Styrene 18.0 parts • Methacrylic acid 2.0 parts • Polymerization initiator t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 0.5 parts

[0137] (Preparation of resin B1) The following materials were added to an autoclave equipped with a vacuum device, a water separator, a nitrogen gas introduction device, a temperature measuring device, and a stirring device. Terephthalic acid 25.3 parts • Bisphenol A-propylene oxide 2 molar adduct 74.7 parts • Potassium titanium oxalate (catalyst) 0.02 parts Next, the reaction was carried out under a nitrogen atmosphere and atmospheric pressure at 220°C for 5 hours, and then under reduced pressure at 220°C for 3 hours. After cooling, the mixture was pulverized to obtain resin B1 (amorphous polyester).

[0138] (Preparation of resin B2) The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. • Solvent: Toluene 100.0 parts, Styrene 60.0 parts, Acrylonitrile 35.0 parts, Methacrylic acid 2.0 parts, 2-Hydroxyethyl methacrylate 3.0 parts, Polymerization initiator: t-Butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 5.0 parts The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer polymer was dissolved in toluene. Subsequently, the solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain resin B2 (amorphous vinyl).

[0139] (Preparation of resin B3) Resin B3 (amorphous vinyl) was obtained using the same manufacturing method as described below, except that the raw material composition of resin B2 was changed. • Styrene 54.0 parts • Acrylonitrile 41.0 parts • Methacrylic acid 2.0 parts • 2-Hydroxyethyl methacrylate 3.0 parts • Polymerization initiator t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 5.0 parts

[0140] (Preparation of resin B4) The following materials were added to an autoclave equipped with a vacuum device, water separator, nitrogen gas introduction device, temperature measuring device, and stirring device. • Sebacic acid 64.2 parts 1,6-Hexanediol 35.8 parts • Potassium titanium oxalate (catalyst) 0.06 parts Next, the reaction was carried out under a nitrogen atmosphere and atmospheric pressure at 220°C. After cooling, the mixture was pulverized to obtain resin B4 (crystalline polyester (PES)).

[0141] [Table 1] Resins A1 to A11 exhibited distinct endothermic peaks in differential scanning calorimeter (DSC) measurements.

[0142] <Example 1> [Toner manufacturing by suspension polymerization method] (Manufacturing of toner particles 1) A mixture of the following materials was prepared. • Styrene 45.0 parts • n-butyl acrylate 15.0 parts Pigment blue 15:3 (coloring agent) 6.4 parts The mixture was placed in an attritor (manufactured by Nippon Coke Industries Co., Ltd.) and dispersed using 5 mm diameter zirconia beads at 200 rpm for 2 hours to obtain a raw material dispersion.

[0143] Meanwhile, 735.0 parts of deionized water and 16.0 parts of trisodium phosphate (dodecahydrate) were added to a container equipped with a high-speed stirring device homomixer (manufactured by Primix Co., Ltd.) and a thermometer, and the temperature was raised to 60°C while stirring at 12,000 rpm. Then, an aqueous calcium chloride solution, prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of deionized water, was added, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining the temperature at 60°C. Then, 10% hydrochloric acid was added to adjust the pH to 6.0, and an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water was obtained.

[0144] Next, the raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and heated to 60°C while being stirred at 100 rpm. • Resin A1 40.0 parts ·Resin B1 4.0 parts • DP18 (Dipentaerythritol stearate wax, melting point 79°C, manufactured by Nisshin Oillio Group Ltd.) 9.0 parts • HDDA (Hexanediol diacrylate) 0.1 part • Behenyl alcohol 0.52 parts The above materials were added to the mixture and stirred at 100 rpm for 30 minutes while maintaining a temperature of 60°C. Then, t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) was added as a polymerization initiator. 8.0 parts were added and stirred for a further minute, then it was added to the aqueous medium being stirred at 12,000 rpm using the high-speed stirring device. Stirring was continued at 12,000 rpm for 20 minutes while maintaining a temperature of 60°C using the high-speed stirring device to obtain granulated liquid.

[0145] The granulated liquid was transferred to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube, and heated to 76°C while stirring at 150 rpm under a nitrogen atmosphere. The polymerization reaction was carried out at 150 rpm for 6 hours while maintaining the temperature at 76°C to obtain a toner particle dispersion.

[0146] The obtained toner particle dispersion was cooled to 48°C while being stirred at 150 rpm, and then annealed for 8 hours while maintaining the temperature at 48°C. After that, while maintaining stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid components were filtered off, thoroughly washed with deionized water, and then vacuum dried at 30°C for 24 hours to obtain toner particles 1.

[0147] Analysis of toner particle 1 revealed that it contained 4920 ppm of behenyl alcohol based on the mass of the binder resin. Furthermore, toner particle 1 contained both crystalline vinyl resin and amorphous vinyl resin. In toner particle 1, the crystalline vinyl resin and amorphous vinyl resin were present in the mass proportions corresponding to the number of units added. The monomer units constituting the amorphous vinyl resin were present in the same proportion (mass ratio) as the monomers from which each monomer unit originated.

[0148] (Preparation of Toner 1) For every 1:98.0 parts of toner particles, an external additive is provided: silica microparticles (hydrophobically treated with hexamethyldisilazane, primary particle number average particle size: 10 nm, BET specific surface area: 170 m²). 22.0 parts of ( / g) were added and mixed for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Industries Co., Ltd.) to obtain Toner 1. The evaluation results of the obtained Toner 1 are shown in Table 3.

[0149] <Examples 2-35> In Example 1, toner particles 2 to 35 were obtained in the same manner as in Example 1, except that the type and amount of resin used, the type and amount of polymerizable monomer used, and the type and amount of aliphatic alcohol used were changed as shown in Tables 2-1 and 2-2. Furthermore, the same external additive procedure as in Example 1 was performed to obtain toners 2-35. The toner evaluation results are shown in Table 3.

[0150] <Example 36> [Toner manufacturing using the grinding method] (Preparation of amorphous vinyl resin 1) The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. • Solvent: Toluene 100.0 parts • Styrene 45.0 parts • n-butyl acrylate 15.0 parts • HDDA (Hexanediol diacrylate) 0.1 part • Polymerization initiator: t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 8.0 parts The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer polymer was dissolved in toluene. Subsequently, the solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain amorphous vinyl resin 1. Amorphous vinyl resin 1 was analyzed by NMR, and when the mole percentage was converted to mass percentage, styrene was found to be heavy The compound contained 45.0% by mass of combined monomer units and 15.0% by mass of monomer units polymerized from n-butyl acrylate.

[0151] (Manufacturing of toner particles 36) Amorphous vinyl resin 1:60.0 parts • Resin A1: 40.0 parts • DP18 (Dipentaerythritol stearate wax, melting point 79°C, manufactured by Nisshin Oillio Group Ltd.) 9.0 parts Pigment blue 15:3 (coloring agent): 6.4 parts Behenyl alcohol 0.50 parts The above materials were mixed using a Henschel mixer (FM-75 model, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 1500 rpm for a rotation time of 5 min, and then kneaded in a twin-screw kneader (PCM-30 model, manufactured by Ikegai Co., Ltd.) set to a temperature of 130°C. The resulting kneaded material was cooled and coarsely ground to a size of 1 mm or less using a hammer mill to obtain coarse material.

[0152] The obtained coarse material was finely ground using a mechanical crusher (T-250, manufactured by Turbo Industries Co., Ltd.). Further classification was performed using a Faculty (F-300, manufactured by Hosokawa Micron Corporation) to obtain toner particles 36. The operating conditions were a classification rotor speed of 11,000 rpm and a dispersion rotor speed of 7,200 rpm.

[0153] (Manufacturing of Toner 36) Toner particles 36 were subjected to the same external additive treatment as in Example 1 to obtain toner 36. The evaluation results of the toner are shown in Table 3.

[0154] <Comparative Examples 1-9, 11> In Example 1, all procedures were carried out in the same manner except for changing the type and amount of resin used, the type and amount of polymerizable monomer used, and the type and amount of aliphatic alcohol used, as shown in Tables 2-1 and 2-2, to obtain comparative toner particles 1-9 and 11. Furthermore, the same external additive procedure as in Example 1 was performed to obtain comparative toners 1-9 and 11. The evaluation results of the toners are shown in Table 3.

[0155] <Comparative Example 10> [Toner manufacturing by suspension polymerization method] (Preparation of comparative toner particles 10) The following materials were added to an attritor (manufactured by Nippon Coke Co., Ltd.). • Methacrylonitrile 30.0 parts • Styrene 13.0 parts • Ethyl methacrylate 7.0 parts • Coloring agent (pigment blue 15:3) 6.4 parts A dispersion of raw materials was obtained by dispersing 5 mm diameter zirconia beads at 200 rpm for 2 hours.

[0156] Meanwhile, 735.0 parts of deionized water and 16.0 parts of trisodium phosphate dodecahydrate were added to a container equipped with a high-speed stirring device homomixer (manufactured by Primix) and a thermometer, and the temperature was raised to 60°C while stirring at 12,000 rpm. Subsequently, a calcium chloride aqueous solution, prepared by dissolving 9.0 parts of calcium chloride dihydrate in 65.0 parts of deionized water, was added to the above container, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining a temperature of 60°C, thereby obtaining an aqueous medium in which a dispersion stabilizer containing hydroxyapatite was dispersed in water.

[0157] Next, the above raw material dispersion is transferred to a container equipped with a stirring device and a thermometer, and stirred at 100 rpm. The temperature was raised to 60°C while stirring. Behenyl acrylate 50.0 parts • DP18 (Dipentaerythritol stearate wax, melting point 79°C, manufactured by Nisshin Oillio Group Ltd.) 10.0 parts Behenyl alcohol 0.50 parts The above materials were added to the mixture and stirred at 100 rpm for 30 minutes while maintaining a temperature of 60°C. Then, 8.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) were added as a polymerization initiator and stirred for another minute. The mixture was then added to an aqueous medium being stirred at 12,000 rpm using the high-speed stirring device. Stirring was continued at 12,000 rpm for 20 minutes while maintaining a temperature of 60°C to obtain a granulated liquid.

[0158] The granulated liquid was transferred to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube, and heated to 76°C while stirring at 150 rpm under a nitrogen atmosphere. The polymerization reaction was carried out at 150 rpm for 6 hours while maintaining the temperature at 76°C to obtain a toner particle dispersion. The obtained toner particle dispersion was cooled to 48°C while being stirred at 150 rpm, and then annealed for 8 hours while maintaining the temperature at 48°C. After that, while maintaining stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid components were filtered off, thoroughly washed with deionized water, and then vacuum dried at 30°C for 24 hours to obtain comparative toner particles 10.

[0159] Furthermore, comparative toner particles 10 were subjected to the same external additive as in Example 1 to obtain comparative toner 10. The evaluation results of the toners are shown in Table 3.

[0160] <Comparative Example 12> (Manufacturing of comparison toner 12) Comparative toner particles 12 were obtained in the same manner as in Example 36, except that resin A1 and amorphous vinyl resin 1, which are used, were all replaced with resin A10. Furthermore, a comparative toner 12 was obtained by performing the same external additive procedure as in Example 1. The evaluation results of the toners are shown in Table 3.

[0161] <Comparative Example 13> (Preparation of comparative crystalline polyester resin 1) • 1,6-Hexanediol: 34.5 parts (0.29 moles; 100.0 mol% of the total number of moles of polyhydric alcohols) Dodecanediic acid: 65.5 parts (0.28 moles; 100.0 mol% of the total number of moles of polycarboxylic acids) • Tin 2-ethylhexanoate: 0.5 parts The above materials were weighed into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet tube, and thermocouple. After replacing the inside of the flask with nitrogen gas, the temperature was gradually increased while stirring, and the reaction was carried out for 3 hours at a temperature of 140°C while stirring. Next, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200°C. After that, the pressure in the reaction vessel was reduced to 5 kPa or less, and the reaction was carried out at 200°C for 3 hours to obtain comparative crystalline polyester resin 1.

[0162] (Manufacturing of comparison toner 13) Comparative toner particles 13 were obtained in the same manner as in Example 1, except that comparative crystalline polyester resin 1 was added instead of resin A1. Furthermore, the same external additive procedure as in Example 1 was performed to obtain comparative toner particles 13. The evaluation results of the toners are shown in Table 3. <Comparative Example 14>

[0163] (Preparation of comparative amorphous polyester resin 1) • Bisphenol A propylene oxide adduct (average number of moles added: 2.0): 37.0 parts (13.6 mol%) Ethylene glycol: 13.0 parts (35.5 mol%) Terephthalic acid: 50.0 parts (50.9 mol%) Titanium tetrabutoxide (esterification catalyst): 0.5 parts The above materials were weighed into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet tube, and thermocouple. Next, the flask was purged with nitrogen gas, and the temperature was gradually increased while stirring. The mixture was then reacted at 200°C while stirring for 2 hours. Furthermore, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 5 hours while maintaining the temperature at 200°C. After confirming that the softening point, measured according to ASTM D36-86, reached 100°C, the temperature was lowered to stop the reaction and comparative amorphous polyester resin 1 was obtained.

[0164] (Manufacturing of comparison toner 14) In Example 36, comparative toner particles 14 were obtained in the same manner as in Example 36, except that comparative amorphous polyester resin 1 was added instead of amorphous vinyl resin 1. Furthermore, a comparative toner 14 was obtained by performing the same external additive procedure as in Example 1. The evaluation results of the toners are shown in Table 3.

[0165] <Comparative Example 15> (Production of Comparative Toner Particles 15) · 15.0 parts of n-dodecyl acrylate · 45.0 parts of styrene · 6.5 parts 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.

[0166] On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts 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 of calcium chloride (dihydrate) was dissolved in 65.0 parts 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 aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water was obtained.

[0167] 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. · 40.0 parts of crystalline resin A11 · 9.0 parts of release agent 1 (Release agent 1: DP18 (dipentaerythritol stearate wax), melting point 79°C, manufactured by Nippon Seiro Co., Ltd.) The above materials were added thereto, and after stirring at 100 rpm for 30 minutes while maintaining 60°C, 9.0 parts of t-butyl peroxy pivalate (manufactured by NOF Corporation: Perbutyl PV) as a polymerization initiator was added and stirred for another 1 minute, and then it was put into the aqueous medium being stirred at 12,000 rpm in the above high-speed stirring device. Stirring was continued at 12,000 rpm for 20 minutes in the above high-speed stirring device while maintaining 60°C to obtain a granulation liquid.

[0168] The above granulated liquid was transferred to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube, and heated to 70°C while stirring at 150 rpm under a nitrogen atmosphere. While maintaining the temperature at 70°C A polymerization reaction was carried out at 150 rpm for 12 hours to obtain a toner particle dispersion. The obtained toner particle dispersion was cooled to 45°C while being stirred at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. After that, while maintaining stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid components were filtered off, thoroughly washed with deionized water, and then vacuum-dried at 30°C for 24 hours to obtain comparative toner particles 15.

[0169] (Preparation of comparative toner 15) A comparative toner 15 was obtained by performing the same external additive procedure as in Example 1. The evaluation results of the toner are shown in Table 3.

[0170] [Table 2-1] In the table, in the manufacturing method column, SP indicates suspension polymerization and P indicates grinding method. m1 is m1 in formula (1), and m2 is m2 in formula (2). The CV ratio is the binder resin. The AV ratio is the percentage of crystalline vinyl resin content (mass%) based on the mass of the binder resin, while the AV ratio is the percentage of amorphous vinyl resin content (mass%) based on the mass of the binder resin.

[0171] [Table 2-2]

[0172] In Table 2-2, the amount of aliphatic alcohol added is expressed as parts by mass per 100 parts by mass of the binder resin. The amount detected from the toner is the amount of aliphatic alcohol (mass ppm) relative to the mass of the binder resin. SPS-SPA is SP S -SP A (J / cm 3 ) 0.5 This indicates.

[0173] The toners for Examples 1-36 and Comparative Examples 1-15 were evaluated as follows. The evaluation results for each are shown in Table 3. Furthermore, it was confirmed that in each toner using resin B, the toner particles had a shell made of resin B.

[0174] <Toner Evaluation Method> <1> Evaluation of low-temperature fixation properties A toner-filled process cartridge (a process cartridge for a laser beam printer (LBP-712Ci, manufactured by Canon Inc.)) was left at 25°C and 40% RH humidity for 48 hours. Using a modified Canon laser beam printer (LBP-712Ci) that was modified to operate even without the fuser, an unfixed image of an image pattern with 10mm x 10mm squares evenly distributed at 9 points across the entire transfer paper was printed. The amount of toner adhering to the transfer paper was 0.80 mg / cm². 2 The fixing start temperature was then evaluated. The transfer paper used was A4 paper (Proverbond paper: 105 g / m²). 2 (Fox River Industries) was used.

[0175] The fuser used was an external fuser, which was created by removing the fuser from a laser beam printer (LBP-712Ci, manufactured by Canon Inc.) and modifying it to operate outside the laser beam printer. The external fuser was used to perform fixing by increasing the fixing temperature from 90°C in 5°C increments, at a process speed of 360 mm / s. The fixed image was visually inspected, and the lowest temperature at which no cold offset occurred was defined as the fixing start temperature to evaluate low-temperature fixing performance. A fixing start temperature of 120°C or lower was considered good. The evaluation results are shown in Table 3.

[0176] <2> Evaluation of hot offset resistance The highest temperature at which no hot offset was observed under the same conditions as for low-temperature fixing was defined as the maximum fixing temperature, and the difference between the maximum fixing temperature and the fixing start temperature was defined as the fixable region. A fixable region of 40°C or higher was considered good. The evaluation results are shown in Table 3.

[0177] <3> Evaluation of Gross Stability As a fuser, the above <1> The external fuser used in the evaluation was used. A5 paper (PB PAPER, manufactured by Canon Inc.) was used as transfer paper, as described above. <1> At the fixing start temperature used in the evaluation, 100 fixed images were output consecutively at a paper feeding interval of 38 sheets / minute. For the evaluation, an unfixed image was used, which was an image pattern in which 10mm x 10mm square images were evenly arranged at 9 points across the entire transfer paper. At this time, the image pattern was formed so that the centers of the square images at both ends (6 points) were located 7mm from both ends of the paper. For the 100th image that was fixed, the gloss value was measured using a handheld gloss meter PG-1 (manufactured by Nippon Denshoku Industries Co., Ltd.). The measurement conditions involved setting the light projection angle and light reception angle to 75°, measuring all 9-point image patterns, and evaluating the average gloss value. The standard deviation of the measured values ​​was used as the gloss unevenness to evaluate gloss stability. A standard deviation (gloss unevenness) of less than 3.00 was considered good. The evaluation results are shown in Table 3.

[0178] <4> Evaluation of bending resistance The bending resistance was evaluated using a commercially available Canon LBP-712Ci printer. A process cartridge filled with toner was left for 48 hours at 25°C and 40% RH. Using the above printer, a 50mm x 50mm sample with a toner load of 0.8mg / cm² was tested. 2 Two copies of the solid color image were printed on the center of the transfer paper at a fixing start temperature of +10°C, as measured in the low-temperature fixing performance evaluation above. One of the printed solid color images underwent the following folding operation. The folding operation involved folding the transfer paper so that the valley fold lines formed the diagonals of the solid color image, and folding the transfer paper so that the mountain fold lines bisected each side of the transfer image, forming a cross in the center of the solid color image. In other words, after one folding operation, two valley folds were formed on the solid color image. A line and two mountain fold lines were formed.

[0179] The folding operation was performed five times. That is, after performing the above folding, the transfer paper was unfolded, and folding was repeated at the same location again, for a total of five foldings. After the folding operation was completed, the transfer paper was unfolded, covered with a soft tissue paper (product name "Dasper", manufactured by Otsu Sangyo Co., Ltd.), and rubbed back and forth eight times while applying a load of 4.9 kPa from above the tissue paper. The image density was measured with the intersection of the four folding lines as the center of the solid image. For one of the printed solid images, no folding operation was performed, and only the above rubbing operation was performed, and the image density was measured in alignment with the center of the solid image. The image density at the center of the solid image of the transfer paper with the folding operation performed and the transfer paper without the folding operation was compared, and the image density reduction rate ΔD (%) was evaluated. This ΔD (%) was used as an index for the folding resistance. An image density reduction rate of 9.0% or less was judged to be good. The image density reduction rate was calculated by the following formula. ΔD (%) = {(image density of the transfer paper without folding - image density of the transfer paper with folding) / image density of the transfer paper without folding} × 100 The image density was measured with a color reflection densitometer (Color reflection densitometer X-Rite 404A, manufactured by X-Rite). The evaluation results are shown in Table 3.

[0180] <5>Evaluation of Charge Stability Using the LBP-712Ci, in a high-temperature and high-humidity environment (HH) (temperature 32.5 °C, humidity 80% RH), 3000 images with a printing rate of 1% were printed out using the printer. After leaving it for three days, one image with a white background was printed out. For the obtained image, reflectance measurement was performed using a reflectometer (Reflectometer model TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.). An amber filter was used as the filter for measurement. The worst value Ds (%) during the five-point measurement of the white background reflectance and Dr - Ds when the reflectance of the transfer material before image formation was Dr (%) were evaluated as fogging after leaving it in HH. The evaluation results are shown in Table 3. A fogging of 2.2% or less was judged to be good.

[0181] <6> Evaluation of heat resistance and preservation properties To evaluate the stability during storage, a heat resistance evaluation was conducted. 5g of toner was placed in a 100ml plastic cup and left for 3 days at a temperature of 50°C and a humidity of 70%RH. The degree of toner aggregation was then measured as follows and evaluated according to the following criteria. The measuring device used was a "Powder Tester" (Hosokawa Micron Corporation) with a digital display vibration meter "DigiVibro MODEL1332A" (Showa Sokki Co., Ltd.) connected to the side of the vibration table. Then, on the vibration table of the powder tester, the sieves were stacked from bottom to top in the following order: a 38 μm (400 mesh) sieve, a 75 μm (200 mesh) sieve, and a 150 μm (100 mesh) sieve. The measurements were performed in an environment of 23°C and 60% RH as follows. (1) The vibration amplitude of the vibration table was pre-adjusted so that the displacement value of the digital display vibration meter was 0.60 mm (peak-to-peak). (2) The toner that had been left for 3 days as described above was then left for 24 hours in an environment of 23°C and 60% RH. Then, 5.00 g of toner was weighed and gently placed on the top sieve with a mesh size of 150 μm. (3) After vibrating the sieves for 15 seconds, the mass of toner remaining on each sieve was measured, and the degree of cohesion was calculated based on the following formula. The evaluation results are shown in Table 3. A lower cohesion degree (%) indicates better heat resistance and storage performance. A cohesion degree of 15.0% or less was considered good. Degree of aggregation (%) = {(Sample mass on a sieve with a mesh size of 150 μm (g)) / 5.00 (g)} × 100 + {(Sample mass on a sieve with a mesh size of 75 μm (g)) / 5.00 (g)} × 100 × 0. 6 + {(Sample mass on a sieve with a mesh size of 38 μm (g)) / 5.00 (g)} × 100 × 0.2

[0182] [Table 3]

[0183] In the table, the difference in the evaluation of hot offset resistance is the difference between the maximum fixing temperature and the fixing start temperature.

[0184] This disclosure relates to the following configuration. (Composition 1) A toner having toner particles, The toner particles contain a binder resin and an aliphatic alcohol, The binder resin contains crystalline vinyl resin and amorphous vinyl resin, The crystalline vinyl resin contains a monomer unit (a) represented by the following formula (1), The amorphous vinyl resin contains a monomer unit (b) represented by the following formula (2), The aliphatic alcohol is a compound represented by the following formula (3): A toner characterized in that the toner particles contain 100 to 10,000 ppm of the aliphatic alcohol based on the mass of the binder resin. TIFF2026054074000013.tif104153(In formula (1), R1 represents a hydrogen atom or a methyl group, L1 represents a single bond, an ester bond, or an amide bond, and m1 represents an integer from 15 to 29.) In formula (2), R2 represents a hydrogen atom or a methyl group, L2 represents a single bond, an ester bond, or an amide bond, and m2 represents an integer from 0 to 13. In equation (3), m3 represents an integer between 15 and 29. (Configuration 2) The toner according to configuration 1, wherein the toner particles contain 100 to 6000 ppm of the aliphatic alcohol based on the mass of the binder resin. (Composition 3) The toner according to configuration 1, wherein the content ratio of the amorphous vinyl resin, based on the mass of the binder resin, is 25.0 to 95.0% by mass. (Composition 4) The toner according to any of configurations 1 to 3, wherein m1 and m3 satisfy the following formula (4). |m1-m3|≦2 ···(4) (Composition 5) The toner according to configuration 4, wherein m2 and m3 satisfy the following formula (5). |m2-m3|≧6 ···(5) (Composition 6) The toner according to any one of configurations 1 to 5, wherein the content of the monomer unit (a) represented by formula (1) in the crystalline vinyl resin is 5.0 to 100.0% by mass. (Composition 7) The toner according to any one of configurations 1 to 6, wherein the content of the crystalline vinyl resin, based on the mass of the binder resin, is 5.0 to 75.0% by mass. (Composition 8) The toner described in any of configurations 1 to 7, wherein m2 represents an integer from 3 to 13. (Composition 9) The toner according to any one of configurations 1 to 8, wherein the amorphous vinyl resin contains 20.0 to 90.0% by mass of monomer units made of styrene. (Composition 10) The toner according to any one of configurations 1 to 9, wherein the toner particles are toner particles having a core-shell structure comprising a core particle and a shell formed on the surface of the core particle. (Composition 11) The shell is made of amorphous resin, and the SP value of the amorphous resin of the shell is SP S (J / cm 3 ) 0.5 year, The SP value of the crystalline vinyl resin is SP A (J / cm 3 ) 0.5 In that case, The SP S and the SP A The toner described in configuration 10 satisfies the following formula (6). SP S -SP A ≤5.0 ···(6)

Claims

1. A toner having toner particles, The toner particles contain a binder resin and an aliphatic alcohol, The binder resin contains crystalline vinyl resin and amorphous vinyl resin, The crystalline vinyl resin contains a monomer unit (a) represented by the following formula (1), The amorphous vinyl resin contains a monomer unit (b) represented by the following formula (2), The aliphatic alcohol is a compound represented by the following formula (3): A toner characterized in that the toner particles contain 100 to 10,000 ppm of the aliphatic alcohol based on the mass of the binder resin. (In formula (1), R １ L represents a hydrogen atom or a methyl group. １ m1 represents a single bond, ester bond, or amide bond, and m1 represents an integer between 15 and 29. In formula (2), R ２ L represents a hydrogen atom or a methyl group. ２ m² represents a single bond, ester bond, or amide bond, and m² represents an integer from 0 to 13. In equation (3), m3 represents an integer between 15 and 29.

2. The toner according to claim 1, wherein the toner particles contain 100 to 6000 ppm of the aliphatic alcohol based on the mass of the binder resin.

3. The toner according to claim 1, wherein the content ratio of the amorphous vinyl resin, based on the mass of the binder resin, is 25.0 to 95.0% by mass.

4. The toner according to any one of claims 1 to 3, wherein m1 and m3 satisfy the following formula (4). |m1-m3|≦2...(4)

5. The toner according to claim 4, wherein m2 and m3 satisfy the following formula (5). |m2-m3|≧6...(5)

6. The content of the monomer unit (a) represented by formula (1) in the crystalline vinyl resin The toner according to any one of claims 1 to 3, wherein the proportion is 5.0 to 100.0% by mass.

7. The toner according to any one of claims 1 to 3, wherein the content of the crystalline vinyl resin, based on the mass of the binder resin, is 5.0 to 75.0% by mass.

8. The toner according to any one of claims 1 to 3, wherein m2 represents an integer from 3 to 13.

9. The toner according to any one of claims 1 to 3, wherein the amorphous vinyl resin contains 20.0 to 90.0% by mass of monomer units made of styrene.

10. The toner according to any one of claims 1 to 3, wherein the toner particles are toner particles having a core-shell structure comprising a core particle and a shell formed on the surface of the core particle.

11. The shell is made of amorphous resin, and the SP value of the amorphous resin of the shell is SP Ｓ (J / cm ３ ) ０．５ year, When the SP value of the crystalline vinyl resin is SP Ａ (J / cm ３ ) ０．５ then The SP Ｓ and the SP Ａ The toner according to claim 10, wherein the following formula (6) is satisfied. SP Ｓ - SP Ａ ≦5.0 ・・・(6)

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