Toner

Abstract

To provide a toner which suppresses aggregation of a pigment and is excellent in coloring power.SOLUTION: A toner includes toner particles containing a binder resin, a pigment, and a pigment dispersant, wherein the pigment dispersant has a structure represented by formula (1) and a polymer moiety containing a structure represented by formula (3).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to toners used to form toner images by developing electrostatic latent images formed by methods such as electrophotography, electrostatic recording, and toner jet recording. [Background technology]

[0002] As electrophotographic technology used in copiers, printers, facsimile receiving devices, etc. advances, the demands of users are becoming more stringent year by year. In recent years, there has been a strong demand for compact designs so that devices can be installed anywhere.

[0003] To meet the above demands, one method is to improve the coloring power of the toner and form an image using a smaller amount of toner, thereby reducing the size of the toner container.

[0004] In order to improve the coloring power of a toner, it is effective to finely disperse the pigment. As a means for improving pigment dispersibility, for example, Patent Document 1 proposes a toner in which the relationship between the hydrophobic parameters of the crystalline polyester and the pigment dispersant is specified in toner particles containing a binder resin, a crystalline polyester, and a pigment dispersant.

[0005] The above measures have made it possible to obtain a toner with high coloring power and excellent low-temperature fixability, and toner containers can be made smaller. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-157104 Summary of the Invention [Problem to be solved by the invention]

[0007] However, from the viewpoint of further miniaturization, there is a demand for image formation with a smaller amount of toner. The pigment dispersant disclosed in Patent Document 1 has a limited effect of suppressing pigment aggregation, and further improvement in coloring power cannot be expected. Therefore, there is still a demand for improvement in coloring power by improving pigment dispersibility.

[0008] The present disclosure provides a toner that suppresses pigment aggregation in the toner and has excellent coloring power. [Means for solving the problem]

[0009] The present disclosure provides a toner having toner particles containing a binder resin, a pigment, and a pigment dispersant, The toner is characterized in that the pigment dispersant has a structure represented by the following formula (1) and a polymer moiety containing a structure represented by the following formula (3).

[0010] [ka]

[0011] (In formula (1), R1 represents a substituted alkyl group, an unsubstituted alkyl group, a substituted phenyl group, or an unsubstituted phenyl group; R2~R 11 At least one of these is a moiety that links to the polymer moiety, and the remaining moieties each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an amino group, a cyano group, a trifluoromethyl group, a carboxy group, or a structure represented by the following formula (2-1), or R to R 11 The adjacent groups among these have a structure represented by the following formula (2-2):

[0012] [ka]

[0013] (In formula (2-1), * indicates a benzene ring having R2 to R6 in formula (1), or R7 to R 11 represents the bonding position to the benzene ring having R 12 represents a hydrogen atom, a substituted alkyl group, an unsubstituted alkyl group, a substituted aralkyl group, an unsubstituted aralkyl group, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group, A1 is an oxygen atom, a sulfur atom, or NR 13 represents a group, R 13 represents a hydrogen atom, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group.

[0014] [ka]

[0015] (In formula (2-2), ** and *** represent a benzene ring having R2 to R6 in formula (1), or R7 to R 11 represents a bonding site with a benzene ring having A2 is an oxygen atom, a sulfur atom, or NR 13 represents a group, R 13 represents a hydrogen atom, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group.

[0016] [ka]

[0017] (In formula (3), R 14 ~R 17 At least two of them are -X-COOR18 and the rest each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0018] X represents a single bond or an alkylene group having 1 to 2 carbon atoms; R 18 represents an alkyl group having 16 to 30 carbon atoms. [Effects of the Invention]

[0019] According to the present disclosure, a toner with excellent coloring power can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0020] The present disclosure will be described in detail below, but is not limited to these descriptions. In the present disclosure, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints, unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined arbitrarily. Furthermore, a monomer unit refers to a structure formed by the reaction of a monomer in a polymer.

[0021] Each of the above requirements will be explained in detail below.

[0022] The toner of the present disclosure is A toner having toner particles containing a binder resin, a pigment, and a pigment dispersant, The pigment dispersant is characterized by having a structure represented by the following formula (1) and a polymer moiety containing a structure represented by the following formula (3).

[0023] [ka]

[0024] (In formula (1), R1 represents a substituted alkyl group, an unsubstituted alkyl group, a substituted phenyl group, or an unsubstituted phenyl group; R2~R 11 At least one of these is a moiety that links to the polymer moiety, and the remaining moieties each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an amino group, a cyano group, a trifluoromethyl group, a carboxy group, or a structure represented by the following formula (2-1), or R to R 11 The adjacent groups among these have a structure represented by the following formula (2-2):

[0025] [ka]

[0026] (In formula (2-1), * indicates a benzene ring having R2 to R6 in formula (1), or R7 to R 11 represents a bonding site with a benzene ring having R 12 represents a hydrogen atom, a substituted alkyl group, an unsubstituted alkyl group, a substituted aralkyl group, an unsubstituted aralkyl group, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group, A1 is an oxygen atom, a sulfur atom, or NR 13 represents a group, R 13 represents a hydrogen atom, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group.

[0027] [ka]

[0028] (In formula (2-2), ** and *** represent a benzene ring having R2 to R6 in formula (1), or R7 to R 11 represents a bonding site with a benzene ring having A2 is an oxygen atom, a sulfur atom, or NR 13 represents a group, R 13 represents a hydrogen atom, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group.

[0029] [ka]

[0030] (In formula (3), R 14 ~R 17 At least two of them are -X-COOR 18 and the rest each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0031] X represents a single bond or an alkylene group having 1 to 2 carbon atoms; R 18 represents an alkyl group having 16 to 30 carbon atoms. It has been found that a toner having excellent coloring power can be obtained by satisfying the above requirements. The present inventors consider the mechanism as follows.

[0032] The pigment dispersant of the present disclosure has a structure represented by formula (1) and a polymer moiety containing a structure represented by formula (3).

[0033] The structure represented by formula (1) has a portion that exhibits strong π-π interactions, and therefore easily interacts strongly with pigments, allowing pigment dispersants containing the structure represented by formula (1) to exist in the vicinity of pigments.

[0034] The structure represented by formula (3) has at least two long-chain alkyl groups, so the long-chain alkyl groups within the structure are close to each other. The action of these close long-chain alkyl groups easily generates steric repulsion. Therefore, pigment dispersants containing the structure represented by formula (3) can improve the dispersion stability of pigments by the elimination effect of steric repulsion.

[0035] By using the pigment dispersant of the present disclosure, it is possible to suppress aggregation of pigment particles and stabilize the dispersed state of the pigment, thereby obtaining a toner with excellent coloring power.

[0036] <Pigment dispersant> The structure of the pigment dispersant represented by formula (1) and preferred embodiments thereof will be described in detail below.

[0037] The structure of the pigment dispersant represented by formula (1) is a site that adsorbs to the pigment, and is also called a pigment adsorption site.

[0038] The alkyl group for R1 in formula (1) includes linear, branched, and cyclic alkyl groups, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a cyclohexyl group.

[0039] The alkyl group or phenyl group of R1 in the above formula (1) may be further substituted with a substituent, as long as it does not significantly impair the affinity for the pigment. In this case, the substituent may be, for example, a halogen atom, a nitro group, an amino group, a hydroxy group, a cyano group, or a trifluoromethyl group.

[0040] Among the above, R1 in the above formula (1) is preferably a methyl group from the viewpoint of affinity to the pigment.

[0041] R2 to R in the above formula (1) 11is a moiety that constitutes a bonding site with the polymer moiety. The bond with the polymer moiety may be a single bond or a bond via a linking group present at the end of the polymer moiety.

[0042] From the viewpoint of affinity to the pigment, it is preferable that at least one of R2 to R6 is a moiety that forms a bonding site with the polymer moiety.

[0043] R2 to R are not the bonded portion with the polymer moiety. 11 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an amino group, a cyano group, a trifluoromethyl group, a carboxy group, a structure represented by the above formula (2-1), or a structure represented by the above formula (2-2).

[0044] In addition, from the viewpoint of affinity with pigments, R7 to R 11 At least one of the above is preferably a structure represented by the above formula (2-1) or formula (2-2).

[0045] R2 to R3 are not the above specific structures (the portion constituting the bond with the polymer portion, the structure represented by formula (2-1), or the structure represented by formula (2-2)). 11 are more preferably all hydrogen atoms.

[0046] R in the above formula (2-1) 12 The alkyl group in the formula (I) includes linear, branched, and cyclic alkyl groups, such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a cyclohexyl group.

[0047] R in the above formula (2-1) 12 Examples of the aralkyl group in the formula (I) include a benzyl group and a phenethyl group.

[0048] R in the above formula (2-1) 12Examples of the alkyloxycarbonyl group (—C(═O)—OAlkyl) in the above formula include a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an n-pentyloxycarbonyl group, and an n-hexyloxycarbonyl group.

[0049] R in the above formula (2-1) 12 Examples of the aralkyloxycarbonyl group (-C(=O)-O-Ararkyl) in the above formula include a benzyloxycarbonyl group and a phenethyloxycarbonyl group.

[0050] Among the above, R is the most popular from the viewpoint of affinity with pigments. 12 is preferably a hydrogen atom, a methyl group, or an ethyl group.

[0051] A1 in the above formula (2-1) and A2 in the above formula (2-2) are each an oxygen atom, a sulfur atom, or NR 13 R 13 is preferably a hydrogen atom, a tert-butoxycarbonyl group, or a benzyloxycarbonyl group. Among these, from the viewpoint of affinity to the pigment, A1 and A2 are more preferably oxygen atoms.

[0052] R in the above formula (2-1) and formula (2-2) 12 and R 13 Examples of the substituent in include a halogen atom, a nitro group, an amino group, a hydroxy group, a cyano group, and a trifluoromethyl group.

[0053] The structure represented by the formula (1) and the polymer moiety are connected by a single bond or a linking group constituting the terminal of the polymer moiety. The linking group is not particularly limited as long as it is a divalent linking group. Examples include an ester bond (-COO-), a thioester bond (-COS-), or a carboxylic acid amide bond (-CONH-). Among these, an ester bond or a carboxylic acid amide bond is preferred.

[0054] Specifically, a linking group represented by the following formula (L1) or (L2) is particularly preferred.

[0055] [ka]

[0056] (In formulas (L1) and (L2), * indicates a bonding site with a carbon atom in the polymer moiety. ※※ indicates the bonding site with the carbon atom in the benzene ring of the structure represented by formula (1). In view of the above, the pigment dispersant of the present disclosure preferably has a structure represented by the following formula (4).

[0057] [ka]

[0058] (In formula (4), Z is a moiety that links to the polymer moiety, R 20 represents a substituted alkyl group, an unsubstituted alkyl group, a substituted phenyl group, or an unsubstituted phenyl group. When the pigment dispersant has the structure represented by formula (4), the pigment dispersion has improved adsorption to the pigment, which makes it easier to obtain a toner with good coloring power.

[0059] R in the above formula (4) 20The alkyl group or phenyl group may be further substituted with a substituent, as long as it does not significantly impair the affinity for the pigment. In this case, the substituent may be, for example, a halogen atom, a nitro group, an amino group, a hydroxy group, a cyano group, or a trifluoromethyl group.

[0060] R in the above formula (4) 20 Among the above, is preferably a methyl group from the viewpoint of affinity to the pigment.

[0061] Next, the structure of the pigment dispersant represented by formula (3) and a preferred embodiment thereof will be described in detail.

[0062] R in equation (3) 14 ~R 17 At least two of the -X-COOR 18 (X represents a single bond or an alkylene group having 1 to 2 carbon atoms. R 18 represents an alkyl group having 16 to 30 carbon atoms. ) and the rest are hydrogen atoms or alkyl groups having 1 to 4 carbon atoms. As mentioned above, the adjacent long-chain alkyl groups generate steric repulsion, which provides the exclusion effect necessary for pigment dispersion. R 18 When the carbon number of R is 16 or more, a steric repulsion sufficient for pigment dispersion is obtained, and a toner having high coloring power is obtained. In addition, the Tg of the pigment dispersant is increased, and the storage stability of the toner is improved. 18 When the carbon number of R is 30 or less, the interaction between the structure represented by formula (1) and the pigment is not inhibited, and the pigment dispersant can be present around the pigment, resulting in a toner with excellent coloring power. 18 The number of carbon atoms is more preferably 18 to 28, and even more preferably 20 to 24.

[0063] In order to incorporate the structure represented by formula (3) into a pigment dispersant, the following formula (3')

[0064] [ka]

[0065] (In formula (3'), R 14 '~R 17 At least two of the groups -X-COOH are -X-COOH, and the remaining groups each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0066] X represents a single bond or an alkylene group having 1 to 2 carbon atoms. and a long-chain alkyl monoalcohol having 16 to 30 carbon atoms (hereinafter referred to as the polymerizable ester of the present disclosure) is used as a polymerizable monomer.

[0067] Examples of polycarboxylic acids represented by formula (3') include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, glutaconic acid, trans-aconitic acid, and cis-aconitic acid. Acid anhydrides and lower alkyl (having 1 to 4 carbon atoms) esters (e.g., methyl ester, ethyl ester, isopropyl ester, etc.) of these polycarboxylic acids may also be used. The polycarboxylic acids may be used alone or in combination of two or more. Of these, maleic acid, fumaric acid, itaconic acid, and their acid anhydrides are preferred to achieve the effects of the present disclosure.

[0068] Examples of the long-chain alkyl monoalcohol having 16 to 30 carbon atoms include cetanol, stearyl alcohol, 1-eicosanol, behenyl alcohol, 1-tetracosanol, and 1-triacontanol.

[0069] The method for producing the polymerizable ester is not particularly limited except for using a polycarboxylic acid represented by formula (3') and a monoalcohol having 16 to 30 carbon atoms. It is preferable to use an esterification catalyst and a stabilizer (polymerization inhibitor) to ensure that the condensation reaction is carried out and to suppress the reaction of carbon-carbon double bonds.

[0070] The content (mass %) of the structure represented by formula (1) in the pigment dispersant is preferably 1.3 mass % or more and 15.0 mass % or less. When the content of the structure represented by formula (1) is 1.3 mass % or more, the proportion of sites in the pigment dispersant that interact with the pigment increases, making it easier for the pigment dispersant to be present near the pigment. This makes it easier to obtain toner coloring power. When the content of the structure represented by formula (1) is 15.0 mass % or less, the length of the polymer chain (also referred to as loop length) of the polymer site between the structures represented by formula (1) in the pigment dispersant becomes sufficient, making it easier to suppress aggregation of pigments due to steric hindrance. This makes it easier to obtain toner coloring power. A more preferred content is 2.8 mass % or more and 12.0 mass % or less.

[0071] Furthermore, the content (mass %) of the structure represented by formula (3) in the pigment dispersant is preferably 5.0 mass % or more and 70.0 mass % or less. When the content of the structure represented by formula (3) is 5.0 mass % or more, an exclusion effect is obtained due to the steric repulsion of the adjacent long-chain alkyl groups, resulting in good toner coloring power and color unevenness (described later). When the content of the structure represented by formula (3) is 70.0 mass % or less, the interaction with the pigment is not inhibited, allowing the pigment dispersant to be present around the pigment, making it easier to obtain good toner coloring power. A more preferred content is 10.0 mass % or more and 60.0 mass % or less.

[0072] The polymer portion of the pigment dispersant preferably contains, in addition to the structures represented by the above formulas (1) and (3), a monomer unit derived from the following monomer.

[0073] Monomers include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, and styrene derivatives such as p-phenylstyrene; acrylic polymerizable monomers such as acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-lauryl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate; Methacrylic polymerizable monomers such as methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, 2-methoxyethyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate; acrylonitrile, and methacrylonitrile.

[0074] The weight average molecular weight (Mw) of the pigment dispersant is preferably 10,000 or more and 50,000 or less, and more preferably 15,000 or more and 40,000 or less.

[0075] The pigment dispersant can be obtained by pre-polymerizing a polymer moiety containing a functional group capable of reacting with a precursor of the pigment adsorption moiety and a structure represented by formula (3), and then adding the precursor of the pigment adsorption moiety to the polymer moiety.

[0076] <Pigments> The pigment preferably includes a pigment selected from the following group:

[0077] Carbon black, CI Pigment Yellow 74, 93, 139, 155, 180, 185; CI Pigment Red 31, 122, 150, 170, 185, 258, 269; CI Pigment Blue 15:3, 15:4.

[0078] When the pigment is selected from the above group, adsorption due to π-π interactions and hydrogen bonding is stronger, so the pigment dispersant is more likely to be present near the pigment, and pigment dispersibility is more likely to be improved.

[0079] More preferred are carbon black, CI Pigment Yellow 74, 93, 155, 180, 185; CI Pigment Red 122, 150; and CI Pigment Blue 15:3.

[0080] The content (mass %) of the pigment dispersant in the toner particles is preferably 1.5% by mass to 30.0% by mass, more preferably 5.0% by mass to 25.0% by mass, and even more preferably 10.0% by mass to 20.0% by mass, based on the total mass of the pigment, from the viewpoint of the coloring power of the toner and color unevenness described below.

[0081] <Crystalline materials> From the viewpoint of low-temperature fixability, the toner of the present disclosure preferably contains a crystalline material, which is a material such as wax or crystalline resin that exhibits an endothermic peak in differential scanning calorimetry (DSC).

[0082] The content (mass %) of the crystalline material in the toner particles is preferably 20.0% by mass or more and 50.0% by mass or less from the viewpoint of low-temperature fixability. The crystalline material in the toner particles tends to crystallize and form domains when it melts during fixation and then cools and solidifies. If the content of the crystalline material in the toner particles is high, the domains of the crystalline material present in the toner layer after fixation cause diffuse reflection, which tends to result in color unevenness in the image. When the above-mentioned pigment dispersant and crystalline material are contained in the toner, the long-chain alkyl group in the structure represented by formula (3) acts as a nucleating agent for the crystalline material. Because the pigment dispersant is finely dispersed in the toner particles, it can suppress the crystal growth of the crystalline material and the formation of domains. Therefore, diffuse reflection does not occur in the image, and color unevenness can be suppressed.

[0083] Specific examples of crystalline materials include waxes such as hydrocarbon waxes or ester waxes, and crystalline resins such as crystalline vinyl resins, crystalline polyesters, crystalline polyurethanes, and crystalline epoxy resins. Among these, crystalline vinyl resins or crystalline polyesters are preferred, and crystalline vinyl resins are more preferred.

[0084] When the crystalline resin is a crystalline vinyl resin, it preferably contains a structure represented by formula (5) or a structure represented by formula (6).

[0085] [ka]

[0086] (In formula (5), R 21 represents a hydrogen atom or a methyl group, L1 represents a single bond, -COO-, or -CONH-; n represents an integer between 15 and 30.

[0087] [ka]

[0088] (In formula (6), R 22 ~R 25 At least two of them are -Y-COOR 26 and the remainder represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y represents a single bond or an alkylene group having 1 to 2 carbon atoms; R 26 represents an alkyl group having 16 to 30 carbon atoms. When a crystalline vinyl resin has the above structure, it is easy to form a side chain crystalline structure, which makes it possible to obtain sharp melting properties and further improve low-temperature fixability. Furthermore, the side chain crystalline structure has a higher crystallinity than a folded main chain crystalline structure, which makes it excellent in durability and storage stability. n in formula (5) is preferably 17 or more and 29 or less, more preferably 19 or more and 23 or less. Furthermore, R in formula (6) 26 is preferably an alkyl group having 18 to 28 carbon atoms, more preferably an alkyl group having 20 to 24 carbon atoms.

[0089] The crystalline vinyl resin may have, in addition to the above structure, a monomer unit derived from another monomer.

[0090] Other polymerizable monomers include the following:

[0091] Monomers include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, and styrene derivatives such as p-phenylstyrene; acrylic polymerizable monomers such as acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, n-lauryl acrylate, cyclohexyl acrylate, 2-methoxyethyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate, and acrylonitrile; methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, 2-methoxyethyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate; and methacrylonitrile and other methacrylic polymerizable monomers.

[0092] Of these, styrene, methacrylic acid, acrylic acid, methyl methacrylate, methyl acrylate, acrylonitrile, and methacrylonitrile are preferred.

[0093] The crystalline vinyl resin described here has a structure different from that of the pigment dispersant, and is a polymer that does not contain the structure represented by formula (1).

[0094] When wax is used as the crystalline material, the type of wax is not particularly limited, but hydrocarbon wax or ester wax is preferred.

[0095] Examples of hydrocarbon waxes include the following:

[0096] Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, Fischer-Tropsch wax, paraffin wax, or waxes obtained by oxidizing or adding an acid thereto.

[0097] The ester wax may be any wax having at least one ester bond in one molecule, and either a natural ester wax or a synthetic ester wax may be used.

[0098] Examples of ester waxes include the following:

[0099] Esters of monohydric alcohols and monocarboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate; Esters of dicarboxylic acids and monoalcohols, such as dibehenyl sebacate; Esters of dihydric alcohols and monocarboxylic acids, such as ethylene glycol distearate and hexanediol dibehenate; Esters of trihydric alcohols and monocarboxylic acids, such as glycerin tribehenate; Esters of tetrahydric alcohols and monocarboxylic acids, such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate; Esters of hexahydric alcohols and monocarboxylic acids, such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabehenate; Esters of polyfunctional alcohols and monocarboxylic acids, such as polyglycerin behenate; natural ester waxes, such as carnauba wax and rice wax.

[0100] <Method of manufacturing toner particles> The manufacturing method for manufacturing the toner particles according to the present disclosure may be any manufacturing method, but it is preferable to obtain the toner particles by a manufacturing method in which the toner particles are granulated in an aqueous medium, such as a suspension polymerization method, an emulsion polymerization method, or a suspension granulation method.

[0101] Hereinafter, the suspension polymerization method that is most suitable for producing the toner particles used in the present disclosure will be described.

[0102] In addition to the pigment dispersant, pigment, crystalline material, and wax, the polymerizable monomer that forms the binder resin, and other additives as necessary, are uniformly dissolved or dispersed using a dispersing machine such as a homogenizer, ball mill, colloid mill, or ultrasonic disperser. A polymerization initiator is dissolved in the resulting solution to prepare a polymerizable monomer composition. Next, the polymerizable monomer composition is suspended in an aqueous medium containing a dispersion stabilizer, and the polymerizable monomer is polymerized to produce toner particles.

[0103] Examples of monofunctional polymerizable monomers include styrene derivatives such as styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene; acrylic polymerizable monomers such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate; Methacrylic polymerizable monomers such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl phosphate ethyl methacrylate.

[0104] Further, examples of polyfunctional polymerizable monomers 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 diacrylate, ethylene 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, and divinyl ether.

[0105] These polymerizable monomers can be used alone or in combination of two or more.

[0106] The polymerization initiator may be added simultaneously with the addition of other additives to the polymerizable monomer, or may be mixed immediately before suspending the polymerizable monomer in an aqueous medium. Alternatively, the polymerization initiator may be added in the form of a solution in the polymerizable monomer or a solvent immediately after granulation and before starting the polymerization reaction.

[0107] Examples of the polymerization initiator include organic peroxide initiators and azo polymerization initiators. Examples of organic peroxide initiators include benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, bis(4-t-butylcyclohexyl)peroxydicarbonate, 1,1-bis(t-butylperoxy)cyclododecane, t-butylperoxymaleic acid, bis(t-butylperoxy)isophthalate, methyl ethyl ketone peroxide, tert-butylperoxy-2-ethylhexanoate, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and tert-butylperoxypivalate.

[0108] Examples of the azo polymerization initiator include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobismethylbutyronitrile.

[0109] Alternatively, a redox initiator, which combines an oxidizing substance and a reducing substance, can be used as the polymerization initiator. Examples of oxidizing substances include inorganic peroxides such as hydrogen peroxide, persulfates (sodium, potassium, and ammonium salts), and oxidizing metal salts such as tetravalent cerium salts. Examples of reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, and trivalent chromium salts), ammonia, lower amines (amines having approximately 1 to 6 carbon atoms, such as methylamine and ethylamine), amino compounds such as hydroxylamine, reducing sulfur compounds such as sodium thiosulfate, sodium hydrosulfite, sodium bisulfite, sodium sulfite, and sodium formaldehyde sulfoxylate, lower alcohols (having 1 to 6 carbon atoms), ascorbic acid or its salts, and lower aldehydes (having 1 to 6 carbon atoms).

[0110] The polymerization initiator is selected with reference to its 10-hour half-life temperature and is used alone or in combination. The amount of the polymerization initiator added varies depending on the desired degree of polymerization, but is generally 0.5 to 20.0 parts by mass per 100.0 parts by mass of the polymerizable monomer.

[0111] In addition, known chain transfer agents and polymerization inhibitors may be further added to control the degree of polymerization.

[0112] Various crosslinking agents can be used when polymerizing the polymerizable monomers, including polyfunctional compounds such as divinylbenzene, 4,4'-divinylbiphenyl, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, glycidyl acrylate, glycidyl methacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate.

[0113] The pigment is preferably used in an amount of 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.

[0114] The dispersion stabilizer used in preparing the aqueous medium may be a known inorganic dispersion stabilizer or an organic dispersion stabilizer. Examples of inorganic dispersion stabilizers include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. Examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salts, and starch. The amount of these dispersion stabilizers used is preferably 0.2 to 20 parts by mass per 100 parts by mass of the polymerizable monomer.

[0115] When an inorganic dispersion stabilizer is used among these dispersion stabilizers, a commercially available one may be used as it is, but in order to obtain a dispersion stabilizer with a finer particle size, the inorganic compound may be produced in an aqueous medium. For example, tricalcium phosphate can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution under high agitation.

[0116] In the present disclosure, the toner preferably has an external additive present on the surface of the toner particles in order to improve image quality. As the external additive, either an organic fine powder or an inorganic fine powder can be used, but inorganic fine powders such as silica fine powder, titanium oxide fine powder, or aluminum oxide fine powder are preferred.

[0117] These inorganic fine powders are preferably subjected to a hydrophobic treatment with a hydrophobizing agent such as a silane coupling agent, silicone oil, or a mixture thereof.

[0118] The amount of inorganic fine powder added is preferably 1.0 part by mass or more and 5.0 parts by mass or less with respect to 100.0 parts by mass of toner particles (base particles before adding external additives).

[0119] Hereinafter, methods for measuring various physical properties according to the present disclosure will be described.

[0120] <Composition analysis method> The structure determination of the pigment dispersant and crystalline material was carried out using the following equipment. 1 H NMR: JEOL Ltd. ECA-400 (solvent: deuterated chloroform) 13 C-NMR: Bruker Biospin FT-NMR AVANCE-600 (solvent: deuterated chloroform) In addition, 13 C-NMR was quantified by the inverse gated decoupling method using chromium(III) acetylacetonate as a relaxation reagent, and compositional analysis was performed.

[0121] The molar composition ratio of each monomer unit of the pigment dispersant and the crystalline material was calculated by the above measurement, and then the mass composition ratio was determined from the molecular weight of each monomer unit.

[0122] <Method for measuring molecular weight> The weight average molecular weight (Mw) of the toner and the pigment dispersant is measured using gel permeation chromatography (GPC) as follows.

[0123] The sample is dissolved in tetrahydrofuran (THF) at room temperature. The resulting solution is then filtered through a solvent-resistant membrane filter "Myshoridisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is 0.8 mass%. This sample solution is used for measurements under the following conditions. Equipment: High-speed GPC equipment "HLC-8220GPC" [manufactured by Tosoh Corporation] Column: LF-604 (two columns, manufactured by Showa Denko K.K.) Eluent:THF Flow rate: 0.6mL / min Oven temperature: 40°C Sample injection volume: 0.020 mL To calculate the molecular weight of a sample, a molecular weight calibration curve prepared using standard polystyrene resins (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0124] <Method for measuring weight average particle diameter (D4) and number average particle diameter (D1) of toner particles> A precision particle size distribution analyzer using the pore electrical resistance method (trade name: Coulter Counter Multisizer 3) and dedicated software (trade name: Beckman Coulter Multisizer 3 Version 3.51, manufactured by Beckman Coulter, Inc.) are used. Measurements are performed with an aperture diameter of 100 μm and an effective number of measurement channels of 25,000. The measurement data are analyzed and calculated. The electrolyte solution used for the measurements is prepared by dissolving special-grade sodium chloride in ion-exchange water to a concentration of 1% by mass; for example, ISOTON II (trade name) manufactured by Beckman Coulter, Inc. can be used. Before performing measurements and analysis, the dedicated software is configured as follows:

[0125] On the "Change Standard Measurement Method (SOM) screen" of the dedicated software, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using standard particles (10.0 μm, Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II (trade name), and check the option to flush the aperture tube after measurement.

[0126] In the dedicated software's "Pulse to particle size conversion setting screen," set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

[0127] The specific measurement method is as follows.

[0128] (1) Pour 200 mL of the electrolyte solution into a 250 mL round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture flush" function of the analysis software to remove any dirt or air bubbles from inside the aperture tube.

[0129] (2) 30 mL of the aqueous electrolyte solution is placed in a 100 mL flat-bottom glass beaker, and 0.3 mL of a diluted solution prepared by diluting Contaminon N (trade name) (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments, manufactured by Wako Pure Chemical Industries, Ltd.) three times by mass with ion-exchanged water is added thereto.

[0130] (3) A predetermined amount of ion-exchanged water and 2 mL of Contaminon N (trade name) are added to the water tank of an ultrasonic disperser (trade name: Ultrasonic Dispersion System Tetora150, manufactured by Nikkaki Bios Co., Ltd.) that has two oscillators with an oscillation frequency of 50 kHz built in with a phase shift of 180 degrees and an electrical output of 120 W.

[0131] (4) The beaker (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized.

[0132] (5) While the electrolyte solution in the beaker in (4) is being irradiated with ultrasonic waves, 10 mg of toner (particles) is added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to 10°C to 40°C.

[0133] (6) Using a pipette, the electrolytic solution (5) containing dispersed toner particles is dropped into the round-bottom beaker (1) placed in the sample stand, and the measurement concentration is adjusted to 5%. Then, measurements are continued until the number of particles measured reaches 50,000.

[0134] (7) The measurement data is analyzed using the dedicated software provided with the device to calculate the weight average particle size (D4). When the dedicated software is set to Graph / Volume %, the "Average diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen is the weight average particle size (D4). When the dedicated software is set to Graph / Number %, the "Average diameter" on the Analysis / Number Statistics (Arithmetic Mean) screen is the number average particle size (D1).

[0135] <Method for measuring the endothermic peak temperature of toner> The peak temperature of the maximum endothermic peak of the toner is measured using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments) in accordance with ASTM D3418-82. The melting points of indium and zinc are used to correct the temperature of the detector, and the heat of fusion of indium is used to correct the amount of heat.

[0136] Specifically, approximately 10 mg of toner is weighed out and placed in an aluminum pan. An empty aluminum pan is used as a reference, and measurements are performed at a temperature rise rate of 10°C / min within a measurement temperature range of 30 to 200°C. In the measurement, the temperature is raised to 200°C once, then lowered to 30°C, and then raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 200°C during this second temperature rise is taken as the maximum endothermic peak of the endothermic curve in the DSC measurement of the toner of the present disclosure. [Example]

[0137] The present disclosure will be specifically explained by the following Production Examples and Examples. However, these do not limit the present disclosure in any way. In the Production Examples and Examples, "parts" and "%" are all by mass unless otherwise specified.

[0138] [Synthesis of pigment adsorption site precursor] <Production Example of Pigment Adsorption Site Precursor (A-1)> First, 25.0 parts of m-nitroaniline, 15.4 parts of diketene, and 15.0 parts of acetone were added to 140 parts of acetic acid, and the mixture was stirred for 3 hours at 65° C. After completion of the reaction, the mixture was poured into 1,200 parts of water and then filtered to obtain 38.4 parts of compound (1) (yield 96.0%).

[0139] Next, 142 parts of N,N-dimethylformamide and 30.8 parts of concentrated hydrochloric acid were added to 15.0 parts of 5-amino-2-benzimidazolinone, and the mixture was ice-cooled to below 5°C. A solution of 7.25 parts of sodium nitrite dissolved in 50.0 parts of water was added to this solution and stirred at the same temperature for 1 hour (diazonium salt solution). 21.9 parts of compound (1) and 68.4 parts of calcium carbonate were added to 142 parts of N,N-dimethylformamide, and the mixture was ice-cooled to below 5°C. The diazonium salt solution was added and reacted at below 5°C for 3 hours. After completion of the reaction, the reaction solution was filtered, and the solvent was distilled off under reduced pressure. The precipitate was washed with dilute hydrochloric acid, water, and methanol to obtain 36.0 parts of compound (2) (yield 94.3%).

[0140] The resulting compound (2) was added to 203 parts of 1,4-dioxane, and a solution of 12.4 parts of sodium hydrosulfide dissolved in 80 parts of water was added dropwise at room temperature. After the dropwise addition, the solution was heated and stirred at 50°C for 26 hours. After the reaction was completed, the reaction solution was poured into water, and the precipitate was filtered off and washed with dilute hydrochloric acid, water, and methanol to obtain 10.0 parts of pigment adsorption site precursor (A-1) (compound (3)) (yield: 50.6%). The structure of the pigment adsorption site precursor (A-1) is shown in Table 1.

[0141] <Production Examples of Pigment Adsorption Site Precursors (A-2) and (A-3)> Pigment adsorption site precursors (A-2) and (A-3) were obtained in the same manner as in the production example of pigment adsorption site precursor (A-1), except that the compounds used were changed so that the composition was as shown in Table 1.

[0142] [Table 1]

[0143] <Production Example of Pigment Adsorption Site Precursor (A-4)> A pigment adsorption site precursor (A-4) was synthesized according to the following procedure.

[0144] Synthesis of intermediate (1): To 22.0 parts of p-phenylenediamine, 70.0 parts of dilute hydrochloric acid was added and cooled to below 5°C. 37.0 parts of 19.0% aqueous sodium nitrite solution was added dropwise to this solution while cooling with ice to prepare a diazonium salt solution. Next, 237 parts of ethanol and 126.0 parts of 36.5% aqueous sodium acetate solution were added to 10.0 parts of acetylacetone, stirred, and cooled to below 5°C. The previously prepared diazonium salt solution was slowly added dropwise to this solution, and the mixture was stirred for 30 minutes under ice cooling and then at room temperature for 1 hour. The resulting precipitate was then collected by filtration, washed with water, and dried to obtain intermediate (1).

[0145] Synthesis of intermediate (2): 15.6 parts of the intermediate (1) obtained above was dissolved in 80.6 parts of methanol, and 86.0 parts of a 2 mol / L aqueous sodium hydroxide solution was added. The mixture was cooled to 5°C or below. A mixture of 30.5 parts of benzaldehyde and 20.5 parts of ethanol was added dropwise to the solution, and the mixture was allowed to react under ice cooling for 3 hours, and then allowed to stand overnight in a refrigerator. After standing, the reaction solution was poured into 500 parts of cold water and neutralized with acetic acid. The resulting precipitate was separated and purified using silica gel column chromatography to obtain intermediate (2).

[0146] Synthesis of pigment adsorption site precursor (A-4): 14.4 parts of the intermediate (2) obtained above was dissolved in 170 parts of pyridine and then cooled to below 5°C. A solution of 4.21 parts of methacryloyl chloride in 30.0 parts of pyridine was added dropwise to this solution and stirred for 1 hour. 200 parts of water was then added to terminate the reaction, and the mixture was extracted with chloroform, washed with water, and concentrated to obtain a pigment adsorption site precursor (A-4) having the following structure:

[0147] [ka]

[0148] [Synthesis of polymerizable ester compound] <Polymerizable ester compound 1> A pressure reactor equipped with a stirrer, temperature controller, thermometer, air inlet tube, pressure reducer, and water reducer was charged with 980.0 parts of behenyl alcohol, 175.0 parts of fumaric acid, 2.5 parts of dibutyltin oxide, and 1.0 part of 2,6-di-tert-butyl-p-cresol, and the mixture was stirred at 120°C to homogenize. The mixture was then heated to 165°C and esterified at 21 kPa for 3 hours while removing distilled water, followed by esterification at 3 kPa or less for 12 hours while removing distilled water. The mixture was discharged to obtain polymerizable ester compound 1.

[0149] <Synthesis of polymerizable ester compounds 2 to 4> Polymerizable ester compounds 2 to 4 were synthesized in the same manner as in the synthesis of polymerizable ester compound 1, except that the unsaturated polycarboxylic acid and long-chain alkyl alcohol used in the synthesis of polymerizable ester compound 1 were changed as shown in Table 2. The obtained polymerizable ester compounds had the structure of the following formula (3').

[0150] [ka]

[0151] [Table 2]

[0152] <Production example of polymer part (P-1)> 100.0 parts of xylene, 32.3 parts of polymerizable ester compound 1, 65.9 parts of styrene, and 1.8 parts of methacrylic acid were added to a reaction vessel and kept at 70 ° C while purging with nitrogen. Then, 1.5 parts of azobis(isobutyrate)dimethyl as a polymerization initiator dissolved in 1.0 parts of xylene was added dropwise to the reaction vessel over 3 hours. After the dropwise addition, the reaction vessel was maintained at 70 ° C for 3 hours to carry out polymerization. Then, the liquid temperature was raised to 170 ° C, and the solvent was removed by distillation under a reduced pressure of 1 hPa for 3 hours to obtain a polymer portion (P-1).

[0153] <Production examples of polymer segments (P-2) to (P-15)> Polymer segments (P-2) to (P-15) were obtained in the same manner as in the production example of polymer segment (P-1), except that the raw materials were changed as shown in Table 3.

[0154] [Table 3]

[0155] The terms in the table have the following meanings: St: styrene MAA: methacrylic acid BEA: Behenyl acrylate <Production example of pigment dispersant (Sy-1)> 93.0 parts of the polymer moiety (P-1) were dissolved in 100 parts of chloroform, and 1.5 parts of thionyl chloride were added dropwise. The mixture was stirred at room temperature for 24 hours. The reaction mixture was then concentrated to remove the chloroform and excess thionyl chloride. The resulting resin solid was recovered and redissolved in 60.0 parts of N,N-dimethylacetamide at 70°C under a nitrogen atmosphere. 7.0 parts of the pigment adsorption moiety precursor (A-1) were added and the mixture was stirred at 70°C under a nitrogen atmosphere for 3 hours. After the reaction was complete, the reaction mixture was concentrated and then reprecipitated with methanol to obtain 8.25 parts of pigment dispersant (Sy-1). The composition of the resulting pigment dispersant (Sy-1) is shown in Table 4.

[0156] In the pigment dispersant (Sy-1), a polymer moiety having a carboxylic acid amide bond (-CONH-) at the end is bonded to R3 in formula (1).

[0157] <Production Examples of Pigment Dispersants (Sy-2) to (Sy-16)> Pigment dispersants (Sy-2) to (Sy-16) were obtained in the same manner as in the production example of pigment dispersant (Sy-1), except that the composition was changed to that shown in Table 4.

[0158] [Table 4]

[0159] The terms in the table have the following meanings: St: styrene MAA: methacrylic acid BEA: Behenyl acrylate [Synthesis of crystalline resin] <Crystalline resin C1> The following materials were placed in 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 Behenyl acrylate 80.0 parts Styrene 20.0 parts Polymerization initiator: 0.5 parts t-butyl peroxypivalate (NOF Corporation: Perbutyl PV) The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours, resulting in a solution in which the polymer of the monomer composition was dissolved in toluene. Toluene and residual monomers were then removed by distillation at 160°C and 1 hPa to obtain crystalline resin C1. The weight average molecular weight (Mw) of the obtained crystalline resin C1 was 30,000, and the melting point (Tm) was 60°C.

[0160] <Crystalline resin C2> 118.0 parts of sebacic acid and 69.0 parts of 1,6-hexanediol were added to a reaction vessel equipped with a stirrer, thermometer, nitrogen inlet tube, dehydration tube, and pressure reducing device, and the mixture was heated to 130°C with stirring. After adding 0.7 parts of titanium (IV) isopropoxide as an esterification catalyst, the mixture was heated to 160°C and subjected to condensation polymerization over 5 hours. The mixture was then heated to 180°C and reacted under reduced pressure until the desired molecular weight was reached, yielding crystalline resin C2. The resulting crystalline resin C2 had a weight average molecular weight (Mw) of 28,000 and a melting point (Tm) of 69°C.

[0161] <Crystalline resin C3> The following materials were placed in 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 Polymerizable ester compound 1 50.0 parts Styrene 50.0 parts Polymerization initiator: 0.5 parts t-butyl peroxypivalate (NOF Corporation: Perbutyl PV) The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours, resulting in a solution in which the polymer of the monomer composition was dissolved in toluene. Toluene and residual monomers were then removed by distillation at 160°C and 1 hPa to obtain crystalline resin C3. The weight average molecular weight (Mw) of the obtained crystalline resin C3 was 32,000, and the melting point (Tm) was 65°C.

[0162] <Production example of black toner 1> [Preparation step of colorant dispersion 1] Styrene monomer 100.0 parts Carbon black (CB) 20.0 parts (Nipex35: Orion Engineered Carbons) Pigment dispersant (Sy-1) 2.0 parts The above materials were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.) and stirred at 200 rpm at 25° C. for 180 minutes using zirconia beads (200 parts) with a radius of 2.5 mm to prepare colorant dispersion liquid 1.

[0163] [Preparation of toner composition solution] Colorant dispersion 1 41.8 parts Styrene 8.6 parts n-Butyl acrylate (BA) 14.6 parts ·Crystalline resin C1 27.4 parts Dipentaerythritol hexastearate 7.7 parts The above materials were mixed and heated to 65° C., and dissolved and dispersed for 60 minutes at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain toner composition solution 1.

[0164] [Preparation process of dispersion liquid (aqueous medium)] In a 2-liter four-neck flask equipped with a high-speed stirring device TK-Homomixer, 450 parts of a 0.1 mol / L NaPO aqueous solution were added to 710 parts of ion-exchanged water and heated to 60° C. Then, 67.7 parts of a 1.0 mol / L CaCl aqueous solution were gradually added to obtain an aqueous medium 1 containing a calcium phosphate compound.

[0165] [Granulation process] While maintaining the temperature of the aqueous medium 1 at 60°C and the rotation speed of the stirrer at 12,500 rpm, the toner composition solution 1 was poured into the aqueous medium 1, and 3.5 parts of t-butyl peroxypivalate as a polymerization initiator was added. Granulation was continued for 10 minutes while maintaining the stirring speed at 12,500 rpm.

[0166] [Polymerization process] The high-speed stirrer was changed to a stirrer equipped with a propeller stirring blade, and polymerization was carried out for 5.0 hours while stirring at 200 rpm and maintaining the temperature at 70°C. Thereafter, the temperature was raised to 98°C and heated for 3.0 hours to remove residual monomers, yielding black toner particle dispersion 1 in which black toner particles were dispersed.

[0167] Hydrochloric acid was added to the obtained black toner particle dispersion 1 to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. This was subjected to solid-liquid separation in a pressure filter at a pressure of 0.4 MPa, yielding toner cake 1. Next, ion-exchanged water was added to the pressure filter until it was filled with water, and toner cake 1 was washed at a pressure of 0.4 MPa. This washing procedure was repeated three times, and then the mixture was dried to yield black toner particles 1.

[0168] To 100.0 parts of the obtained black toner particles 1, 1.5 parts of hydrophobic silica fine powder (number average particle size of primary particles: 10 nm) that had been surface-treated with hexamethyldisilazane was added, and the mixture was mixed for 300 seconds in a Mitsui Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain black toner 1. The composition and physical properties of black toner 1 are shown in Table 5.

[0169] <Production example of black toner 2 to 29> Black toners 2 to 29 were obtained in the same manner as in the production example of black toner 1, except that the composition of black toner particles 1 was changed as shown in Table 5. Table 5 shows the compositions and physical properties of black toners 2 to 29.

[0170] [Table 5-1]

[0171] [Table 5-2]

[0172] <Production example of magenta toner 1> [Preparation step of colorant dispersion 2] Styrene monomer 100.0 parts Pigment Red 122 (PR-122) 12.5 parts (Toner Magenta E [Clariant]) Pigment Red 150 (PR-150) 7.5 parts (Fuji Fast Carmine 522 [manufactured by Fuji Pigment Co., Ltd.]) Pigment dispersant (Sy-1) 2.0 parts The above materials were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.) and stirred at 200 rpm at 25° C. for 180 minutes using zirconia beads (200 parts) with a radius of 2.5 mm to prepare colorant dispersion liquid 2.

[0173] Thereafter, magenta toner 1 was obtained in the same manner as in the production example of black toner 1, except for using colorant dispersion liquid 2. The composition and physical properties of magenta toner 1 obtained are shown in Table 6.

[0174] <Production Example of Magenta Toners 2 and 3> Magenta toners 2 and 3 were obtained in the same manner as in the production example of magenta toner 1, except that the composition was changed as shown in Table 6. The compositions and physical properties of magenta toners 2 and 3 are shown in Table 6.

[0175] [Table 6]

[0176] <Production example of yellow toner 1> [Preparation step of colorant dispersion 3] Styrene monomer 100.0 parts Pigment Yellow 155 (PY-155) 20.0 parts (Paliotol Yellow D1155 [BASF]) Pigment dispersant (Sy-1) 2.0 parts The above materials were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.) and stirred at 200 rpm at 25° C. for 180 minutes using zirconia beads (200 parts) with a radius of 2.5 mm to prepare colorant dispersion 3.

[0177] Thereafter, yellow toner 1 was obtained in the same manner as in the production example for black toner 1, except that colorant dispersion liquid 3 was used. The composition and physical properties of yellow toner 1 obtained are shown in Table 7.

[0178] <Production example of yellow toners 2 to 7> Yellow toners 2 to 7 were obtained in the same manner as in the production example of yellow toner 1, except that the composition was changed as shown in Table 7. The compositions and physical properties of yellow toners 2 to 7 are shown in Table 7.

[0179] [Table 7]

[0180] <Production example of cyan toner 1> [Preparation step of colorant dispersion 4] Styrene monomer 100.0 parts Pigment Blue 15:3 20.0 parts (ECB-308 [manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.]) Pigment dispersant (Sy-1) 2.0 parts The above materials were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.) and stirred at 200 rpm at 25° C. for 180 minutes using zirconia beads (200 parts) with a radius of 2.5 mm to prepare colorant dispersion liquid 4.

[0181] Thereafter, cyan toner 1 was obtained in the same manner as in the production example for black toner 1, except that colorant dispersion liquid 4 was used. The composition and physical properties of the obtained cyan toner 1 are shown in Table 8.

[0182] <Production Example of Cyan Toners 2 and 3> Cyan toners 2 and 3 were obtained in the same manner as in the production example of cyan toner 1, except that the composition was changed as shown in Table 8. The compositions and physical properties of cyan toners 2 and 3 are shown in Table 8.

[0183] [Table 8]

[0184] <Evaluation> A commercially available color laser printer (HP LaserJet Enterprise Color M555dn) was partially modified for evaluation. The printer was modified so that it could operate with only one color process cartridge installed. The printer was also modified so that the fixing unit temperature could be adjusted as desired.

[0185] All process cartridges installed in the printer were removed and replaced. The toner inside the black toner process cartridge was removed and the interior was cleaned with an air blower, after which the toner (250 g) to be evaluated was introduced into the process cartridge. Only the refilled black toner process cartridge was installed in the printer, and the following evaluations were carried out. The specific evaluation methods are as follows:

[0186] <Coloring strength evaluation method> A rectangular solid image of 6.5 cm x 14.0 cm (toner amount: 0.45 mg / cm) was printed in the center of the transfer material. 2) was output and used as an evaluation image. The image density in the evaluation image was measured to evaluate coloring power. The image density was measured using an X-Rite color reflection densitometer (X-Rite 404A). The density was measured at five points in the solid image area: the top right, top left, center, bottom right, and bottom left, and the average value was used to evaluate the image density. Letter-size glossy paper (HP Brochure Paper 150g, Glossy) was used as the transfer material.

[0187] (Evaluation criteria) A: Image density is 1.70 or more B: Image density is 1.65 or more and less than 1.70 C: Image density is 1.60 or more and less than 1.65 D: Image density is less than 1.60 <Color unevenness evaluation method> Solid image on transfer material (toner amount: 0.45 mg / cm 2 ) was fixed at a fixing temperature of 200°C to obtain a print image. After leaving the print image in a high-temperature, high-humidity environment (temperature 32°C / humidity 85% RH) for one month, the solid image was divided into 15 sections (5 sections lengthwise and 3 sections widthwise), and the gloss value of the center of each section was measured using a PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.). The maximum, minimum, and average gloss values ​​of the 15 sections were used to calculate the difference between the average and maximum values, and the difference between the average and minimum values. The larger absolute value of the calculated difference was used to calculate the percentage of the difference relative to the average value, and color unevenness was evaluated according to the following criteria. Letter-size glossy paper (HP Brochure Paper 150g, Glossy) was used as the transfer material.

[0188] (Evaluation criteria) A: 3.0% or less B: 3.1% or more and 5.0% or less C: 5.1% or more and 10.0% or less D: 10.1% or more <Low temperature fixability evaluation method> Solid image on transfer material (toner amount: 0.45 mg / cm 2The fixing temperature was changed from 115°C in 5°C increments to carry out a fixing test. The density of the resulting fixed image was measured, and a 50 g / cm 2 After applying a load of 1000 kJ / cm2 and rubbing five times with Silbon paper (Lenz Cleaning Paper "dasper(R)" (Ozu Paper Co. Ltd.), the image density was measured again. The temperature at which the density reduction rate before and after rubbing was 10% or less was taken as the fixing start temperature. The fixing temperature was measured on the surface of the fixing roller using a non-contact thermometer. The transfer material was LETTER size plain paper (Vitality, manufactured by XEROX, 75 g / m2) 2 ) was used.

[0189] (Evaluation criteria) A: Fixing start temperature is 115℃ B: Fixing start temperature is 120℃ to 130℃ C: Fixing start temperature is 135℃ to 145℃ D: Fixing start temperature is 150°C or higher <Streak (developability) evaluation method> After printing 30,000 sheets of horizontal line images with a 1% print ratio in a high temperature and humidity environment (temperature 32°C / humidity 85%RH), the print quality was measured on letter-size plain paper (Vitality, manufactured by XEROX, 75g / m 2 ) and halftone (toner amount: 0.25 mg / cm 2 The halftone image was observed for the presence or absence of vertical streaks in the paper ejection direction, and the developability was evaluated as follows.

[0190] (Evaluation criteria) A: Not occurred B: Vertical streaks occur in 1 to 3 places C: Vertical streaks occur in 4 to 6 places D: Vertical lines appear in 7 or more places, or vertical lines with a width of 0.5 mm or more appear. <Evaluation method for storage stability (heat resistance)> 5 g of each toner was placed in a 50 mL resin cup and left to stand for 3 days at a temperature of 60° C. and a humidity of 10% RH, and the occurrence of agglomerates was checked and evaluated according to the following criteria.

[0191] (Evaluation criteria) A: No clumps formed. B: Slight clumps formed, but crumbled when lightly pressed with a finger. C: Agglomerates form that do not crumble even when lightly pressed with a finger. D: Cohesion and does not crumble.

[0192] Examples 1 to 25 In Examples 1 to 25, the above evaluations were carried out using black toners 1 to 25, respectively. The evaluation results are shown in Table 9.

[0193] Comparative Examples 1 to 4 In Comparative Examples 1 to 4, the above evaluations were carried out using black toners 26 to 29, respectively. The evaluation results are shown in Table 9.

[0194] [Table 9]

[0195] Examples 26 to 38 In Examples 26 to 32, the above evaluations were performed using Yellow Toners 1 to 7, respectively. In Examples 33 to 35, the above evaluations were performed using Magenta Toners 1 to 3, respectively. In Examples 36 to 38, the above evaluations were performed using Cyan Toners 1 to 3, respectively. The evaluation results are shown in Table 10.

[0196] [Table 10]

[0197] The present disclosure relates to the following configurations.

[0198] (Configuration 1) A toner having toner particles containing a binder resin, a pigment, and a pigment dispersant, The toner is characterized in that the pigment dispersant has a structure represented by the following formula (1) and a polymer moiety containing a structure represented by the following formula (3):

[0199] [ka]

[0200] (In formula (1), R1 represents a substituted alkyl group, an unsubstituted alkyl group, a substituted phenyl group, or an unsubstituted phenyl group; R2~R 11 At least one of these is a moiety that links to the polymer moiety, and the remaining moieties each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an amino group, a cyano group, a trifluoromethyl group, a carboxy group, or a structure represented by the following formula (2-1), or R to R 11 The adjacent groups among these have a structure represented by the following formula (2-2):

[0201] [ka]

[0202] (In formula (2-1), * indicates a benzene ring having R2 to R6 in formula (1), or R7 to R 11 represents a bonding site with a benzene ring having R 12 represents a hydrogen atom, a substituted alkyl group, an unsubstituted alkyl group, a substituted aralkyl group, an unsubstituted aralkyl group, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group, A1 is an oxygen atom, a sulfur atom, or NR 13 represents a group, R 13represents a hydrogen atom, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group.

[0203] [ka]

[0204] (In formula (2-2), ** and *** represent a benzene ring having R2 to R6 in formula (1), or R7 to R 11 represents a bonding site with a benzene ring having A2 is an oxygen atom, a sulfur atom, or NR 13 represents a group, R 13 represents a hydrogen atom, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group.

[0205] [ka]

[0206] (In formula (3), R 14 ~R 17 At least two of them are -X-COOR 18 and the rest each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0207] X represents a single bond or an alkylene group having 1 to 2 carbon atoms; R 18 represents an alkyl group having 16 to 30 carbon atoms. (Configuration 2) 2. The toner according to configuration 1, wherein the content (% by mass) of the structure represented by formula (1) in the pigment dispersant is 1.3% by mass or more and 15.0% by mass or less.

[0208] (Configuration 3) 3. The toner according to configuration 1 or 2, wherein the content (% by mass) of the structure represented by formula (3) in the pigment dispersant is 5.0% by mass or more and 70.0% by mass or less.

[0209] (Configuration 4) In the structure represented by the formula (1), R2 to R 11 At least one of R to R represents a structure represented by the formula (2-1), or 11 4. The toner according to any one of configurations 1 to 3, wherein adjacent groups are the structure represented by formula (2-2).

[0210] (Configuration 5) 5. The toner according to any one of configurations 1 to 4, wherein the structure represented by formula (1) is a structure represented by formula (4):

[0211] [ka]

[0212] (In formula (4), Z is a moiety that links to the polymer moiety, R 20 represents a substituted alkyl group, an unsubstituted alkyl group, a substituted phenyl group, or an unsubstituted phenyl group. (Configuration 6) 6. The toner according to any one of configurations 1 to 5, wherein the content (mass %) of the pigment dispersant in the toner particles is 1.5 mass % or more and 30.0 mass % or less with respect to the total mass of the pigment.

[0213] (Configuration 7) The pigment is 7. The toner according to any one of configurations 1 to 6, wherein the pigment is at least one pigment selected from the group consisting of carbon black, CI Pigment Yellow 74, 93, 139, 155, 180, and 185; CI Pigment Red 31, 122, 150, 170, 258, and 269; and CI Pigment Blue 15:3 and 15:4.

[0214] (Configuration 8) 8. The toner according to any one of embodiments 1 to 7, wherein the toner particles contain a crystalline material.

[0215] (Configuration 9) 9. The toner according to configuration 8, wherein the content (mass %) of the crystalline material in the toner particles is 20.0 mass % or more and 50.0 mass % or less based on the toner particles.

[0216] (Configuration 10) 10. The toner according to configuration 8 or 9, wherein the crystalline material is a crystalline resin.

[0217] (Configuration 11) 11. The toner according to configuration 10, wherein the crystalline resin is a crystalline vinyl resin having a structure represented by the following formula (5) or a crystalline vinyl resin having a structure represented by the following formula (6):

[0218] [ka]

[0219] (In formula (5), R 21 represents a hydrogen atom or a methyl group, L1 represents a single bond, -COO-, or -CONH-; n represents an integer between 15 and 30.

[0220] [ka]

[0221] (In formula (6), R 22 ~R 25 At least two of them are -Y-COOR 26 and the remainder represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y represents a single bond or an alkylene group having 1 to 2 carbon atoms; R 26represents an alkyl group having 16 to 30 carbon atoms.

Claims

1. A toner having toner particles containing a binder resin, a pigment, and a pigment dispersant, The toner is characterized in that the pigment dispersant has a structure represented by the following formula (1) and a polymer moiety containing a structure represented by the following formula (3). 【Chemistry 1】 (In formula (1), R １ represents a substituted alkyl group, an unsubstituted alkyl group, a substituted phenyl group, or an unsubstituted phenyl group, R ２ ~R １１ At least one of these is a moiety connecting to the polymer moiety, and the remaining moieties each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, an amino group, a cyano group, a trifluoromethyl group, a carboxy group, or a structure represented by the following formula (2-1), or R ２ ~R １１ The adjacent groups among these have a structure represented by the following formula (2-2): 【Chemistry 2】 (In formula (2-1), * represents R in formula (1). ２ ~R ６ a benzene ring having R ７ ~R １１ represents a bonding site with a benzene ring having R １２ represents a hydrogen atom, a substituted alkyl group, an unsubstituted alkyl group, a substituted aralkyl group, an unsubstituted aralkyl group, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group, A １ is an oxygen atom, a sulfur atom, or NR １３ represents a group, R １３ represents a hydrogen atom, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group. 【Transformation 3】 (In formula (2-2), ** and *** represent R in formula (1). ２ ~R ６ a benzene ring having R ７ ~R １１ represents a bonding site with a benzene ring having A ２ represents an oxygen atom, a sulfur atom, or NR １３ represents a group, R １３ represents a hydrogen atom, a substituted alkyloxycarbonyl group, an unsubstituted alkyloxycarbonyl group, a substituted aralkyloxycarbonyl group, or an unsubstituted aralkyloxycarbonyl group. 【Chemistry 4】 (In formula (3), R １４ ~R １７ At least two of them are -X-COOR １８ and the rest each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X represents a single bond or an alkylene group having 1 to 2 carbon atoms; R １８ represents an alkyl group having 16 to 30 carbon atoms.

2. 2. The toner according to claim 1, wherein the content (% by mass) of the structure represented by formula (1) in the pigment dispersant is 1.3% by mass or more and 15.0% by mass or less.

3. 3. The toner according to claim 1, wherein the content (% by mass) of the structure represented by formula (3) in the pigment dispersant is 5.0% by mass or more and 70.0% by mass or less.

4. In the structure represented by the formula (1), R ２ ~R １１ At least one of the groups represented by formula (2-1) is a structure represented by formula (2-1), or R ２ ~R １１ 3. The toner according to claim 1, wherein adjacent groups of the formula (2-2) are represented by the formula (2-2).

5. 3. The toner according to claim 1, wherein the structure represented by formula (1) is a structure represented by formula (4): 【Transformation 5】 (In formula (4), Z is a moiety that links to the polymer moiety, R ２０ represents a substituted alkyl group, an unsubstituted alkyl group, a substituted phenyl group, or an unsubstituted phenyl group.

6. 3. The toner according to claim 1, wherein the content (mass %) of the pigment dispersant in the toner particles is 1.5 mass % or more and 30.0 mass % or less with respect to the total mass of the pigment.

7. The pigment is 3. The toner according to claim 1, wherein the pigment is at least one pigment selected from the group consisting of carbon black, C. I. Pigment Yellow 74, 93, 139, 155, 180, and 185; C. I. Pigment Red 31, 122, 150, 170, 258, and 269; and C. I. Pigment Blue 15:3 and 15:

4.

8. 3. The toner according to claim 1, wherein the toner particles contain a crystalline material.

9. 9. The toner according to claim 8, wherein the content (% by mass) of the crystalline material in the toner particles is 20.0% by mass or more and 50.0% by mass or less, based on the toner particles.

10. 10. The toner according to claim 8, wherein the crystalline material is a crystalline resin.

11. 11. The toner according to claim 10, wherein the crystalline resin is a crystalline vinyl resin having a structure represented by the following formula (5) or a crystalline vinyl resin having a structure represented by the following formula (6): 【Transformation 6】 (In formula (5), R ２１ represents a hydrogen atom or a methyl group, L １ represents a single bond, —COO—, or —CONH—; n represents an integer of 15 or more and 30 or less. 【Transformation 7】 (In formula (6), R ２２ ~R ２５ At least two of the ２６ and the remainder represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Y represents a single bond or an alkylene group having 1 to 2 carbon atoms; R ２６ represents an alkyl group having 16 to 30 carbon atoms.

Images