toner

Abstract

To provide a toner that exhibits excellent low temperature fixability and electrification maintainability and exhibits excellent scratch resistance even for a fixed image on thick coated paper.SOLUTION: A toner has toner particles containing a binder resin. The binder resin contains amorphous polyester and crystalline polyester. The weight average molecular weight of an o-dichlorobenzene soluble matter at 100°C of the crystalline polyester is 1500 or more and 4900 or less. The crystalline polyester contains a modified crystalline polyester having at least one of a structure in which a hydroxy group at a main chain end of the crystalline polyester is end-modified with an aliphatic monocarboxylic acid having 16-31 carbon atoms, and a structure in which a carboxy group at a main chain end of the crystalline polyester is end-modified with an aliphatic monoalcohol having 15-30 carbon atoms. The content ratio of the end-modified structure in the crystalline polyester is 80.0 mol% or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to toners used in electrophotography, electrostatic recording, electrostatic printing, and the like. [Background technology]

[0002] In recent years, as electrophotographic full-color copiers have become more widespread, there has been a demand for not only higher speeds and higher image quality, but also additional performance improvements such as energy saving, shorter recovery times from sleep mode, and compatibility with a wide variety of media.

[0003] Specifically, toners that can be fixed at lower temperatures and have excellent low-temperature fixability are required to reduce power consumption in the fixing process as energy-saving toners. Also, toners that have excellent charge retention properties and little change in charge amount throughout a long period of sleep mode are required to shorten the recovery time from a sleep mode.

[0004] Furthermore, thick coated paper, which is one of the diverse media, contains a large amount of inorganic fine particles such as calcium carbonate to increase whiteness, which increases the coefficient of friction when paper sheets rub against each other, making the toner in the fixed image more likely to peel off from the paper. Therefore, in order to prevent toner peeling due to friction between paper sheets, there is a demand for a toner with excellent abrasion resistance that can reduce the coefficient of friction by coating the surface of the fixed image with wax and promoting the exudation of the wax.

[0005] Therefore, a toner using a crystalline polyvinyl resin has been proposed as a toner with excellent low-temperature fixing ability, charge retention, and abrasion resistance (Patent Document 1). Also, a toner having alkenyl succinic acid as a carboxylic acid component of polyester has been proposed as a toner with excellent abrasion resistance (Patent Document 2). [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2018-156074 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-197207 Summary of the Invention [Problem to be solved by the invention]

[0007] The toner described in Patent Document 1 uses a crystalline polyvinyl resin that has sharp melting properties and high hydrophobicity, and therefore exhibits excellent low-temperature fixability and charge retention. Meanwhile, the crystalline polyvinyl resin has a high affinity for wax, which inhibits wax from seeping out and makes it difficult for a wax layer to form on the surface of the fixed image. Therefore, the coefficient of friction caused by rubbing between sheets of paper does not decrease, and it was found that the toner in the fixed image may peel off from the paper.

[0008] Furthermore, in the toner described in Patent Document 2, the alkenyl succinic acid has a high affinity with wax, so that during fixing, the wax is more likely to be retained on the fixed image rather than being transferred to the fixing roller, and therefore a certain degree of abrasion resistance can be achieved on paper types such as plain paper. However, because the binder resin has a high affinity with wax, the wax also is inhibited from seeping out of the surface of the fixed image, and it has been found that abrasion resistance may be poor on thick coated paper.

[0009] As mentioned above, it is difficult to provide a toner that satisfies all of the following requirements: low-temperature fixability, charge retention, and abrasion resistance. There is an urgent need to develop a toner that exhibits excellent abrasion resistance even when fixed on coated paper, etc. The present disclosure provides a toner that not only exhibits excellent low-temperature fixability and charge retention, but also exhibits excellent abrasion resistance even when fixed on thick coated paper, etc. [Means for solving the problem]

[0010] The present disclosure provides a toner having toner particles containing a binder resin, the binder resin contains an amorphous polyester and a crystalline polyester, (i) the weight average molecular weight of the crystalline polyester soluble in o-dichlorobenzene at 100°C is 1500 or more and 4900 or less; (ii) The crystalline polyester has a structure in which the hydroxyl group at the end of the main chain of the crystalline polyester is terminally modified with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms. Construction The modified crystalline polyester has the following structure: (iii) the content of the terminal-modified structure in the crystalline polyester is 95 0 mol% or more the law of nature, the content of the crystalline polyester in the binder resin is 3.0% by mass or more and 14.6% by mass or less, the main chain of the crystalline polyester is a condensation polymer of an aliphatic dicarboxylic acid and an aliphatic diol, and the difference in the number of carbon atoms between the aliphatic dicarboxylic acid and the aliphatic diol is 4 or less; The SP value of the crystalline polyester is C [(cal / cm 3 ) 0.5 ], and the SP value of the amorphous polyester was A [(cal / cm 3 ) 0.5 ], then the SP A and the SP C satisfies the following formula (1): Regarding toner. 1.6≦SP A -SP C ≦1.9···(1) [Effects of the Invention]

[0011] According to the present disclosure, it is possible to provide a toner that not only exhibits excellent low-temperature fixability and charge retention, but also exhibits excellent abrasion resistance even in fixed images on thick coated paper and the like. DETAILED DESCRIPTION OF THE INVENTION

[0012] In this disclosure, unless otherwise specified, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range refer to a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined. Furthermore, a monomer unit refers to the reacted form of a monomer substance in a polymer. Furthermore, a crystalline polyester is a resin that exhibits a clear endothermic peak in differential scanning calorimetry (DSC).

[0013] The present inventors have conducted research into toners that have excellent low-temperature fixability, charge retention, and abrasion resistance. As a result, the present inventors have found that the crystallinity of the material is important for achieving a high level of image abrasion resistance. Therefore, the present inventors have focused on crystalline polyesters, which have affinity with paper and crystallinity, as crystalline materials that do not inhibit fixation. One way to increase the crystallinity of crystalline materials is to lower the molecular weight of the material, which increases the diffusion coefficient of the material and makes it easier to form a folded structure.

[0014] However, simply lowering the molecular weight of crystalline polyester increases the ratio of terminal hydroxyl and carboxyl groups relative to the hydrocarbon portion contained in the main chain, etc., and increases the polarity of the crystalline polyester. Therefore, when an amorphous polyester is further used as a binder resin, the crystalline polyester and the amorphous polyester become compatible with each other during the fixing process. As a result, it has become clear that the crystallization of the crystalline polyester in the toner image does not proceed, making it impossible to provide an image with a low friction coefficient.

[0015] Therefore, the present inventors further investigated ways to reduce the proportion of terminal hydroxyl and carboxyl groups by blocking them to the utmost while attempting to lower the molecular weight of the crystalline polyester. In this way, they discovered that by reducing the polarity of the crystalline polyester, the crystalline polyester crystallizes instantly after the fixing process, allowing images with a low coefficient of friction to be provided. Specifically, they discovered that it is important to react a monomer having an aliphatic hydrocarbon group with 15 to 30 carbon atoms with the crystalline polyester. This monomer is highly reactive with the terminal hydroxyl and carboxyl groups, and can act as a crystal nucleating agent to initiate the folding structure of the main chain of the crystalline polyester. Furthermore, by reducing the polarity of the crystalline polyester itself, It is possible.

[0016] The toner particles contain a binder resin. The binder resin contains an amorphous polyester and a crystalline polyester. (i) The weight-average molecular weight of the crystalline polyester soluble in o-dichlorobenzene at 100°C is 1,500 or more and 4,900 or less. When the weight-average molecular weight of the crystalline polyester soluble in o-dichlorobenzene at 100°C is within the above range, the diffusion coefficient of the crystalline polyester is increased, making it easier to form a folded structure, and the crystallinity can be increased. This enables the formation of images with a low coefficient of friction, resulting in excellent abrasion resistance. In addition, the increased crystallinity suppresses molecular motion, making it difficult for charge paths to be formed, resulting in excellent charge retention.

[0017] The weight-average molecular weight of the crystalline polyester soluble in o-dichlorobenzene at 100°C is preferably 1800 or more and 2500 or less. Furthermore, by forming a structure in which the hydroxyl group at the end of the main chain of the crystalline polyester is terminally modified with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms, and a structure in which the carboxyl group at the end of the main chain of the crystalline polyester is terminally modified with an aliphatic monoalcohol having 15 to 30 carbon atoms, as described below, the weight-average molecular weight of the crystalline polyester can be easily controlled within the above range.

[0018] The crystalline polyester contains (ii) a modified crystalline polyester having at least one of a structure in which a hydroxy group at the end of the main chain of the crystalline polyester is terminally modified with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms (preferably 18 to 26, more preferably 20 to 24 carbon atoms) and a structure in which a carboxy group at the end of the main chain of the crystalline polyester is terminally modified with an aliphatic monoalcohol having 15 to 30 carbon atoms (preferably 18 to 26, more preferably 20 to 24 carbon atoms), and (iii) the content of the terminally modified structure in the crystalline polyester is 80.0 mol % or more.

[0019] When the hydroxyl group and carboxyl group at the end of the main chain are modified, a highly polar functional group is modified, which can suppress compatibility with the amorphous polyester binder resin. This can increase the crystallinity of the crystalline polyester, allowing the formation of an image with a low coefficient of friction, resulting in excellent abrasion resistance. Furthermore, the increased crystallinity suppresses molecular motion, making it difficult for charge paths to be formed, resulting in excellent charge retention.

[0020] When the carbon number of the terminal-modified aliphatic monocarboxylic acid or aliphatic monoalcohol is within the above range, it can serve as the starting point for the folding structure of the main chain of the crystalline polyester, like a crystal nucleating agent. Furthermore, the polarity of the crystalline polyester itself can be reduced, suppressing its compatibility with amorphous polyesters. As a result, the crystallinity of the crystalline polyester can be increased, allowing the formation of images with a low friction coefficient, resulting in excellent abrasion resistance. Furthermore, the increased crystallinity suppresses molecular motion, making it difficult for charge paths to be formed, resulting in excellent charge retention.

[0021] Furthermore, when the content of the terminal-modified structure is 80.0 mol% or more, the effect of increasing the degree of crystallinity and the effect of reducing the polarity of the crystalline polyester and suppressing its compatibility with the amorphous polyester are exerted. Therefore, excellent abrasion resistance and charge retention are obtained. The content of the terminal-modified structure is preferably 90.0 mol% or more, more preferably 95.0 mol% or more, and even more preferably 98.0 mol% or more. There is no particular upper limit, but it is preferably 100.0 mol% or less, more preferably 99.0 mol% or less. The content of the terminal-modified structure can be controlled by the amount of the terminal-modifying aliphatic monocarboxylic acid or aliphatic monoalcohol added.

[0022] The crystalline polyester preferably has a structure in which the hydroxy group at the end of the main chain is terminally modified with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms. The structure terminally modified with an aliphatic monocarboxylic acid is represented by the following formula (I): Furthermore, the structure in which the carboxy group at the end of the main chain is terminally modified with an aliphatic monoalcohol having 15 to 30 carbon atoms is represented by the following formula (II): [ka]

[0023] In the formula, P represents the main chain structure of the crystalline polyester. 1 R is a (preferably linear) alkyl group having 15 to 30 carbon atoms (preferably 17 to 25, more preferably 19 to 23). 2 is a (preferably linear) alkyl group having 15 to 30 carbon atoms (preferably 18 to 26, more preferably 20 to 24). 1 is a monomer unit of an aliphatic monocarboxylic acid, and in (II), -OR 2 is a monomer unit of an aliphatic monoalcohol.

[0024] In the crystalline polyester, the total content of the monomer units derived from aliphatic monocarboxylic acid and the monomer units derived from aliphatic monoalcohol contained in the terminally modified structure is preferably 30.0% by mass or more, more preferably 33.0% by mass or more. There is no particular upper limit, but it is preferably 70.0% by mass or less, more preferably 65.0% by mass or less, and even more preferably 40.0% by mass or less.

[0025] When the total content of the aliphatic monocarboxylic acid monomer unit and the aliphatic monoalcohol monomer unit contained in the terminally modified structure is within the above range, it indicates that the hydroxyl group and carboxyl group at the main chain end are more sufficiently modified. Therefore, the compatibility of the crystalline polyester with the amorphous polyester can be further suppressed. Furthermore, the crystallinity of the crystalline polyester can be increased, allowing the formation of images with a lower friction coefficient, resulting in better abrasion resistance. Furthermore, the increased crystallinity suppresses molecular motion, making it difficult for charge paths to be formed, resulting in better charge retention.

[0026] The total acid value and hydroxyl value of the crystalline polyester is preferably 0.1 mgKOH / g to 5.0 mgKOH / g. When the total acid value and hydroxyl value of the crystalline polyester is within the above range, the hydroxyl and carboxyl groups at the ends of the main chain are more fully modified, and compatibility with amorphous polyesters can be suppressed. This increases the crystallinity of the crystalline polyester, allowing for the formation of images with a lower coefficient of friction, resulting in better abrasion resistance. Furthermore, increased crystallinity suppresses molecular mobility, making it difficult for charge paths to be formed, resulting in better charge retention.

[0027] The total acid value and hydroxyl value of the crystalline polyester is more preferably 0.1 mgKOH / g to 3.0 mgKOH / g, and even more preferably 0.2 mgKOH / g to 2.0 mgKOH / g. The total acid value and hydroxyl value of the crystalline polyester can be controlled by the type and amount of monomer added.

[0028] The SP value of crystalline polyester is C Then, SP C However, preferably 8.8 (cal / cm 3 ) 0.5 ~9.4(cal / cm 3 ) 0.5 SP C is in the above range In this case, the hydroxyl and carboxyl groups at the ends of the main chain are more fully modified, and compatibility with the amorphous polyester can be suppressed. This increases the crystallinity of the crystalline polyester, allowing the formation of images with a lower coefficient of friction, resulting in better abrasion resistance. Furthermore, the increased crystallinity suppresses molecular motion, making it difficult for charge paths to be formed, resulting in better charge retention.

[0029] SP C is preferably 8.8 (cal / cm 3 ) 0.5 ~9.2(cal / cm 3 ) 0.5 and more preferably 8.9 (cal / cm 3 ) 0.5 ~9.1(cal / cm 3 ) 0.5 SP C can be controlled by the type and amount of monomer added.

[0030] In addition, the SP value of amorphous polyester is A Then, SP A However, preferably 10.5 (cal / cm 3 ) 0.5 ~11.5(cal / cm 3 ) 0.5 SP AWhen the temperature is within the above range, the amorphous polyester and the crystalline polyester have a certain affinity, so that the crystalline polyester exhibiting a low coefficient of friction is supported on the amorphous polyester, thereby achieving a more excellent abrasion resistance effect. Furthermore, during fixing, the molten crystalline polyester is compatible with the amorphous polyester, resulting in a more excellent low-temperature fixing effect.

[0031] SP A is preferably 10.6 (cal / cm 3 ) 0.5 ~11.1(cal / cm 3 ) 0.5 and more preferably 10.7 (cal / cm 3 ) 0.5 ~11.0(cal / cm 3 ) 0.5 SP A can be controlled by the type and amount of monomer added.

[0032] Crystalline polyester and amorphous polyester are SP A and SP C It is preferable that satisfies the following formula (1). 1.5≦SP A -SP C ≦2.1 (1)

[0033] SP A and SP C When the crystalline polyester is in the above range, the amorphous polyester and the crystalline polyester have a certain affinity, so that the crystalline polyester exhibiting a low coefficient of friction is easily supported on the amorphous polyester, and thus a superior abrasion resistance effect is obtained. Furthermore, during fixing, the molten crystalline polyester is compatible with the amorphous polyester, so that a superior low-temperature fixing effect is obtained.

[0034] SP A -SP C More preferably, SP satisfies the following formula (4), and even more preferably satisfies the following formula (5): A -SP C can be controlled by the type and amount of monomer added. 1.6≦SP A -SP C ≦2.0 (4) 1.7≦SP A -SP C ≦1.9 (5)

[0035] The toner preferably has an endothermic heat ΔH derived from the crystalline polyester measured by differential scanning calorimetry (DSC) of 5.0 J / g to 15.0 J / g. ΔH in the above range indicates that the toner contains a sufficient amount of crystals to reduce the coefficient of friction, thereby achieving better abrasion resistance.

[0036] The endothermic heat ΔH derived from the crystalline polyester is preferably 7.0 J / g to 15.0 J / g, more preferably 9.0 J / g to 12.0 J / g. The ΔH derived from the crystalline polyester varies depending on the amount of the crystalline polyester added and the SP A -SP C It can be controlled by

[0037] The main chain of the crystalline polyester is preferably a condensation polymer of an aliphatic dicarboxylic acid and an aliphatic diol. The difference in the number of carbon atoms between the aliphatic dicarboxylic acid and the aliphatic diol is 4 or less. When the difference in the number of carbon atoms is 4 or less, a folded structure of the main chain of the crystalline polyester is easily formed, the degree of crystallization can be increased, and an image with a low coefficient of friction can be formed. A more excellent abrasion resistance effect can be obtained. Furthermore, the increased crystallinity suppresses molecular motion, making it difficult for charge paths to be formed, resulting in a more excellent charge retention effect. The difference in the number of carbon atoms is more preferably 2 or less. There is no particular lower limit, but it is preferably 0 or more. The difference in the number of carbon atoms is even more preferably 0.

[0038] The toner particles preferably contain a hydrocarbon wax. W Then, SP W and SP C It is preferable that satisfies the following formula (2). 0.7≦SPC -SP W ≦1.2 (2)

[0039] SP W and SP C When the crystalline polyester has a certain affinity with the hydrocarbon wax, the hydrocarbon wax acts as a crystal nucleus, which serves as the starting point for the folding structure of the main chain of the crystalline polyester, thereby further increasing the degree of crystallinity. As a result, an image with a lower coefficient of friction can be formed, resulting in better abrasion resistance. Furthermore, the increased crystallinity suppresses molecular motion, making it difficult for a charge path to be formed, resulting in better charge retention.

[0040] SP C -SP W More preferably, SP satisfies the following formula (6), and even more preferably, SP satisfies the following formula (7): C -SP W can be controlled by the type and amount of monomer added. 0.8≦SP C -SP W ≦1.2 (6) 0.9≦SP C -SP W ≦1.1 (7)

[0041] The melting point of hydrocarbon wax is T W The melting point of the crystalline polyester is T C When T W and T C It is preferable that satisfies the following formula (3). 0.0≦|T C -T W |≦25.0 (3)

[0042] T W and T CWhen the crystalline polyester has a certain affinity with the hydrocarbon wax, the wax acts as a crystal nucleus, which serves as the starting point for the folding structure of the main chain of the crystalline polyester, thereby further increasing the degree of crystallinity. As a result, an image with a lower coefficient of friction can be formed, resulting in better abrasion resistance. Furthermore, the increased crystallinity suppresses molecular motion, making it difficult for a charge path to be formed, resulting in better charge retention.

[0043] |T C -T W More preferably, | satisfies the following formula (8), and even more preferably, |T C -T W can be controlled by the type and molecular weight of the monomer. 1.0≦|T C -T W |≦10.0 (8) 2.0≦|T C -T W |≦6.0 (9)

[0044] <Amorphous polyester> The amorphous polyester is preferably a condensation polymer of a polyhydric alcohol (dihydric, trihydric or higher alcohol) and a polycarboxylic acid (dihydric, trihydric or higher carboxylic acid), its acid anhydride or its lower alkyl ester.

[0045] The following polyhydric alcohol monomers can be used as the polyhydric alcohol monomer for the amorphous polyester: Dihydric alcohol components include, for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenols represented by formula (A) and derivatives thereof; [ka]

[0046] (In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x+y is 0 or more and 10 or less.) Examples include diols represented by formula (B). [ka]

[0047] Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene. Among these, glycerol, trimethylolpropane, and pentaerythritol are preferred. These dihydric and trihydric or higher alcohols can be used alone or in combination.

[0048] The following polycarboxylic acid monomers can be used as the polycarboxylic acid monomer for the polyester resin. Examples of dicarboxylic acid components include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids, and lower alkyl esters thereof. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenylsuccinic acid are preferred.

[0049] Examples of trivalent or higher carboxylic acids, their acid anhydrides, and their lower alkyl esters include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimer acid, and their acid anhydrides and lower alkyl esters. Among these, 1,2,4-benzenetricarboxylic acid, i.e., trimellitic acid or its derivatives, is particularly preferred. These dicarboxylic acids and tricarboxylic or higher carboxylic acids can be used alone or in combination.

[0050] The method for producing the polyester resin is not particularly limited, and known methods can be used. For example, the aforementioned alcohol monomer and carboxylic acid monomer are simultaneously charged and polymerized via an esterification reaction or transesterification reaction and a condensation reaction to produce the polyester resin. The polymerization temperature is not particularly limited, but is preferably in the range of 180°C to 290°C. Polymerization of the polyester resin can use polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide. In particular, the polyester resin is preferably a polyester resin polymerized using a tin-based catalyst.

[0051] The amorphous polyester preferably contains a monomer unit represented by the following formula (F) and a monomer unit represented by the following formula (G), and more preferably contains a monomer unit represented by the following formula (E), a monomer unit represented by the following formula (F), and a monomer unit represented by the following formula (G). These monomer units make it easier to achieve excellent low-temperature fixability, charge retention, and abrasion resistance. The monomer unit refers to the form in which a monomer substance in a polymer is reacted. The content of the monomer unit represented by formula (E) in the amorphous polyester is preferably 20% by mass or more and 60% by mass or less, and more preferably 30% by mass or more and 50% by mass or less. The content of the monomer unit represented by formula (F) in the amorphous polyester is preferably 20% by mass or more and 65% by mass or less, and more preferably 30% by mass or more and 50% by mass or less. The content of the monomer unit represented by formula (G) in the amorphous polyester is preferably 7% by mass or more and 30% by mass or less, more preferably 10% by mass or more and 30% by mass or less, and even more preferably 15% by mass or more and 25% by mass or less.

[0052] In the formula, R 3 represents a benzene ring, and is preferably bonded at the para position. 4 R represents an ethylene group or a propylene group, x and y each represent an integer of 1 or more, and the average value of x+y is 2 to 10. 5 represents an ethylene group or a propylene group, preferably an ethylene group. [ka]

[0053] The amorphous polyester may be a hybrid resin containing other resin components as long as the amorphous polyester is the main component. The term "main component" refers to a content ratio of 50% by mass or more and 100% by mass or less, preferably 80% by mass or more and 100% by mass or less, and more preferably 90% by mass or more and 100% by mass or less. For example, a hybrid resin of a polyester resin and a vinyl resin can be used. The following methods can be used to obtain a reaction product of a vinyl resin and a polyester resin, such as a hybrid resin. A preferred method involves carrying out a polymerization reaction of one or both of the vinyl resin and the polyester resin in the presence of monomer components that can react with each of the vinyl resin and the polyester resin.

[0054] For example, among the monomers constituting the polyester resin component, those capable of reacting with the vinyl copolymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof, etc. Among the monomers constituting the vinyl copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxyl group, and acrylic acid or methacrylic acid esters.

[0055] In addition to the crystalline polyester and the amorphous polyester, various resin compounds known as binder resins can be used in combination to the extent that the above-mentioned effects are not impaired. Examples of such resin compounds include phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic resins, acrylic resins, methacrylic resins, polyvinyl acetate resins, silicone resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumaroindene resins, and petroleum-based resins.

[0056] The content ratio of the crystalline polyester and the amorphous polyester in the binder resin is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and still more preferably 95% by mass or more and 100% by mass or less.

[0057] The content of the amorphous polyester in the binder resin is preferably 80.0% by mass or more and 97.0% by mass or less, more preferably 85.4% by mass or more and 95.1% by mass or less, and even more preferably 88.0% by mass or more and 92.0% by mass or less.

[0058] The peak molecular weight of the amorphous polyester is preferably 3,500 to 20,000 in terms of low-temperature fixability and abrasion resistance. The acid value of the amorphous polyester is preferably 5 mgKOH / g to 30 mgKOH / g in terms of charge retention in a high-temperature, high-humidity environment. The hydroxyl value of the amorphous polyester is preferably 20 mgKOH / g to 70 mgKOH / g in terms of low-temperature fixability and charge retention.

[0059] <Crystalline polyester> Monomers used for the crystalline polyester include polyhydric alcohols (divalent, trivalent or higher alcohols), polycarboxylic acids (divalent, trivalent or higher carboxylic acids), their acid anhydrides or their lower alkyl esters. The main chain of the crystalline polyester is preferably a condensation polymer of an aliphatic dicarboxylic acid and an aliphatic diol.

[0060] The polyhydric alcohol monomer used in the crystalline polyester may be any of the following polyhydric alcohol monomers. The polyhydric alcohol monomer is not particularly limited, but is preferably a chain (more preferably a linear) aliphatic diol, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, and neopentyl glycol. Among these, linear aliphatic α,ω-diols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol are particularly preferred.

[0061] Polyhydric alcohol monomers other than the above polyhydric alcohols can also be used. Among the polyhydric alcohol monomers, dihydric alcohol monomers include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol; and the like. Furthermore, among the polyhydric alcohol monomers, trihydric or higher polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; and aliphatic alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

[0062] The polycarboxylic acid monomer used in the crystalline polyester may be any of the following polycarboxylic acid monomers. While the polycarboxylic acid monomer is not particularly limited, it is preferably a chain (more preferably a linear) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, as well as hydrolyzed versions of these acid anhydrides or lower alkyl esters.

[0063] Polycarboxylic acids other than the above polycarboxylic acid monomers can also be used. Among other polycarboxylic acid monomers, examples of dicarboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; and aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid. Acids: alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, and also acid anhydrides or lower alkyl esters thereof.

[0064] Furthermore, among the other carboxylic acid monomers, examples of trivalent or higher polyvalent carboxylic acids include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic acid, and aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, as well as derivatives such as acid anhydrides and lower alkyl esters of these.

[0065] The aliphatic dicarboxylic acid is a linear aliphatic dicarboxylic acid having 2 to 16 carbon atoms (preferably 8 to 14). The aliphatic diol is a linear aliphatic diol having 2 to 16 carbon atoms (preferably 8 to 14). The content of monomer units polymerized from linear aliphatic dicarboxylic acids having 2 to 16 carbon atoms (preferably 8 to 14) in the crystalline polyester is preferably 8% by mass to 45% by mass, more preferably 20% by mass to 35% by mass. The content of monomer units polymerized from linear aliphatic diols having 2 to 16 carbon atoms (preferably 8 to 14) in the crystalline polyester is preferably 15% by mass to 50% by mass, more preferably 25% by mass to 45% by mass.

[0066] The crystalline polyester contains (ii) a modified crystalline polyester having at least one of a structure in which a hydroxy group at the end of the main chain is terminally modified with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms and a structure in which a carboxy group at the end of the main chain is terminally modified with an aliphatic monoalcohol having 15 to 30 carbon atoms. Preferably, the modified crystalline polyester is a crystalline polyester. The content of the modified crystalline polyester in the crystalline polyester is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, still more preferably 95% by mass or more and 100% by mass or less, and particularly preferably 100% by mass.

[0067] Examples of aliphatic monocarboxylic acids having 16 to 31 carbon atoms include palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadecylic acid, arachidic acid (icosanoic acid), henicosanoic acid, behenic acid (docosanoic acid), tetracosanoic acid, hexacosanoic acid, octacosanoic acid, and triacontanoic acid.

[0068] Examples of aliphatic monoalcohols having 15 to 30 carbon atoms include palmityl alcohol (hexadecanol), margaryl alcohol (heptadecanol), stearyl alcohol (octadecanol), nonadecanol, arachidyl alcohol (icosanol), heneicosanol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, 1-heptacosanol, montanyl alcohol, 1-nonacosanol, and myricyl alcohol.

[0069] The content of the crystalline polyester in the binder resin is preferably 3.0% by mass or more and 20.0% by mass or less, more preferably 4.9% by mass or more and 14.6% by mass or less, and even more preferably 8.0% by mass or more and 12.0% by mass or less. The above ranges are preferred from the viewpoints of low-temperature fixability, abrasion resistance, and charge retention in high-temperature, high-humidity environments. The melting point of the crystalline polyester is preferably 60 to 100°C, more preferably 65 to 90°C, and even more preferably 70 to 85°C.

[0070] The crystalline polyester can be produced by a conventional polyester synthesis method. For example, the carboxylic acid monomer and the alcohol monomer are subjected to an esterification reaction or an ester exchange reaction, and then the resulting mixture is subjected to a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. Thereafter, the above-mentioned aliphatic compound is further added to carry out an esterification reaction, thereby obtaining the desired crystalline polyester.

[0071] The above esterification or transesterification reaction can be carried out, if necessary, using a conventional esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, or magnesium acetate.

[0072] The polycondensation reaction can be carried out using a conventional polymerization catalyst, such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide, etc. The polymerization temperature and the amount of catalyst are not particularly limited and may be determined appropriately.

[0073] In the esterification or transesterification reaction or polycondensation reaction, in order to increase the strength of the resulting crystalline polyester, it is also possible to use a method in which all of the monomers are charged at once, or in order to reduce the amount of low-molecular-weight components, a divalent monomer is reacted first, and then a trivalent or higher valent monomer is added and reacted.

[0074] In the synthesis of crystalline polyesters, including modified crystalline polyesters, it is preferable to polycondense at least one selected from the group consisting of the above-mentioned aliphatic monocarboxylic acids and aliphatic monoalcohols (preferably the above-mentioned aliphatic monocarboxylic acids), with an aliphatic diol and an aliphatic dicarboxylic acid. The proportion of the aliphatic diol is preferably 30 to 50 mol%, more preferably 35 to 45 mol%, and the proportion of the aliphatic dicarboxylic acid is preferably 5 to 45 mol%, more preferably 10 to 35 mol%. Furthermore, the proportion of at least one selected from the group consisting of the above-mentioned aliphatic monocarboxylic acids and aliphatic monoalcohols (preferably the above-mentioned aliphatic monocarboxylic acids) is preferably 15 to 60 mol%, more preferably 20 to 30 mol%.

[0075] The toner particles may contain a wax, for example: hydrocarbon waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes containing fatty acid esters as the main component such as carnauba wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax. Saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and valinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscaprolactone Saturated fatty acid bisamides such as phosphoric acid amide, ethylene bislauric acid amide, and hexamethylene bisstearic acid amide; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipic acid amide, and N,N'-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide and N,N'-distearyl isophthalic acid amide; fatty acid metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acid and glycerin such as behenic acid monoglyceride. Partially esterified polyhydric alcohols; methyl ester compounds with hydroxyl groups obtained by hydrogenation of vegetable oils.

[0076] Among these waxes, ester wax or hydrocarbon wax is preferred. Hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are more preferred from the viewpoint of abrasion resistance. The melting point of the wax is preferably 60 to 120°C, more preferably 65 to 90°C, and even more preferably 70 to 90°C. The content of the wax is preferably 3 to 8 parts by mass per 100 parts by mass of the binder resin from the viewpoint of abrasion resistance.

[0077] <Coloring agent> The toner particles may contain a colorant as needed. Examples of colorants include the following: Black colorants include carbon black; and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, or a dye and a pigment may be used in combination. From the viewpoint of the image quality of full-color images, it is preferable to use a dye and a pigment in combination.

[0078] Examples of pigments for magenta toner include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0079] Dyes for magenta toner include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0080] Examples of pigments for cyan toners include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; CI Acid Blue 45; and copper phthalocyanine pigments in which one to five phthalimidomethyl groups are substituted on the phthalocyanine skeleton. Examples of dyes for cyan toners include CI Solvent Blue 70.

[0081] Yellow toner pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Vat Yellow 1, 3, 20. Yellow toner dyes include CI Solvent Yellow 162.

[0082] These colorants can be used alone or in combination, or in the form of a solid solution. The colorants are selected from the viewpoints of hue angle, chroma, brightness, lightfastness, transparency on overhead projectors, and dispersibility in toner particles. The content of the colorant is preferably 0.1 to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0083] <Charge control agent> The toner particles may contain a charge control agent as needed. By incorporating a charge control agent, the charging characteristics can be stabilized and the amount of triboelectric charge can be optimally controlled according to the development system. As the charge control agent, known agents can be used, but particularly, metal compounds of aromatic carboxylic acids are preferred because they are colorless, have a high charging speed of the toner, and can stably maintain a constant amount of charge.

[0084] Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate salts or sulfonate esters on the side chain, polymeric compounds having carboxylate salts or carboxylate esters on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0085] The charge control agent may be added internally or externally to the toner particles. The content of the charge control agent is preferably 0.2 to 10.0 parts by mass, more preferably 0.5 to 10.0 parts by mass, per 100 parts by mass of the binder resin.

[0086] <Inorganic fine particles> The toner may contain inorganic fine particles as needed. The inorganic fine particles may be added internally to the toner particles or may be mixed with the toner as an external additive. Examples of inorganic fine particles include silica fine particles, titanium oxide fine particles, alumina fine particles, and fine particles of their double oxides. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferred for improving flowability and uniform charging. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0087] From the viewpoint of improving fluidity, inorganic particles as external additives should have a specific surface area of 50m 2 / g~400m 2 From the viewpoint of improving durability and stability, the inorganic fine particles as the external additive preferably have a specific surface area of 10 m 2 / g~50m 2 In order to achieve both improved fluidity and durability and stability, inorganic fine particles having a specific surface area within the above range may be used in combination.

[0088] The content of the external additive is preferably 0.1 to 10.0 parts by mass with respect to 100 parts by mass of toner particles. The toner particles and the external additive can be mixed using a known mixer such as a Henschel mixer.

[0089] <Developer> The toner can be used as a one-component developer, but in order to further improve dot reproducibility and to provide stable images over a long period of time, it is preferable to mix the toner with a magnetic carrier and use it as a two-component developer.

[0090] Examples of magnetic carriers that can be used include generally known ones such as iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, and oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) containing magnetic materials and a binder resin that holds the magnetic materials in a dispersed state.

[0091] When toner is mixed with a magnetic carrier to be used as a two-component developer, The mixing ratio of the carrier is preferably 2% by mass to 15% by mass, and more preferably 4% by mass to 13% by mass, in terms of the toner concentration in the two-component developer.

[0092] <Method of manufacturing toner particles> The method for producing toner particles is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a solution suspension method, an emulsion aggregation method, and a dispersion polymerization method can be used. The procedure for producing toner using the pulverization method will be described below. The pulverization method includes, for example, a step of melting and kneading a crystalline polyester and an amorphous polyester as binder resins, and, if necessary, other components such as a wax, a colorant, and a charge control agent, to obtain a resin composition, and a step of pulverizing the obtained resin composition to obtain toner particles.

[0093] In the raw material mixing process, materials constituting the toner particles, such as binder resin and, if necessary, other components such as wax, colorant, charge control agent, etc., are weighed out in predetermined amounts, blended, and mixed. Examples of mixing devices include a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.).

[0094] Next, the mixed materials are melt-kneaded to disperse the materials in the binder resin. In this melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Single- or twin-screw extruders are the mainstream due to their advantage of continuous production. Examples include a KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Iron Works), a twin-screw extruder (manufactured by KCK Corporation), a Ko-Kneader (manufactured by Buss Co., Ltd.), and a Kneadex (manufactured by Nippon Coke and Engineering Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled using a twin roll or the like and cooled with water or the like in a cooling process.

[0095] The cooled resin composition is then crushed to the desired particle size in a crushing process. In the crushing process, the resin composition is coarsely crushed using a crusher such as a crusher, hammer mill, or feather mill. The resin composition is then finely crushed using a crusher such as a Kryptron System (Kawasaki Heavy Industries), a Super Rotor (Nisshin Engineering), a Turbo Mill (Turbo Kogyo), or an air jet type fine crusher.

[0096] Thereafter, as necessary, the mixture is classified using a classifier or sieve such as an inertial classification type Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification type Turboplex (manufactured by Hosokawa Micron Corporation), a TSP Separator (manufactured by Hosokawa Micron Corporation), or a Faculty (manufactured by Hosokawa Micron Corporation).

[0097] The obtained toner particles may be used as they are. If necessary, external additives may be added to the surface of the toner particles to obtain a toner. Examples of methods for externally adding additives include blending the classified toner with predetermined amounts of various known external additives, and stirring and mixing the resulting mixture using a mixer such as a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation).

[0098] The methods for measuring various physical properties are explained below. (Method of separating each material from toner) The materials contained in the toner can be separated from the toner by utilizing the difference in solubility in the solvent of each material. First separation: Toner is dissolved in methyl ethyl ketone (MEK) at 23°C, and the soluble matter (amorphous polyester) and insoluble matter (crystalline polyester, release agent, colorant, inorganic particles, etc.) are separated. Separate. Second separation: The insoluble matter obtained in the first separation (crystalline polyester, release agent, colorant, inorganic fine particles, etc.) is dissolved in MEK at 100°C, and the soluble matter (crystalline polyester, release agent) is separated from the insoluble matter (colorant, inorganic fine particles, etc.). Third separation: The soluble matter (crystalline polyester, release agent) obtained in the second separation is dissolved in chloroform at 23°C, and the soluble matter (crystalline polyester) is separated from the insoluble matter (release agent).

[0099] <Method for measuring the content of monomer units of various polymerizable monomers in amorphous polyester and crystalline polyester> The content ratio of monomer units of various polymerizable monomers in amorphous polyester and crystalline polyester is measured as follows: 1 H-NMR was performed 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 Accumulation count: 64 times Measurement temperature: 30℃ Sample: 50 mg of the measurement sample is placed in a sample tube with an inner diameter of 5 mm, deuterated chloroform (CDCl3) is added as a solvent, and the sample is dissolved in a thermostatic bath at 40°C.

[0100] obtained 1 From the H-NMR chart, the integral value S of the peaks assigned to the constituent elements of the monomer units of various polymerizable monomers 1、 S 2、 S3, S n where S1 is the integral value of the peaks attributable to the constituent elements of the monomer unit of the first polymerizable monomer, S2 is the integral value of the peaks attributable to the constituent elements of the monomer unit of the second polymerizable monomer, and S n is the integral value of the peak attributed to the constituent element of the monomer unit of the nth polymerizable monomer. The content ratio of the monomer units of various polymerizable monomers is determined by the integral values S1, S2, S3 and S n It is calculated as follows using the following: 2、 n3···n n is the number of hydrogen atoms in the constituent element to which the peak of interest for each site is assigned. Content ratio (mol%) of monomer unit of nth polymerizable monomer= {(S n / n n ) / ((S1 / n1)+(S2 / n2)+(S3 / n3)...+(S n / n n ))}×100

[0101] Change the molecular terms of the same operation and calculate the amount of monomer units by various polymerizable monomers. When a polymerizable monomer that does not contain a hydrogen atom is used in the monomer unit by various polymerizable monomers, 13 using C-NMR, the measured nuclear 13 is C, and measurement is performed in single pulse mode, 1 and calculated in the same manner by H-NMR.

[0102] <SP value calculation method> The SP of amorphous polyester A value, the SP of the monomer unit by each polymerizable monomer of amorphous polyester A1 , SP A2 , SP A3 , SP An , the SP of crystalline polyester C value, the SP of the monomer unit by each polymerizable monomer of crystalline polyester C1 , SP C2 , SP C3 , SP Cn , the SP of wax W value is obtained as follows according to the calculation method proposed by Fedors.

[0103] For each polymerizable monomer or wax, for the atoms or atomic groups in the molecular structure, the evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm 3 / mol) are obtained from the table described in "Polym. Eng. Sci., 14(2), 147-154(1974)", and (ΣΔei / ΣΔvi) 0.5 is defined as the SP value (cal / cm 3 ) 0.5 and calculated.

[0104] SP A , SP C , SP WIt is calculated as follows. First, the evaporation energy (Δei) and molar volume (Δvi) of the monomer units composed of the polymerizable monomers are determined for each monomer unit, and the product of each with the molar ratio (j) in the amorphous polyester, crystalline polyester or hydrocarbon wax of each monomer unit is calculated respectively. Then, the SP value of each is calculated by substituting the sum of the evaporation energies and the sum of the molar volumes of each monomer unit into the following formula. SP value = {(Σj × ΣΔei) / (Σj × ΣΔvi)} 0.5

[0105] <Measurement of weight-average molecular weight of amorphous polyester by GPC> The molecular weight (Mw) of the THF-soluble component of the amorphous polyester is measured by gel permeation chromatography (GPC) as follows. First, the toner is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. Then, the resulting solution is filtered through a solvent-resistant membrane filter "Micron Disc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the components soluble in THF is about 0.8 mass%. Using this sample solution, measurement is performed under the following conditions. Apparatus: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation) Column: 7-series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 ml / min Oven temperature: 40.0 °C Sample injection volume: 0.10 mL

[0106] When calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0107] <Measurement of Weight-Average Molecular Weight of Crystalline Polyester by GPC> The weight-average molecular weight (Mw) of the o-dichlorobenzene-soluble component of crystalline polyester at 100 °C is measured by gel permeation chromatography (GPC) as follows. First, dissolve the crystalline polyester in o-dichlorobenzene over 1 hour at 100 °C. Then, filter the resulting solution through a solvent-resistant membrane filter “MAESORIDISC” with a pore size of 0.2 μm (manufactured by Tosoh Corporation) to obtain a sample solution. Note that the concentration of the components soluble in o-dichlorobenzene in the sample solution is adjusted to be approximately 0.1% by mass. Using this sample solution, measurements are carried out under the following conditions. Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation) Column: TSKgel GMHHR-H HT (7.8 cm I.D × 30 cm) in series of two (manufactured by Tosoh Corporation) Detector: RI for high temperature Temperature: 135 °C Solvent: o-dichlorobenzene Flow rate: 1.0 mL / min Sample: Inject 0.4 mL of a 0.1% sample

[0108] <000063​​​​​​​​​​​​​​​​) is measured using a differential scanning calorimeter "Q2000" (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 calorific value. Specifically, 3 mg of sample is precisely weighed and placed in an aluminum pan. An empty aluminum pan is used as a reference, and the measurement is performed under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 30℃ Measurement end temperature: 180℃

[0110] Measurements are performed over a measurement range of 30 to 180°C at a heating rate of 10°C / min. The temperature is raised to 180°C once and held there for 10 minutes, then lowered to 30°C, and then raised again. During this second heating process, the temperature at which the maximum endothermic peak occurs in the temperature-endothermic curve in the range of 30 to 100°C is the melting point.

[0111] <Measurement of heat absorption (ΔH) of crystalline polyester>> The endothermic heat derived from the crystalline polyester is measured using a differential scanning calorimeter "Q2000" (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 heat quantity. Specifically, 3 mg of toner is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the measurement is performed under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 30℃ Measurement end temperature: 180℃

[0112] Measurements are performed in the measurement range of 30 to 180°C at a heating rate of 10°C / min. The sample is heated to 180°C once and held there for 10 minutes, then cooled to 30°C, and heated again. During this second heating process, an endothermic peak is obtained from the baseline in the range of 30 to 100°C, and the amount of endothermic heat is calculated by integrating the peaks. Whether the obtained endothermic heat is due to the crystalline polyester is determined by checking the melting points of each material separated by the method described above (method for separating each material from the toner) and judging from the obtained melting points.

[0113] <Method for measuring the acid value of crystalline polyester> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of sample. The acid value of crystalline polyester is measured in accordance with JIS K 0070-1992, and specifically, it is measured according to the following procedure.

[0114] (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add ion-exchanged water to make 100 mL, and obtain a phenolphthalein solution. Dissolve 7 g of special-grade potassium hydroxide in 5 mL of water, and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide, etc., and leave to stand for 3 days, then filter to obtain a potassium hydroxide solution. Store the obtained potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by placing 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of phenolphthalein solution, and titrating with potassium hydroxide solution to determine the amount of potassium hydroxide required for neutralization. The concentration of the potassium hydroxide solution is calculated from the amount of the potassium hydroxide solution added. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0115] (2) Operation (A) Main test A 2.0 g sample of ground crystalline polyester was weighed accurately into a 200 mL Erlenmeyer flask, and 100 mL of a 2:1 toluene / ethanol mixture was added and dissolved over 5 hours. A few drops of the phenolphthalein solution were then added as an indicator, and the solution was titrated with the potassium hydroxide solution. The titration endpoint was determined when the indicator remained a pale red color for 30 seconds. (B) Blank test The titration is carried out in the same manner as above, except that no sample is used (i.e., only the toluene / ethanol (2:1) mixed solution is used).

[0116] (3) The obtained results are substituted into the following formula to calculate the acid value. A=[(CB)×f×5.61] / S where A is the acid value (mgKOH / g), B is the amount of potassium hydroxide solution added for the blank test (mL), C is the amount of potassium hydroxide solution added for the main test (mL), f is the factor of the potassium hydroxide solution, and S is the mass of the sample (g).

[0117] <Method for measuring the hydroxyl value of crystalline polyester> The hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when acetylating 1 g of a sample. The hydroxyl value of crystalline polyesters is measured in accordance with JIS K 0070-1992, and specifically, it is measured according to the following procedure. (1) Preparation of reagents Place 25 g of special-grade acetic anhydride in a 100 mL volumetric flask, add pyridine to make the total volume 100 mL, and shake thoroughly to obtain the acetylation reagent. Store the obtained acetylation reagent in an amber bottle to avoid contact with moisture, carbon dioxide, etc. Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution. Dissolve 35 g of special-grade potassium hydroxide in 20 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide and leave for 3 days, then filter to obtain potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by placing 25 mL of 0.5 mol / L hydrochloric acid in an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution, and then determining the amount of potassium hydroxide solution required for neutralization. The 0.5 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0118] (2) Operation (A) Main test Accurately weigh 1.0 g of the ground crystalline polyester sample into a 200 ml round-bottom flask, and accurately add 5.0 ml of the acetylation reagent using a volumetric pipette. If the sample is difficult to dissolve in the acetylation reagent, add a small amount of special-grade toluene to dissolve it. Place a small funnel on the neck of the flask and immerse about 1 cm of the bottom of the flask in a glycerin bath at about 97°C. To prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is recommended to cover the base of the neck of the flask with a piece of cardboard with a round hole. After 1 hour, remove the flask from the glycerin bath and allow it to cool. After allowing it to cool, add 1 ml of water through the funnel and shake to hydrolyze the acetic anhydride. To further complete the hydrolysis, heat the flask again in the glycerin bath for 10 minutes. After allowing it to cool, wash the funnel and the walls of the flask with 5 ml of ethyl alcohol. Add a few drops of the phenolphthalein solution as an indicator and add a few drops of the potassium hydroxide solution. The endpoint of the titration is when the indicator remains a pale red color for approximately 30 seconds. (B) Blank test The titration is carried out in the same manner as above, except that no crystalline polyester sample is used. (3) The obtained results are substituted into the following formula to calculate the hydroxyl value. A = [{(BC) × 28.05 × f} / S] + D where A is the hydroxyl value (mgKOH / g), B is the amount of potassium hydroxide solution added in the blank test (ml), C is the amount of potassium hydroxide solution added in the main test (ml), f is the factor of the potassium hydroxide solution, S is the sample (g), and D is the acid value of the crystalline polyester (mgKOH / g).

[0119] <Method for calculating the percentage of terminally modified structures> The proportion of terminally modified structures in the crystalline polyester is calculated using the acid value, hydroxyl value, and molecular weight determined above. Specifically, the number of moles of terminal functional groups per gram of crystalline polyester is calculated using the following formula: Number of moles of terminal functional groups = (acid value + hydroxyl value) / (1000 x 56.105) Next, the number of moles per 1 g of crystalline polyester is calculated from the molecular weight of the crystalline polyester. Number of moles per 1g of crystalline polyester = 1 / Mw The amount of terminal functional groups is calculated from the ratio of each monomer unit of the crystalline polyester calculated by the above NMR. Specifically, for an ester product of a dicarboxylic acid and a dialcohol, the amount of functional groups is set to 2. When a trivalent or higher monomer is used, the amount of terminal functional groups can be calculated from its molar ratio. Percentage of terminally modified structures in crystalline polyester (mol%) = [1-number of moles of terminal functional groups / (number of moles per 1 g of crystalline polyester × amount of functional groups)] × 100 [Example]

[0120] The present invention will be described in more detail below with reference to examples, but these examples are not intended to limit the scope of the present invention. In the following formulations, parts are by weight unless otherwise specified.

[0121] <Production example of crystalline polyester C1> Dodecanediol: 40.0 parts (42.6 mol%) Dodecanedioic acid: 25.0 parts (30.6 mol%) Behenic acid: 35.0 parts (26.8 mol%) Titanium tetrabutoxide (esterification catalyst): 0.5 parts The above materials were weighed into a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. The flask was then purged with nitrogen gas, and the temperature was gradually increased while stirring. The mixture was allowed to react for 2 hours at 200°C. The pressure in the reaction vessel was then lowered to 8.3 kPa, and the mixture was allowed to react for 5 hours while maintaining the temperature at 200°C. The temperature was then lowered to stop the reaction, yielding crystalline polyester C1. The resulting crystalline polyester C1 had a weight-average molecular weight (Mw) of 2000, a proportion of terminally modified structures of 98.5 mol%, a total acid value and hydroxyl value of 0.8 mgKOH / g, and a melting point (T C was 72.0℃.

[0122] When the crystalline polyester C1 was analyzed by NMR, it was found to contain monomer units of each polymerizable monomer in the same proportions as in the above formulation. C is 9.1(cal / cm 3 ) 0.5 The difference in the number of carbon atoms between the aliphatic dicarboxylic acid and the aliphatic diol was 0.

[0123] <Production Examples of Crystalline Polyesters C2 to C17> The reaction was carried out in the same manner as in the production example of crystalline polyester C1, except that the polymerizable monomers, the amounts of each polymerizable monomer, and the reaction time were changed as shown in Tables 1 and 3. Crystalline polyesters C2 to C17 were obtained. The physical properties of crystalline polyesters C2 to C17 are shown in Tables 2 and 3. Crystalline polyesters C2 to C17 contained monomer units of each polymerizable monomer in the same proportions as in the formulation in Table 1.

[0124] [Table 1] The abbreviations in Tables 1 to 3 are as follows: DDG: Dodecanediol DDA: Dodecanedioic acid BA: Behenic acid PA: Palmitic acid PE: Pentanoic acid MA: Montanic acid LA: Russell's acid OG: Octanediol HG: Hexanediol EG: Ethylenediol

[0125] [Table 2] In the table, SP C The unit is (cal / cm 3 ) 0.5 is.

[0126] [Table 3] The proportion of terminal modification is the "content (mol %) of the terminally modified structure in the crystalline polyester."

[0127] <Production example of amorphous polyester A1> Bisphenol A PO (propylene oxide) adduct (average number of moles added: 2.0): 40.0 parts (12.5mol%) Ethylene glycol: 20.0 parts (39.8 mol%) Terephthalic acid: 40.0 parts (47.7 mol%) Titanium tetrabutoxide (esterification catalyst): 0.5 parts The above materials were weighed into a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. The atmosphere in the flask was then replaced with nitrogen gas, and the temperature was gradually increased while stirring. The mixture was allowed to react for 2 hours at 200°C. The pressure in the reaction vessel was then lowered to 8.3 kPa, and the mixture was allowed to react for 5 hours while maintaining the temperature at 200°C. After confirming that the softening point measured according to ASTM D36-86 had reached 120°C, the temperature was lowered to stop the reaction, yielding amorphous polyester A1.

[0128] When the amorphous polyester A1 was analyzed by NMR, it was found to contain 12.6 mol% of polyoxypropylene(2.0)-2,2-bis(4-hydroxyphenyl)propane monomer units, 39.8 mol% of ethylene glycol monomer units, and 47.7 mol% of terephthalic acid monomer units. A is 11.0 (cal / cm 3 ) 0. 5 It was.

[0129] <Production Examples of Amorphous Polyesters A2 to A7> Amorphous polyesters A2 to A7 were obtained by carrying out the reaction in the same manner as in the production example of amorphous polyester A1, except that the polymerizable monomers and the parts thereof were changed as shown in Table 4. The physical properties of amorphous polyesters A2 to A7 are shown in Table 5.

[0130] [Table 4] The abbreviations in Tables 4 and 5 are as follows: PO2: Bisphenol A·PO adduct (average number of moles added: 2.0) ED: Ethylenediol (ethylene glycol) TPA: Terephthalic acid

[0131] [Table 5] In the table, SP A The unit is (cal / cm 3 ) 0.5 is.

[0132] <Toner 1 manufacturing example> Amorphous polyester A1: 90 parts Crystalline polyester C1: 10 parts Fischer-Tropsch wax (maximum endothermic peak temperature 76°C): 5 parts Carbon black: 10 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 5 minutes, and then mixed in a twin-screw kneader ( The mixture was kneaded using a PCM-30 mill (manufactured by Ikegai Corporation). The resulting mixture was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). The resulting product was further classified using a Faculty mill (F-300, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions were a classifying rotor rotation speed of 11,000 rpm and a dispersing rotor rotation speed of 7,200 rpm.

[0133] Toner particles: 100 parts Silica particle A: Fumed silica surface-treated with hexamethyldisilazane (Median diameter (D50) based on number is 120 nm): 4 parts Small inorganic particles: Titanium oxide particles surface-treated with isobutyltrimethoxysilane (Median diameter (D50) based on number is 10 nm): 1 part The above materials were mixed in a Henschel mixer (FM-75 model, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 1900 rpm for 10 minutes to obtain Toner 1 exhibiting negative charging properties. A -SP C is 1.9, SP C -SP W is 1.1, ΔH is 10.0 J / g, T C -T W was 4.0℃.

[0134] <Production Examples of Toners 2 to 34> Toners 2 to 34 were obtained in the same manner as in Production Example of Toner 1, except that the type and amount of amorphous polyester A, the type and amount of crystalline polyester C, and the type of wax were changed as shown in Table 6. The physical properties obtained are shown in Table 6.

[0135] [Table 6] The abbreviations in Table 6 are as follows: W1: Fischer-Tropsch wax (maximum endothermic peak temperature 76°C) W2: Fischer-Tropsch wax (maximum endothermic peak temperature 100°C) W3: Behenyl behenate wax (maximum endothermic peak temperature 77°C) W4: Paraffin wax (maximum endothermic peak temperature 70°C)

[0136] <Magnetic Carrier 1 Manufacturing Example> Number average particle size: 0.30 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite 1 Number average particle size: 0.50 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite2 To 100 parts of each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was mixed and stirred at high speed in a container at 100° C. or higher to treat each of the fine particles.

[0137] Phenol: 10% by weight Formaldehyde solution: 6% by mass (Formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass) Magnetite treated with the above silane compound 1: 58 mass% Magnetite 2 treated with the above silane compound: 26% by mass 100 parts of the above material, 5 parts of 28% by weight aqueous ammonia, and 20 parts of water were placed in a flask, stirred, and heated to 85°C over 30 minutes. The mixture was then maintained for 3 hours to polymerize and harden the resulting phenolic resin. The hardened phenolic resin was then cooled to 30°C, and water was added. The supernatant was removed, and the precipitate was washed with water and air-dried. This was then dried under reduced pressure (5 mmHg or less) at 60°C to obtain spherical magnetic carrier 1 with dispersed magnetic material. The volume-based 50% particle size (D50) was 34.21 μm.

[0138] <Production example of two-component developer 1> 92.0 parts of magnetic carrier 1 and 8.0 parts of toner 1 were mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain two-component developer 1.

[0139] <Production Examples of Two-Component Developers 2 to 34> In the production example of two-component developer 1, the same procedure was carried out except for the changes shown in Table 7, to obtain two-component developers 2 to 34.

[0140] [Table 7]

[0141] Example 1 The evaluation was carried out using the above two-component developer 1. A modified Canon imageRUNNER ADVANCE C5560 digital commercial printing printer was used as the image forming apparatus, and two-component developer 1 was placed in the cyan developer unit. The modifications to the apparatus included the fixing temperature, process speed, and DC voltage V of the developer carrier. DC , the charging voltage V of the electrostatic latent image carrier D The image output evaluation was carried out by outputting a FFh image (solid image) with the desired image ratio, and adjusting V so that the amount of toner on the FFh image on the paper was the desired amount. DC , V DThe evaluation described below was performed by adjusting the value and laser power. FFh is a value representing 256 gradations in hexadecimal, with 00h being the first gradation of 256 gradations (white background) and FFh being the 256th gradation of 256 gradations (solid area). Evaluation was performed based on the following evaluation method, and the results are shown in Table 10.

[0142] [Abrasion resistance] Paper: Image Coat Gloss 158 (158.0 g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.05 mg / cm 2 (2Fh image) (The DC voltage of the developer carrier V DC , the charging voltage V of the electrostatic latent image carrier D , and adjusted by laser power) Evaluation image: A 3m x 15cm image placed in the center of the A4 paper. Fixing test environment: Normal temperature and humidity environment (temperature 23°C / humidity 50% RH (hereinafter referred to as N / N)) Fixing temperature: 180℃ Process speed: 377 mm / sec

[0143] The evaluation image was printed and the abrasion resistance was evaluated. The difference in reflectance was used as an evaluation index for the abrasion resistance. First, the image portion of the evaluation image was rubbed (10 times back and forth) with a new evaluation paper under a load of 0.5 kgf using a Gakushin-type abrasion fastness tester (AB-301: manufactured by Tester Sangyo Co., Ltd.). Then, the image portion was rubbed with a new evaluation paper using a reflectometer (REFLECTOMETER MODEL Using a tester (TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.), the reflectance of the part that has been rubbed and the reflectance of the part that has not been rubbed are measured using a new evaluation paper.

[0144] The difference in reflectance before and after rubbing was calculated using the following formula. The resulting difference in reflectance was evaluated according to the following evaluation criteria. Evaluations of A to C were judged to be good. Reflectance difference = reflectance before friction - reflectance after friction (Evaluation criteria) A: Less than 1.0% B: 1.0% or more and less than 2.0% C: 2.0% or more and less than 4.0% D: 4.0% or more

[0145] [Low temperature fixability] Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.50 mg / cm 2 (The DC voltage of the developer carrier V DC , the charging voltage V of the electrostatic latent image carrier D , and adjusted by laser power) Evaluation image: A 2cm x 5cm image placed in the center of the A4 paper. Test environment: Low temperature and humidity environment: Temperature 15°C / Humidity 10% RH (hereinafter referred to as "L / L") Fixing temperature: 150℃ Process speed: 377 mm / sec

[0146] The above evaluation image was output, and the low-temperature fixability was evaluated. The value of the image density reduction rate was used as an evaluation index for low-temperature fixability. The image density reduction rate was measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite Corporation) by first measuring the image density at the center. Next, the part where the image density was measured was subjected to pressure of 4.9 kPa (50 g / cm 2 The fixed image is rubbed (five times back and forth) with Silbon paper under a load of 1000 kJ / cm2, and the image density is measured again.

[0147] The rate of decrease in image density before and after rubbing was calculated using the following formula. The obtained rate of decrease in image density was evaluated according to the following evaluation criteria. If the evaluation was A to C, it was judged to be good. Image density reduction rate = (Image density before rubbing - Image density after rubbing) / Image density before rubbing x 100 (Evaluation criteria) A: Image density reduction rate less than 3% B: Image density reduction rate: 3% to less than 5% C: Image density reduction rate: 5% to less than 8% D: Image density reduction rate 8% or more

[0148] [Charge retention rate under high temperature and humidity conditions] Paper: GFC-081 (81.0g / m 2 ) (Canon Marketing Japan Inc.) Toner coverage on paper: 0.35 mg / cm 2 (The DC voltage of the developer carrier V DC , the charging voltage V of the electrostatic latent image carrier D , and adjusted by laser power) Evaluation image: A 2cm x 5cm image placed in the center of the A4 paper. Fixing test environment: High temperature and humidity environment: Temperature 30°C / Humidity 80%RH (hereinafter referred to as "H / H") Process speed: 377 mm / sec

[0149] The toner triboelectric charge was calculated by suction-collecting the toner on the electrostatic latent image carrier using a metal cylindrical tube and a cylindrical filter. Specifically, the triboelectric charge of the toner on the electrostatic latent image carrier was measured using a Faraday cage. A Faraday cage is a coaxial double-cylinder with an insulated inner and outer tube. If a charged object with a charge Q is placed inside the inner tube, electrostatic induction creates the same effect as if a metal cylinder with a charge Q were present. This induced charge was measured using an electrometer (Kesley 6517A, manufactured by Kesley), and the charge Q (mC) divided by the toner mass M (kg) in the inner tube (Q / M) was calculated as the toner triboelectric charge. Toner triboelectric charge (mC / kg) = Q / M

[0150] First, the above-mentioned evaluation image was formed on the electrostatic latent image carrier, and before it was transferred to the intermediate transfer member, the rotation of the electrostatic latent image carrier was stopped, and the toner on the electrostatic latent image carrier was sucked and collected using a metal cylindrical tube and a cylindrical filter, and the [initial Q / M] was measured. The developer was then left in the evaluation machine in a hot / hot environment for two weeks, and the same operations were then performed as before the storage, and the charge amount Q / M (mC / kg) per unit mass on the electrostatic latent image carrier after storage was measured. The initial Q / M per unit mass on the electrostatic latent image carrier was set at 100%, and the maintenance rate of Q / M per unit mass on the electrostatic latent image carrier after storage ([Q / M after storage] / [initial Q / M] x 100) was calculated and evaluated according to the following criteria. A rating of A to C was considered good. (Evaluation criteria) A: Retention rate is over 95% B: Retention rate is between 90% and 95% C: Retention rate is between 85% and 90% D: Retention rate is less than 85%

[0151] <Example 2-2 9 and Comparative Examples 1 to 5> Except for using two-component developers 2 to 34, evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 8. Examples 6, 10, 12 to 16, 19 to 21, 23, and 25 to 29 were evaluated as reference examples.

[0152] [Table 8]

Claims

1. A toner having toner particles containing a binder resin, the binder resin contains an amorphous polyester and a crystalline polyester, (i) the weight average molecular weight of the crystalline polyester soluble in o-dichlorobenzene at 100°C is 1,500 or more and 4,900 or less; (ii) the crystalline polyester contains a modified crystalline polyester having a structure in which a hydroxy group at the end of the main chain of the crystalline polyester is terminally modified with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms; (iii) the content of the terminal-modified structure in the crystalline polyester is 95.0 mol% or more, the content of the crystalline polyester in the binder resin is 3.0% by mass or more and 14.6% by mass or less, the main chain of the crystalline polyester is a condensation polymer of an aliphatic dicarboxylic acid and an aliphatic diol, and the difference in the number of carbon atoms between the aliphatic dicarboxylic acid and the aliphatic diol is 4 or less; The SP value of the crystalline polyester is Ｃ [(cal / cm ３ ) ０．５ ], and the SP value of the amorphous polyester was Ａ [(cal / cm ３ ) ０．５ ], the SP Ａ and the SP Ｃ A toner characterized in that the following formula (1) is satisfied: 1.6≦SP Ａ -SP Ｃ ≦1.9・・・(1)

2. 2. The toner according to claim 1, wherein the total of the acid value and the hydroxyl value of the crystalline polyester is 0.1 mgKOH / g to 5.0 mgKOH / g.

3. The SP Ｃ 8.8 (cal / cm ３ ) ０．５ ~9.4(cal / cm ３ ) ０．５ 3. The toner according to claim 1, wherein

4. The SP Ａ 10.5 (cal / cm ３ ) ０．５ ~11.5(cal / cm ３ ) ０．５ 4. The toner according to claim 1, wherein

5. 5. The toner according to claim 1, wherein the amount of heat absorption ΔH attributed to the crystalline polyester measured by differential scanning calorimetry of the toner is 5.0 J / g to 15.0 J / g.

6. the toner particles contain a hydrocarbon wax; The SP value of the hydrocarbon wax is Ｗ When this is the case, the SP Ｗ and the SP Ｃ 6. The toner according to claim 1, wherein the following formula (2) is satisfied: 0.7≦SP Ｃ -SP Ｗ ≦1.2 ・・・(2)

7. The melting point of the hydrocarbon wax is T Ｗ and the melting point of the crystalline polyester is T Ｃ When this is the case, the T Ｗ and the T Ｃ The toner according to claim 6, wherein the following formula (3) is satisfied: 0.0≦|T Ｃ -T Ｗ |≦25.0 ・・・(3)

8. 8. The toner according to claim 1, wherein the amorphous polyester contains monomer units represented by the following formulas (F) and (G): In the formula, R ４ R represents an ethylene group or a propylene group, x and y each represent an integer of 1 or more, and the average value of x+y is 2 to 10. ５ represents an ethylene group or a propylene group.

9. the content of the crystalline polyester in the binder resin is 3.0% by mass or more and 12.0% by mass or less, the weight average molecular weight of the crystalline polyester soluble in o-dichlorobenzene at 100°C is 1800 or more and 2500 or less; the difference in carbon number between the aliphatic dicarboxylic acid and the aliphatic diol is 0, The SP Ａ and the SP Ｃ The toner according to claim 1, wherein the following formula (5) is satisfied: 1.7≦SP Ａ -SP Ｃ ≦1.9 ・・・(5)

10. the toner particles contain a hydrocarbon wax; The melting point of the hydrocarbon wax is T Ｗ and the melting point of the crystalline polyester is T Ｃ When this is the case, the T Ｗ and the T Ｃ satisfies the following formula (3), 0.0≦|T Ｃ -T Ｗ |≦25.0 ・・・(3) the content of the crystalline polyester in the binder resin is 4.9% by mass or more and 12.0% by mass or less, the proportion of the monomer unit of aliphatic monocarboxylic acid contained in the terminal-modified structure in the crystalline polyester is 33.0% by mass or more and 60.0% by mass or less; The toner according to claim 9.

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