JP5168113B2 - Toner, developer using the toner, image forming method using the toner or developer, and process cartridge - Google Patents

Description

  The present invention relates to a toner suitable for an electrophotographic system such as a copying machine, electrostatic printing, printer, facsimile, electrostatic recording, etc., particularly an ultra-high-speed printing system capable of dealing with the field of print on demand (POD), and uses the toner. The present invention relates to a developer, an image forming method using them, and a process cartridge.

  In recent years, market demands for energy saving and high speed are increasing for image forming apparatuses such as printers, copiers, and facsimiles. As a result, toners for electrophotography (hereinafter sometimes simply referred to as “toners”) are also required to have excellent low-temperature fixability, while being resistant to offset, heat-resistant storage (blocking resistance), There is a demand for anti-contamination property to a developing roller and the like, and a toner having characteristics contrary to the low-temperature fixability is required.

  In response to such demands, a toner containing a linear polyester resin with specified physical properties such as molecular weight (Patent Document 1), a toner containing a non-linear cross-linked polyester resin using rosins as an acid component (Patent Document 1) 2) Toner with improved fixability using maleated rosin-modified polyhydric alcohol (Patent Document 3), polyester comprising alcohol component and carboxylic acid component containing (meth) acrylic acid-modified rosin as binder resin Toners (Patent Documents 4 and 5) used as the above have been proposed. A method of blending a low molecular weight resin and a high molecular weight resin has also been proposed (Patent Document 6).

  On the other hand, in recent years, the field of print on demand (POD) has grown, and the demand for toner from the printing market has become even higher. POD utilizing the electrophotographic method is good at printing a small number of copies and variable printing, and is expected as an alternative to light printing. However, because there is a demand for an ultra-high-speed system that is faster than the printing speed of conventional high-speed copiers and a wide range of paper types, it has good fixability even at lower heat and toner with less contamination to the developing roller. Was newly demanded.

In the field of print on demand (POD) utilizing the electrophotographic system, an ultra-high speed system faster than the printing speed of a conventional high speed copying machine and a wide range of paper types are required, and the amount of toner consumption is large. For this reason, a toner having poor pulverizability and low productivity, such as a toner containing a linear polyester resin that defines physical properties such as molecular weight proposed in Patent Document 1, is not preferable. The rosins used in Patent Documents 2 and 3 are effective in improving the low-temperature fixability, but have a drawback that odor is likely to be generated depending on the type of rosins. Further, in a toner using a polyester composed of an alcohol component proposed in Patent Documents 4 and 5 and a carboxylic acid component containing (meth) acrylic acid-modified rosin as a binder resin, a conventional low speed machine is replaced with a high speed machine. Excellent fixing performance can be demonstrated for a wide range of image forming apparatuses. However, in ultra-high speed systems, it is necessary to achieve both low-temperature fixability and contamination of carriers, developing rollers, etc. It was not possible to meet such new demands.
Note that the present applicant has previously described an alcohol component containing 70 mol% or more of a divalent aliphatic alcohol having 2 to 6 carbon atoms in a divalent alcohol component as a binder resin for a toner used in an image forming apparatus. It was proposed to use a polyester resin obtained by condensation polymerization with a carboxylic acid component containing maleic acid-modified rosin (Patent Document 7). Thereby, low temperature fixability, offset resistance, reduction of odor generation, and storage stability are improved. However, in the ultra-high speed system, the compatibility between the above characteristics and the contamination on the developing roller is not sufficient, and there remains a problem.

JP 2004-245854 A JP-A-4-70765 JP-A-4-307557 JP 2007-292860 A JP 2007-292869 A Japanese Patent Laid-Open No. 2-82267 JP 2007-292863 A

An object of the present invention is to solve various problems in the prior art and achieve the following objects.
In other words, the present invention achieves both low-temperature fixability, offset resistance (hot offset resistance, cold offset resistance) and heat-resistant storage stability at a level compatible with ultra-high-speed systems, and can reduce odor generation. Furthermore, an object of the present invention is to provide a toner excellent in antifouling property to a developing roller and the like in an ultra-high speed system and excellent in productivity, a developer using the toner, an image forming method using the toner, and a process cartridge. And

  As a result of intensive studies, the present inventors have found that the above problems can be solved by the inventions described in the following [1] to [16], and have reached the present invention. Hereinafter, the present invention will be specifically described.

  [1]: The above-described problem is a toner containing at least a binder resin and a colorant, and the binder resin is a divalent alcohol component having 2 to 6 carbon atoms in a divalent alcohol component which is a main component. Polyester resin obtained by condensation polymerization of an alcohol component containing 70 mol% or more of an aliphatic alcohol and a carboxylic acid component containing maleic acid-modified rosin, which is a reaction product of rosin having a conjugated diene and maleic acid or a derivative thereof ( A) and a polyester resin (B) obtained by polycondensation of a carboxylic acid component with an alcohol component containing an alkylene oxide adduct of a bisphenol compound represented by the following general formula (1): To solve the problem.

[In said general formula (1), R < ₁ > and R < ₂ > represents a C2-C4 alkylene group. R ₃ and R ₄ represent a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group. x and y are integers greater than or equal to 0, and the sum is 1-16. ]

  [2]: The toner described in [1] above, wherein the maleic acid-modified rosin has a maleic modification degree represented by the following formula (I) of 30 to 105.

[In the above formula (I), X ₁ is the SP value of maleic acid-modified rosin for calculating the degree of modification, X ₂ is a reaction of 1 mol of maleic acid or its derivative with 1 mol of rosin having a conjugated diene at 230 ° C. The saturated SP value of maleic acid-modified rosin obtained in this manner, Y represents the SP value of rosin having a conjugated diene, and each SP value is measured as follows. ]
<Measurement of SP value>
After each sample 2.1 g in a molten state is poured into a predetermined ring, the sample is cooled to room temperature and then measured under the following conditions based on JIS B7410.
Measuring machine: Ring and ball type automatic softening point tester (ASP-MGK2, manufactured by Meitec Co., Ltd.)
Temperature increase rate: 5 ° C / min
Temperature rising start temperature: 40 ° C
Measuring solvent: Glycerin

  [3]: In the toner according to [1] or [2], the content of maleic acid-modified rosin in the carboxylic acid component in the polyester resin (A) is 15 to 85% by weight. To do.

  [4]: In the toner according to any one of [1] to [3], the maleic acid-modified rosin in the polyester resin (A) is modified with maleic acid or a derivative thereof. It is characterized by that.

  [5]: In the toner according to any one of [1] to [4], the alcohol component and / or carboxylic acid component in the polyester resin (A) is a trivalent or higher alcohol compound and / or a trivalent or higher. The carboxylic acid compound is contained.

  [6]: In the toner according to any one of [1] to [5], the content of the low molecular weight component having a molecular weight of 500 or less contained in the polyester resin (A) is 12% or less. Features.

  [7]: In the toner according to any one of [1] to [6], the polyester resin (A) includes a titanium compound and / or a tin (II) compound having no Sn—C bond. Below, an alcohol component containing 70 mol% or more of a divalent alcohol component having 2 to 6 carbon atoms in a divalent alcohol component as a main component, a rosin having a conjugated diene and maleic acid or a derivative thereof. It is obtained by polymerization.

  [8]: In the toner according to any one of [1] to [7], the polyester resin (B) is a divalent alkylene oxide adduct of the bisphenol compound represented by the general formula (1). It is obtained by condensation polymerization of an alcohol component contained in the alcohol component in an amount of 80 mol% or more and a carboxylic acid component.

  [9]: In the toner according to any one of [1] to [8], the softening point Tm (B) of the polyester resin (B) is 90 ° C. or higher and 160 ° C. or lower.

  [10]: In the toner according to any one of [1] to [9], the acid value of the polyester resin (A) is 25 to 70 mgKOH / g, and the acid value of the polyester resin (B). Is 1 to 25 mg KOH / g.

  [11]: In the toner according to any one of [1] to [10], the weight ratio [(B) / (A)] of the polyester resin (A) to the polyester resin (B) is 1 / 9 to 6/4.

  [12]: The above-described problem is solved by a two-component developer comprising at least the toner according to any one of [1] to [11] and a carrier made of magnetic particles.

  [13]: The above-described problems include a step of charging at least the surface of the photosensitive member by a charging unit, a step of forming an electrostatic latent image on the surface of the photosensitive member by an exposure unit, and a toner by a developing unit on the electrostatic latent image. And developing the toner image as a toner image, a step of transferring the developed toner image onto a recording medium by a transfer unit, and a step of fixing the transferred toner image by a fixing unit. The image forming method is characterized in that the toner used is the toner described in any one of [1] to [11].

  [14]: The above-described problems include a step of charging at least the surface of the photosensitive member with a charging unit, a step of forming an electrostatic latent image on the surface of the photosensitive member with an exposure unit, and a toner with a developing unit on the electrostatic latent image. A step of developing a toner image using a two-component developer containing a carrier, a step of transferring the developed toner image to a recording medium by a transfer unit, and fixing the transferred toner image by a fixing unit An image forming method comprising the steps, wherein the developer used is the two-component developer described in [12].

  [15]: The above-described problems include at least a photoconductor, a charging unit that charges the surface of the photoconductor, an exposure unit that exposes the surface of the charged photoconductor to form an electrostatic latent image, and an electrostatic latent image formed And a developing means for developing with toner, a transferring means for transferring the developed toner image to a recording medium, and a cleaning means for removing the toner remaining on the surface of the photosensitive member after transfer are integrated. The process cartridge is detachable from the main body of the image forming apparatus, and the toner used is the toner described in any one of [1] to [11].

  [16]: The above-described problems are at least a photosensitive member, a charging unit that charges the surface of the photosensitive member, an exposure unit that exposes the charged surface of the photosensitive member to form an electrostatic latent image, and an electrostatic latent image formed Select from developing means for developing using a two-component developer containing toner and carrier, transfer means for transferring the developed toner image to a recording medium, and cleaning means for removing toner remaining on the surface of the photoreceptor after transfer. A process cartridge that can be attached to and detached from an integrated image forming apparatus main body, wherein the developer used is the two-component developer described in [12]. This is solved by the process cartridge.

According to the toner and developer of the present invention, low-temperature fixability, offset resistance (hot offset resistance, cold offset resistance), and heat-resistant storage stability are compatible at a level compatible with an ultra-high-speed image forming system. Furthermore, it can reduce the generation of odors, has a special effect on the anti-contamination property to the developing roller, etc., and is excellent in productivity. For example, a copying machine, electrostatic printing, printer, facsimile, static It is suitable for an electrophotographic system such as electrorecording, particularly an ultra-high-speed printing system that can cope with the field of electrophotographic printing on demand (POD).
According to the image forming method of the present invention, since development is performed using the toner or the developer, a stable image with high quality can be formed even in an ultra high speed image forming system.
According to the process cartridge of the present invention, since toner is supplied from the developing means loaded with the toner or developer, a stable image can be output without occurrence of an abnormal image such as an offset phenomenon even in an ultrahigh-speed image forming system. Can do. In addition, the exchangability can be performed in a short time, and the handleability is excellent.

  As described above, the toner according to the present invention is a toner containing at least a binder resin and a colorant, and the binder resin is a 2 to 6 carbon atom in a divalent alcohol component that is a main component. Polyester obtained by polycondensation of an alcohol component containing 70 mol% or more of a monovalent aliphatic alcohol and a carboxylic acid component containing maleic acid-modified rosin which is a reaction product of rosin having a conjugated diene and maleic acid or a derivative thereof Containing a polyester resin (B) obtained by condensation polymerization of a resin (A), an alcohol component containing an alkylene oxide adduct of a bisphenol compound represented by the following general formula (1), and a carboxylic acid component. It is a feature.

[In said general formula (1), R < ₁ > and R < ₂ > represents a C2-C4 alkylene group. R ₃ and R ₄ represent a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group. x and y are integers greater than or equal to 0, and the sum is 1-16. ]
Specifically, R ₁ and R ₂ shown in the general formula (1) represent an alkylene group such as an ethylene group, a propylene group, or a butylene group. R ₃ and R ₄ represent a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, or a hexyl group. x and y are particularly preferably 2 to 6.
The derivative refers to maleic acid derivatives such as maleic anhydride and maleic acid esters.

As described above, the toner of the present invention contains at least a binder resin and a colorant, and may contain other components such as a release agent, a charge control agent, and an external additive as necessary. Moreover, a polyester resin (A) and a polyester resin (B) are contained as a binder resin.
That is, when the polyester resin (A) and the polyester resin (B) are used in combination as the toner binder resin, the effects of the respective resins act synergistically, and the effects of the present invention are optimally exhibited. Hereinafter, the present invention will be described in more detail.

[Polyester resin (A)]
The polyester resin (A) is obtained by polycondensation of an alcohol component and a carboxylic acid component, preferably in the presence of an esterification catalyst. Here, as the alcohol component, in addition to the divalent alcohol component (divalent alcohol compound) which is the main component, a trivalent or higher alcohol component (trivalent or higher alcohol compound) may be contained. And it is suitable that a C2-C6 bivalent aliphatic alcohol is contained 70 mol% or more in a bivalent alcohol component.
The carboxylic acid component includes a maleic acid-modified rosin which is a reaction product of a rosin having a conjugated diene and maleic acid or a derivative thereof, and contains other divalent or trivalent or higher carboxylic acid compounds. Also good.

  In other words, since the rosin conventionally used is monovalent, the content in the polyester resin cannot be increased. On the other hand, when a rosin modified by reacting with a conventional polyhydric alcohol is used, Although the content in the polyester resin can be increased, because it is used as an alcohol component, it is inferior in the reactivity of the condensation polymerization reaction, and the resulting polyester resin has insufficient low-temperature fixability, and has a large amount of rosin. The preservability tended to deteriorate due to inclusion.

On the other hand, the polyester resin (A) used in the present invention is a maleic acid-modified rosin obtained by a reaction (Diels-Alder reaction) of rosin having a conjugated diene and maleic acid or a derivative thereof (parent diene form: dienophile). It is used as one of the carboxylic acid components and is obtained by polycondensation with an alcohol component containing a specific amount of a divalent aliphatic alcohol, so that the low-temperature fixability of the aliphatic polyester is increased while increasing the rosin content. Can be increased.
In addition, polyesters using divalent aliphatic alcohols have a flexible skeleton and thus have a low glass transition temperature, and a sufficient effect on storage stability was not obtained. However, the maleic acid-modified rosin of the present invention, that is, aromatic In combination with a specific modified rosin having a family skeleton, the reactivity of the condensation polymerization is increased and the glass transition temperature can be increased, so that the storage stability can be improved in spite of the use of rosin. . Furthermore, although a conventional polyester resin obtained using a divalent aliphatic alcohol is excellent in fixability, it easily absorbs moisture, and when used as a toner, the charging characteristics of the toner are affected by the environment. Although the density fluctuates and the environmental stability is inferior, in the present invention, by combining a divalent aliphatic alcohol and a maleic acid-modified rosin, the fixing property of the toner is ensured and the environment is stabilized. It became possible to improve the stability.

[Alcohol component in polyester resin (A)]
As the alcohol component in the polyester resin (A), as described above, a divalent alcohol component (divalent alcohol compound) which is a main component and, if necessary, a trivalent or higher alcohol component (a trivalent or higher alcohol component). Alcohol compounds) can be used.
Examples of the divalent aliphatic alcohol having 2 to 6 carbon atoms include, but are not limited to, ethylene glycol, neopentyl glycol, 1,2-propanediol, 1,3-propanediol, 1,4 -Butanediol, 1,6-hexanediol, 2,3-butanediol and the like. Among these, 1,2-propanediol, 1,3-propanediol, and 2,3-butanediol are preferable, and 1,2-propanediol and 1,3-propanediol are particularly preferable.
The content of the divalent aliphatic alcohol having 2 to 6 carbon atoms is 70 mol% or more, preferably 80 mol% or more, and preferably 90 mol% in the divalent alcohol component from the viewpoint of fixing property and environmental stability. % Or more is more preferable, and substantially 100 mol% is still more preferable.

  The divalent alcohol other than the divalent aliphatic alcohol having 2 to 6 carbon atoms contained in the alcohol component is not particularly limited and may be appropriately selected depending on the purpose. Bisphenol A alkylene (2 to 3 carbon atoms) oxide (average added mole) such as oxypropylene-2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane 1-16) Alkylene oxide adducts of bisphenol A such as adducts, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, or alkylene (2-4 carbon atoms) oxide thereof (average added mole number of 1-16) ) Additives.

The content of the divalent alcohol component is preferably 60 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%, and particularly preferably 90 to 100 mol% in the alcohol component. .
In the alcohol component, the content of the divalent aliphatic alcohol component having 2 to 6 carbon atoms is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, still more preferably 70 to 100 mol%, and 80 ˜100 mol% is particularly preferred.

  Examples of the trihydric or higher alcohol component (trihydric or higher polyhydric alcohol) used as necessary include pentaerythritol, trimethylolpropane, sorbitol, glycerin, and the like, and among these, glycerin is particularly preferable.

[Carboxylic acid component in polyester resin (A)]
As the carboxylic acid component in the polyester resin (A), a maleic acid-modified rosin which is a reaction product of rosin having a conjugated diene and maleic acid or a derivative thereof, and other carboxylic acid components having a valence of 3 or more as necessary. Can be used.
The maleic acid-modified rosin is, for example, maleic acid or maleic anhydride to rosin mainly composed of abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, sandaracopimaric acid, dehydroabietic acid, and repopimaric acid. Obtained by addition reaction of acid. Specifically, among the main components of rosin, lepopimaric acid having a conjugated double bond, abietic acid, neoabietic acid, and parastrinic acid, and maleic acid or a maleic acid derivative (such as maleic anhydride or maleic acid ester) Can be obtained by the Diels-Alder reaction under heating.

The degree of modification of rosin (maleic acid modification degree) with maleic acid or a derivative thereof (maleic anhydride, maleic acid ester, etc.) is preferably 30-105, more preferably 40-105, still more preferably 50-105, 60- 105 is particularly preferable, and 70 to 105 is most preferable. When the maleic modification degree is less than 30, the molecular weight of the polyester resin cannot be increased and the low molecular weight oligomer component cannot be reduced. On the other hand, when the modification degree exceeds 105, the melt viscosity of the modified rosin increases. We are anxious about the inferior productivity at the time of polyester resin manufacture.
Here, the maleic modification degree can be calculated by the following mathematical formula (I).

In the above formula (I), X ₁ is the SP value of maleic acid-modified rosin for calculating the degree of modification, and X ₂ is a reaction of 1 mol of maleic acid or its derivative with 1 mol of rosin having a conjugated diene at 230 ° C. The saturated SP value of maleic acid-modified rosin obtained in this manner, Y represents the SP value of rosin having a conjugated diene, and each SP value is measured as follows.
<Measurement of SP value>
After each sample 2.1 g in a molten state is poured into a predetermined ring, the sample is cooled to room temperature and then measured under the following conditions based on JIS B7410.
Measuring machine: Ring and ball type automatic softening point tester (ASP-MGK2, manufactured by Meitec Co., Ltd.)
Temperature increase rate: 5 ° C / min
Temperature rising start temperature: 40 ° C
Measuring solvent: Glycerin

That is, the SP value means a softening point measured with a ring and ball automatic softening point tester as described above. In the formula (I), (X ₁ -Y) of the molecule means the degree of increase in SP value of rosin modified with maleic acid or maleic anhydride, and the degree of maleic modification represented by the formula (I). A larger value indicates a higher degree of denaturation.

  There is no restriction | limiting in particular in the manufacturing method of the said maleic acid modification rosin, According to the objective, it can select suitably. For example, rosin and maleic acid or maleic anhydride are mixed and heated to about 180 to 260 ° C. to add maleic acid or maleic anhydride to an acid having a conjugated double bond contained in rosin (Diels-Alder reaction) To obtain a maleic acid-modified rosin. The maleic acid-modified rosin may be used as it is, or may be used after purification through an operation such as distillation.

  The rosin used in the maleic acid-modified rosin is natural rosin obtained from pine, isomerized rosin, dimerized rosin, polymerized rosin, disproportionated rosin, etc., such as abietic acid, neoabietic acid, parastrinic acid, pimaric acid As long as it is a rosin mainly composed of isopimaric acid, sandaracopimaric acid, dehydroabietic acid and lepopimaric acid, a known rosin can be used without particular limitation. Natural rosins such as tall rosin obtained from tall oil obtained as a by-product, gum rosin obtained from raw pine sprout, wood rosin obtained from pine stumps are preferred, and tall rosin is more preferred from the viewpoint of low-temperature fixability.

  The maleic acid-modified rosin is obtained through a Diels-Alder reaction under heating, so that impurities that cause odor are reduced and the odor is low, but the odor is further reduced and storage stability is improved. From the viewpoint, the maleic acid-modified rosin is preferably obtained by modifying purified rosin with maleic acid or maleic anhydride, and more preferably obtained by modifying purified tall rosin with maleic acid or maleic anhydride.

  The purified rosin is a rosin whose impurities are reduced by a purification process. By purifying rosin in this manner, impurities contained in rosin are removed. Examples of main impurities include 2-methylpropane, acetaldehyde, 3-methyl-2-butanone, 2-methylpropanoic acid, butanoic acid, pentanoic acid, n-hexanal, octane, hexanoic acid, benzaldehyde, and 2-pentylfuran. 2,6-dimethylcyclohexanone, 1-methyl-2- (1-methylethyl) benzene, 3,5-dimethyl-2-cyclohexene, 4- (1-methylethyl) benzaldehyde and the like.

  In the present invention, among the above impurities, three kinds of peak intensities detected as volatile components by the headspace GC-MS method of hexanoic acid, pentanoic acid, and benzaldehyde can be used as an indicator of purified rosin. Note that the volatile component, not the absolute amount of impurities, is used as an indicator to improve the odor, which is a problem of the conventional polyester resin using rosin, by using the purified rosin in the present invention. Because it is.

Specifically, the purified rosin means that the hexanoic acid peak intensity is 0.8 × 10 ⁷ or less and the pentanoic acid peak intensity is 0 under the measurement conditions of the headspace GC-MS method of Examples described later. .4 × is 10 ⁷ or less, a peak intensity of benzaldehyde refers to rosin is 0.4 × 10 ⁷ or less. Furthermore, from the viewpoint of storage stability and odor, the peak intensity of hexanoic acid is preferably 0.6 × 10 ⁷ or less, and more preferably 0.5 × 10 ⁷ or less. The peak intensity of pentanoic acid is preferably 0.3 × 10 ⁷ or less, and more preferably 0.2 × 10 ⁷ or less. The peak intensity of benzaldehyde is preferably 0.3 × 10 ⁷ or less, and more preferably 0.2 × 10 ⁷ or less.

Furthermore, from the viewpoint of storage stability and odor, it is preferable that n-hexanal and 2-pentylfuran are reduced in addition to the above three kinds of substances. The peak intensity of n-hexanal is preferably 1.7 × 10 ⁷ or less, more preferably 1.6 × 10 ⁷ or less, and even more preferably 1.5 × 10 ⁷ or less. The peak intensity of 2-pentylfuran is preferably 1.0 × 10 ⁷ or less, more preferably 0.9 × 10 ⁷ or less, and further preferably 0.8 × 10 ⁷ or less.

  The method for purifying the rosin is not particularly limited, and a known method can be used. Examples thereof include distillation, recrystallization, extraction, and the like, and purification by distillation is preferable. As the distillation method, for example, the method described in JP-A-7-286139 can be used, and examples thereof include vacuum distillation, molecular distillation, steam distillation, etc., but purification by vacuum distillation is preferable. For example, distillation is usually performed at a still temperature of 200 to 300 ° C. at a pressure of 6.67 kPa or less, and methods such as ordinary simple distillation, thin film distillation, rectification, etc. are applied. In contrast, 2 to 10% by mass of a high molecular weight substance is removed as a pitch component, and at the same time, 2 to 10% by mass of an initial fraction is simultaneously removed.

  The softening point of rosin before modification is preferably 50 to 100 ° C, preferably 60 to 90 ° C, and more preferably 65 to 85 ° C. The softening point of the rosin is a softening point measured when the rosin is once melted and naturally cooled for one hour in an environment of a temperature of 25 ° C. and a relative humidity of 50% by the measurement method shown in the examples described later. means.

  The acid value of rosin before modification is preferably 100 to 200 mgKOH / g, more preferably 130 to 180 mgKOH / g, and still more preferably 150 to 170 mgKOH / g. The acid value of the rosin can be measured based on the method described in JIS K0070, for example.

  The content of the maleic acid-modified rosin is preferably 15% by mass or more and more preferably 25% by mass or more from the viewpoint of low-temperature fixability in the carboxylic acid component. Moreover, from a viewpoint of preservability, 85 mass% or less is preferable, 65 mass% or less is more preferable, and 50 mass% or less is still more preferable. From these viewpoints, the content of the maleic acid-modified rosin is preferably 15 to 85% by mass, more preferably 25 to 65% by mass, and still more preferably 25 to 50% by mass in the carboxylic acid component.

The carboxylic acid compound other than maleic acid-modified rosin contained in the carboxylic acid component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, oxalic acid, malonic acid, maleic acid, fumaric acid Aliphatic dicarboxylic acids such as acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid; phthalic acid, isophthalic acid, terephthalic acid, etc. Aromatic dicarboxylic acid; cycloaliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid; trivalent or higher polyvalent carboxylic acid such as trimellitic acid and pyrrolemetic acid; or anhydride, alkyl (1 to 3 carbon atoms) ester of these acids Etc. Among these, from the viewpoint of further increasing the glass transition temperature of the resin and improving the storage stability, terephthalic acid is preferably contained in the carboxylic acid component in an amount of 30% by mass or more, more preferably 40% by mass or more, and further 45% by mass or more. It is preferred that
In the present specification, the above acids, anhydrides of these acids, or alkyl esters of the acids are collectively referred to as carboxylic acid compounds (carboxylic acid components).

  From the viewpoint of improving offset resistance, the polyester resin (A) is a trivalent or higher raw material monomer other than maleic acid-modified rosin, that is, a trihydric or higher polyhydric alcohol and / or 3 within a range not impairing storage stability. It is preferable that a polyvalent carboxylic acid compound having a valence or higher is contained in the alcohol component and / or the carboxylic acid component. From the viewpoint of preservability and residual monomer reduction, the content of the trivalent or higher polyvalent carboxylic acid compound is preferably 0.001 to 40 mol, more preferably 0.1 to 25 mol, per 100 mol of the alcohol component. . The content of the trihydric or higher polyhydric alcohol is preferably 0.001 to 40 mol%, more preferably 0.1 to 25 mol% in the alcohol component.

  In the trivalent or higher monomer, the trivalent or higher polyvalent carboxylic acid compound is preferably trimellitic acid or a derivative thereof, and the trivalent or higher polyhydric alcohol is, for example, glycerin, pentaerythritol, tritriol. Examples include methylolpropane, sorbitol, or their alkylene (2 to 4 carbon atoms) oxide (average added mole number 1 to 16) adduct. Among these, glycerin, trimellitic acid or a derivative thereof is particularly preferable because it not only serves as a branching site or acts as a crosslinking agent but is also effective in improving low-temperature fixability.

[Esterification catalyst used for polycondensation of polyester resin (A)]
The polycondensation of the polyester component (A) with the alcohol component and the carboxylic acid component is preferably performed in the presence of an esterification catalyst.
Examples of the esterification catalyst include Lewis acids such as p-toluenesulfonic acid, titanium compounds, tin (II) compounds having no Sn-C bond, and these are used alone or in combination. Used. In the present invention, a titanium compound and / or a tin (II) compound having no Sn—C bond is preferred.
As the titanium compound, a titanium compound having a Ti—O bond is preferable, and a compound having an alkoxy group having 1 to 28 carbon atoms, an alkenyloxy group, or an acyloxy group is more preferable.

Examples of the titanium compound include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolaminate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diety rate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) ₂ ], titanium distearate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium triisopropylate triethanolamine [Ti (C ₆ H ₁₄ O ₃ N) ₁ (C ₃ H ₇ O) ₃ ], titanium monopropylate tris (triethanolaminate) [Ti (C ₆ H ₁₄ O ₃ N) ₃ (C ₃ H ₇ O) ₁ ] and the like, and among these, titanium diisopropylate bistriethanolamate, titanium diisopropylate bisdiethanolamate, and titanium dipentylate bistriethanolamate are preferred, such as Matsumoto Trading Co., Ltd. It can also be obtained as a commercial product of the company.
Specific examples of other preferable titanium compounds include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti ( C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti (C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetrastearyl titanate, tetramyristyl titanate, tetraoctyl titanate and dioctyl dihydroxyoctyl titanate are preferable. These can be obtained, for example, by reacting a titanium halide with a corresponding alcohol, or can be obtained as a commercial product such as Nisso.

  The abundance of the titanium compound is preferably 0.01 parts by mass to 1.0 part by mass and more preferably 0.1 parts by mass to 0.7 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. preferable.

  Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Is preferable, and a tin (II) compound having a Sn-O bond is more preferable.

Examples of the tin (II) compound having a Sn-O bond include tin (II) oxalate, tin (II) diacetate, tin (II) dioctanoate, tin (II) dilaurate, and tin distearate (II). ), Carboxylic acid tin (II) having a carboxylic acid group having 2 to 28 carbon atoms such as tin (II) dioleate; dioctyloxy tin (II), dilauroxy tin (II), distearoxy tin (II), dioleiloxy tin (II) Dialkoxytin (II) having an alkoxy group of 2 to 28 carbon atoms such as), tin oxide (II), tin (II) sulfate and the like, and has a Sn-X (X represents a halogen atom) bond. Examples of the tin (II) compound include tin (II) halides such as tin (II) chloride and tin (II) bromide. Among these, fatty acid tin (II) represented by (R ₁ COO) ₂ Sn (wherein R ₁ represents an alkyl group or alkenyl group having 5 to 19 carbon atoms) from the viewpoint of the charge rising effect and catalytic ability. ), (R ₂ O) ₂ Sn (wherein R ₂ represents an alkyl group or alkenyl group having 6 to 20 carbon atoms) and a dialkoxytin (II) represented by SnO and a tin (II) oxide represented by SnO More preferred are fatty acid tin (II) and tin (II) oxide represented by (R ₁ COO) ₂ Sn, and further preferred are tin (II) dioctanoate, tin (II) distearate and tin (II) oxide. preferable.

The abundance of the tin (II) compound is preferably 0.01 parts by mass to 1.0 part by mass, and 0.1 parts by mass to 0.00 parts by mass with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 7 parts by mass is more preferable.
When the titanium compound and the tin (II) compound are used in combination, the total amount of the titanium compound and the tin (II) compound is 0.01 parts by mass to 1. parts by mass with respect to 100 parts by mass of the alcohol component and the carboxylic acid component. 0 mass part is preferable and 0.1 mass part-0.7 mass part are more preferable.
The condensation polymerization of the alcohol component and the carboxylic acid component can be performed, for example, at a temperature of 180 ° C. to 250 ° C. in an inert gas atmosphere in the presence of the esterification catalyst.

[Polyester resin (B)]
The toner binder resin used in the present invention is synergistic in the effect of each resin only when the polyester resin (B) is used in combination with the polyester resin (A) described above. The effect is exhibited optimally. Here, the polyester resin (B) is obtained by polycondensation of an alcohol component containing an alkylene oxide adduct of a bisphenol compound represented by the general formula (1) and a carboxylic acid component.

[Alcohol component in polyester resin (B)]
Examples of the alkylene oxide adduct of the bisphenol compound represented by the general formula (1) include diols obtained by polymerization of ethylene oxide such as bisphenol A and bisphenol F, and cyclic ether such as propylene oxide.
As an alcohol component of the said polyester resin (B), in the range which does not impair the objective and effect of this invention, other than the compound of the said General formula (1), other bivalent or trivalent or more alcohol components as needed. However, the content of the compound of the general formula (1) is preferably 80 mol% or more in the divalent alcohol component.

[Carboxylic acid component in polyester resin (B)]
There is no restriction | limiting in particular as a carboxylic acid component of the said polyester resin (B), The above-mentioned carboxylic acid compound used for a polyester resin (A) can be suitably selected according to the objective.

[Esterification catalyst used for polycondensation of polyester resin (B)]
The polycondensation of the alcohol component and the carboxylic acid component of the polyester resin (B) is preferably performed in the presence of the esterification catalyst described above used in the polyester resin (A).

  Only when the polyester resin (A) and the polyester resin (B) satisfying the above-mentioned conditions are used together as a binder resin, low-temperature fixability, offset resistance (hot offset resistance, cold offset resistance), and heat resistance. Achieves the provision of a toner that is both storable, can reduce odor generation, has excellent anti-contamination properties to the developing roller, and has excellent productivity even in an ultra-high speed system, and a developer using the toner. Is done.

That is, according to the toner and developer of the present invention, the polyester resin (A) containing an aliphatic polyhydric alcohol excellent in the dispersibility of the release agent and the polyester resin having a bisphenol A skeleton having high mechanical strength ( B) was dispersed in a microphase-separated state, and contained a divalent aliphatic alcohol (containing 70 mol% or more of a divalent aliphatic alcohol having 2 to 6 carbon atoms) in the divalent alcohol component. With the general formula (1) having high mechanical strength, the polyester resin (A) obtained by polycondensation of an alcohol component and a carboxylic acid component containing a maleic acid-modified rosin, while taking advantage of the fixability and grindability of the polyester resin (A). By a polyester resin (B) obtained by condensation polymerization of an alcohol component containing an alkylene oxide adduct of a bisphenol compound and a carboxylic acid component Heat-resistant storage stability, is believed to enhance the anti-fouling property to developing roller or the like.
On the other hand, as a binder resin, the polyester resin (A) and the polyester resin (B) are contained only by using a resin having both an aliphatic polyhydric alcohol skeleton and a bisphenol skeleton in one molecule. The effect of the present invention cannot be obtained by using the binding resin.

Further, as a more preferable condition for achieving both low temperature fixability, hot offset resistance, and heat resistant storage stability, the mass ratio of the polyester resin (A) and the polyester resin (B) [(B) / (A)] Is preferably 1/9 to 6/4.
The glass transition temperature of the polyester resin (A) and the polyester resin (B) is preferably 45 ° C. to 75 ° C., more preferably 50 ° C. to 70 ° C., from the viewpoints of fixability, heat resistant storage stability and durability.
The softening point of the polyester resin (B) is preferably 90 to 160 ° C, more preferably 95 to 155 ° C, and still more preferably 100 to 150 ° C, from the viewpoints of fixability, storage stability and durability.

  The acid value of the polyester resin (A) and the polyester resin (B) is preferably 1 mgKOH / g to 70 mgKOH / g, and the acid value of the polyester resin (A) is 25 mgKOH / g to 70 mgKOH / g, And when the acid value of the said polyester resin (B) is 1 mgKOH / g-25 mgKOH / g, the dispersion state of resin and a mold release agent becomes optimal.

  In addition, from the viewpoint of low-temperature fixability, offset resistance and heat-resistant storage stability, the content of low molecular weight components having a molecular weight of 500 or less due to residual monomer components and oligomer components is 12% or less in the polyester resin. Is preferably 10% or less, more preferably 9% or less, and still more preferably 8% or less. The content of the low molecular weight component can be reduced by a method such as increasing the degree of maleic modification of rosin. Here, content of a low molecular weight component is based on the area ratio of the molecular weight measured by the below-mentioned gel permeation chromatography (GPC).

  In the present invention, the polyester resin refers to a resin having a polyester unit. The polyester unit refers to a portion having a polyester structure, and the polyester resin includes not only polyester but also polyester modified to such an extent that the properties thereof are not substantially impaired. In the present invention, the polyester resin ( Both A) and (B) are preferably modified polyesters. Examples of the modified polyester include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. And a composite resin having two or more kinds of resin units including a polyester unit.

  In the present invention, the polyester resin (A) and the polyester resin (B) are preferably amorphous different from crystallinity. In this specification, an amorphous resin refers to a resin having a difference between the softening point and the glass transition temperature (Tg) of 30 ° C. or more.

  In the present invention, the binder resin may contain other resins other than the polyester resin (A) and the polyester resin (B) as long as the effects of the present invention are not impaired. Other resins include polyester resins and other known binder resins such as vinyl resins such as styrene-acrylic resins, epoxy resins, polycarbonates, polyurethanes, and composite resins having two or more resin units including polyester units. Other resins such as (also referred to as a hybrid resin) may be used in combination.

As described above, the toner of the present invention contains at least a binder resin and a colorant, and may contain other components such as a release agent, a charge control agent, and an external additive as necessary. The components used as necessary will be described below.
(Coloring agent)
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably from well-known dyes and pigments. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL , Isoindolinone yellow, bengara, red lead, red lead, cadmium red, cadmium mercury red, antimony red, permanent red 4R, para red, phise red, parachlor ortho nitroaniline red, risor fast scarlet G, Reliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon , Oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine Range, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo , Ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese violet, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridiane, emerald green, pigment green B, naphthol green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Oxidized Chi Tan, zinc white, litbon, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The color of the colorant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those for black and those for color (for magenta, cyan, yellow, etc.). It is done. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the black color include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), oxidation, and the like. Examples thereof include metals such as titanium, organic pigments such as aniline black (CI pigment black 1), and the like.

  Examples of magenta coloring pigments include C.I. I. 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, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, green 7 and green 36, and the like.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, styrene copolymer, polymethyl methacrylate resin, polybutyl Methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polypropylene resin, polyester resin, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral resin, polyacrylic acid resin, rosin, modified rosin, terpene Examples thereof include resins, aliphatic hydrocarbon resins, alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffins. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the styrene or substituted polymer thereof include polyester resin, polystyrene resin, poly p-chlorostyrene resin, and polyvinyl toluene resin. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - like maleic acid ester copolymer.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and the organic solvent component. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

(Charge control agent)
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. preferable. Examples of such charge control agents include triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, and phosphorus. Examples thereof include simple substances or compounds thereof, tungsten simple substances or compounds thereof, fluorine-based activators, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (all manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415 (all manufactured by Hodogaya Chemical Co., Ltd.), No. Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.); quinacridone, azo pigment, other Examples thereof include polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  The charge control agent may be melted and kneaded together with the master batch and then dissolved and / or dispersed, or may be added together with each component of the toner when directly dissolving and / or dispersing in the organic solvent. Alternatively, it may be fixed to the toner surface after the toner particles are produced.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1 mass part-10 mass parts are preferable, and 0.2 mass part-5 mass parts are more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

(Release agent)
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes, such as carbonyl group containing wax, polyolefin wax, and long-chain hydrocarbon, are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.

  Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.

Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40 to 160 degreeC is preferable, 50 to 120 degreeC is more preferable, and 60 to 90 degreeC is especially preferable. preferable. If the melting point is less than 40 ° C., the heat resistant storage stability may be adversely affected. If the melting point exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.

  The melting point of the release agent is, for example, a sample that is heated up to 200 ° C. using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), and cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. And the maximum peak temperature of the heat of fusion can be determined as the melting point.

  The melt viscosity of the release agent is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as measured at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 40 mass% or less is preferable and 3 mass%-30 mass% are more preferable. When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

(External additive)
The external additive is not particularly limited and may be appropriately selected from known materials according to the purpose. Examples thereof include silica fine particles, hydrophobic silica, and fatty acid metal salts (for example, zinc stearate, stearic acid). Aluminum, etc.); metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers, and the like. Among these, hydrophobized silica fine particles, hydrophobized titania fine particles, hydrophobized titanium oxide fine particles, and hydrophobized alumina fine particles are preferable.

  Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Nippon Aerosil Co., Ltd.). Further, as the titania fine particles, P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.), Examples include MT-150W, MT-500B, MT-600B, and MT-150A (all manufactured by Teika Corporation). Among these, as hydrophobized titanium oxide fine particles, T-805 (made by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both made by Titanium Industry Co., Ltd.); TAF-500T, TAF -1500T (all manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (manufactured by Ishihara Sangyo Co., Ltd.), and the like.

  In order to obtain the hydrophobized oxide fine particles, hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles, the hydrophilic fine particles are methyltrimethoxysilane, methyltriethoxysilane. It can be obtained by treatment with a silane coupling agent such as octyltrimethoxysilane. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino acid. Modified silicone oil, epoxy modified silicone oil, epoxy / polyether modified silicone oil, phenol modified silicone oil, carboxyl modified silicone oil, mercapto modified silicone oil, acrylic or methacryl modified silicone oil, α-methylstyrene modified silicone oil, etc. can be used. .

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, Examples include wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.

The amount of the external additive added is preferably 0.1% by mass to 5% by mass and more preferably 0.3% by mass to 3% by mass with respect to the toner. The average particle size of the primary particles of the inorganic fine particles is preferably 100 nm or less, and more preferably 3 nm to 70 nm. If it is smaller than this range, the inorganic fine particles are buried in the toner, and the function is hardly exhibited effectively. If it is larger than this range, the surface of the electrostatic latent image carrier is undesirably damaged. As the external additive, inorganic fine particles and hydrophobized inorganic particles can be used in combination. The average particle size of the hydrophobized primary particles is preferably 1 nm to 100 nm, particularly at least 5 nm to 70 nm inorganic fine particles. It is more preferable to include two types. Further, it is more preferable that at least two types of inorganic fine particles having an average particle diameter of 20 nm or less of the primary particles subjected to the hydrophobization treatment and at least one type of inorganic fine particles of 30 nm or more are included. In addition, the specific surface area by BET method is preferably 20m ² / g~500m ² / g.

  Examples of the surface treatment agent for the external additive containing fine oxide particles include silane coupling agents such as dialkyl dihalogenated silane, trialkyl halogenated silane, alkyl trihalogenated silane, and hexaalkyldisilazane, silylating agents, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and silicone varnish.

  Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; polycondensation system such as silicone, benzoguanamine, nylon; polymer particles made of thermosetting resin Can be mentioned. By using in combination with such resin fine particles, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced. The addition amount of the resin fine particles is preferably 0.01% by mass to 5% by mass, and more preferably 0.1% by mass to 2% by mass with respect to the toner.

(Other ingredients)
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, etc. are mentioned.

  The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.

  The cleaning property improver is added to the toner in order to remove the developer after transfer remaining on the electrostatic latent image carrier or the intermediate transfer member. For example, fatty acid such as zinc stearate, calcium stearate, stearic acid, etc. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as metal salts, polymethyl methacrylate fine particles, and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a mass average particle size of 0.01 μm to 1 μm are suitable.

  There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.

<Toner production method>
As a method for producing the toner of the present invention, conventionally known kneading / pulverizing methods, polymerization methods, dissolution suspension methods, spray granulation methods, and the like can be used. From the viewpoint of productivity, the effects of the present invention are exhibited. It is preferable to use a kneading / pulverizing method.

  In the pulverization method, for example, a toner material containing other components such as a binder resin, a colorant, and, if necessary, a release agent is melt-kneaded, and pulverized and classified, whereby the toner base particles are obtained. It is a manufacturing method.

  In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay, PCM type twin screw extruder manufactured by Ikegai Iron Works, Conyder manufactured by Buss, etc. are suitable. Used for. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature is performed with reference to the softening point of the binder resin. If the temperature is higher than the softening point, the binder resin is severely cut, and if the temperature is too low, the dispersion may not proceed.

In the pulverization step, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used. .
In the classification step, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle size. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like. After the pulverization and classification are completed, the pulverized product is classified in an air stream by a centrifugal force or the like to produce toner base particles having a predetermined particle size.

  Next, coating (external addition) of the external additive onto the toner base particles is performed. That is, by mixing and stirring the toner base particles and the external additive using a mixer, the surface of the toner base particles is coated while being crushed. At this time, it is important from the viewpoint of durability that the external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the toner base particles.

The mass average particle diameter of the toner is not particularly limited and can be appropriately selected according to the purpose. Here, the mass average particle diameter of the toner can be determined as follows.
<Measurement device>: Coulter Multisizer II (Beckman Coulter, Inc.)
<Aperture diameter>: 100 μm
<Analysis software>: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter, Inc.)
<Electrolyte>: Isoton II (Beckman Coulter, Inc.)
<Dispersion>: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolytic solution <Dispersion condition>: 10 mg of a measurement sample is added to 5 ml of the dispersion, and the ultrasonic disperser is added. Then, 25 ml of the electrolytic solution is added and further dispersed for 1 minute with an ultrasonic disperser.
<Measurement conditions>: 100 ml of electrolyte solution and dispersion were added to a beaker, and 30,000 particles were measured at a concentration capable of measuring the particle size of 30,000 particles in 20 seconds. Ask for.

[Developer]
The developer of the present invention contains at least the toner and contains other components such as a carrier selected as appropriate.
The developer may be a one-component developer or a two-component developer. However, when used in an ultra-high-speed printing system that can handle recent POD, etc. From the viewpoint of the above, the two-component developer is preferable.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, a manganese-strontium (Mn-Sr) type material of 50 emu / g-90 emu / g, manganese-magnesium ( A Mn—Mg) -based material is preferable, and from the viewpoint of securing image density, a highly magnetized material such as iron powder (100 emu / g or more), magnetite (75 emu / g to 120 emu / g) is preferable. In addition, the copper-zinc (Cu—Zn) system (30 emu / g to 80 emu / g) is advantageous in that it can weaken the contact with the electrostatic latent image bearing member in which the toner is in a spiked state and is advantageous for high image quality. A weakly magnetized material such as These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (mass average particle diameter (D ₅₀ )) of 10 μm to 200 μm, and more preferably 40 μm to 100 μm. When the average particle size (mass average particle size (D ₅₀ )) is less than 10 μm, in the distribution of carrier particles, the number of fine powder systems increases, and the magnetization per particle may be lowered to cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And fluorinated terpolymers (triple fluorinated (multiple) copolymers) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

  The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin; Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.

  Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.

  Commercially available products can be used as the modified silicone resin. For example, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.

  In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

  For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.

  There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.

  The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. 98 mass% is preferable and 93 mass%-97 mass% are more preferable. In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 1 part by mass to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

  The toner and developer of the present invention are compatible with low-temperature fixing properties, offset resistance, and heat-resistant storage stability at a level compatible with ultra-high-speed fixing systems, and various electrophotographic image formations, particularly fixed images. Can achieve a low coefficient of friction (lower μ of the fixed image) and is excellent in productivity. Therefore, it is suitable for an ultra-high-speed printing system that can cope with the field of electrophotographic print on demand (POD).

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

  In the following Examples and Comparative Examples, “softening point of polyester resin”, “glass transition temperature (Tg) of polyester resin”, “softening point of rosin”, “acid value of polyester resin and rosin”, “hydroxyl group of polyester resin” The “value”, “content of low molecular weight component having a molecular weight of 500 or less”, “SP value of rosin”, and “degree of rosin maleic modification” were measured as follows.

<Measurement of softening point of polyester resin>
Using a flow tester (manufactured by Shimadzu Corporation, CFT-500D), as a sample, 1 g of each polyester-based binder resin was heated at a heating rate of 6 ° C./min. Extrusion was performed from a nozzle having a length of 1 mm and a length of 1 mm, and the amount of plunger drop of the flow tester was plotted against the temperature. The temperature at which half of the sample flowed out was taken as the softening point.

<Measurement of glass transition temperature (Tg) of polyester resin>
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), 0.01 to 0.02 g of each polyester-based binder resin was weighed into an aluminum pan as a sample, heated to 200 ° C., and the temperature The sample was cooled to 0 ° C at a rate of temperature decrease of 10 ° C / min, and the temperature was increased at a rate of temperature increase of 10 ° C / min, extending from the baseline extension line below the endothermic peak temperature and from the peak rise to the peak apex. The temperature at the intersection with the tangent showing the maximum inclination was defined as the glass transition temperature.

<Measurement of softening point of rosin>
(1) Preparation of sample 10 g of rosin was melted on a hot plate at 170 ° C. for 2 hours. Thereafter, the sample was naturally cooled for 1 hour in an open state at a temperature of 25 ° C. and a relative humidity of 50%, and pulverized for 10 seconds with a coffee mill (National MK-61M) to prepare a sample.
(2) Measurement Using a flow tester (manufactured by Shimadzu Corporation, CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C./min, a 1.96 MPa load was applied by a plunger, a diameter of 1 mm, a length The sample was extruded from a 1 mm nozzle, and the plunger drop amount of the flow tester was plotted against the temperature. The temperature at which half of the sample flowed out was taken as the softening point.

<Acid value of polyester resin and rosin>
It measured based on the method of JISK0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

<Hydroxyl value of polyester resin>
It measured based on the method of JISK0070.

<Content of low molecular weight component having a molecular weight of 500 or less>
The molecular weight distribution was measured by gel permeation chromatography (GPC). First, 10 mL of tetrahydrofuran is added to 30 mg of each polyester binder resin, mixed for 1 hour with a ball mill, and then filtered through a fluororesin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) with a pore size of 2 μm to remove insoluble components. A sample solution was prepared.
Next, tetrahydrofuran was flowed as an eluent at a flow rate of 1 mL per minute, the column was stabilized in a constant temperature bath at 40 ° C., and 100 μL of the sample solution was injected for measurement. Incidentally, “GMHLX + G3000HXL” (manufactured by Tosoh Corporation) is used as an analytical column, and several types of monodisperse polystyrene (2.63 × 10 ³ , 2.06 × 10 ⁴ , manufactured by Tosoh Corporation) are used as molecular weight calibration curves. 1.02 × 10 ⁵ , 2.10 × 10 ³ , 7.00 × 10 ³ , 5.04 × 10 ⁴ ) manufactured by GL Sciences Inc. were prepared as standard samples.
Next, the content (%) of the low molecular weight component having a molecular weight of 500 or less was calculated as a ratio of the area of the corresponding region in the chart area obtained by the RI (refractive index) detector.

<Measurement of SP value of rosin>
After 2.1 g of each sample in a molten state was poured into a predetermined ring, the sample was cooled to room temperature and then measured under the following conditions based on JIS B7410.
-Measuring machine: Ring and ball type automatic softening point tester (ASP-MGK2, manufactured by Meitec Co., Ltd.)
・ Raising rate: 5 ° C / min
-Temperature rise start temperature: 40 ° C
・ Measurement solvent: Glycerin

<Measurement of degree of maleic acid modification of rosin>
The degree of maleic acid modification of the rosin was calculated by the following mathematical formula (I).

[In the above formula (I), X ₁ is the SP value of maleic acid-modified rosin for calculating the degree of modification, and X ₂ is a reaction of 1 mol of maleic acid or its derivative with 1 mol of rosin having a conjugated diene at 230 ° C.] The saturated SP value of the maleic acid-modified rosin obtained by the above process, Y represents the SP value of the rosin having a conjugated diene, and each SP value is measured as follows. ]
<Measurement of SP value>
After each sample 2.1 g in a molten state is poured into a predetermined ring, the sample is cooled to room temperature and then measured under the following conditions based on JIS B7410.
Measuring machine: Ring and ball type automatic softening point tester (ASP-MGK2, manufactured by Meitec Co., Ltd.)
Temperature increase rate: 5 ° C / min
Temperature rising start temperature: 40 ° C
Solvent for measurement: Glycerin The saturated SP value means the SP value when the reaction of maleic acid or a derivative thereof and rosin is reacted until the SP value of the resulting maleic acid-modified rosin reaches the saturation value. The molecular weight of the rosin 1 mol, when the acid value x (mg KOH / g), potassium hydroxide relative to the rosin 1 g (molecular weight: 56.1) is xmg (x × 10 ^-3 g) reaction Therefore, it can be calculated by the following formula, molecular weight = (56100 ÷ x).

A toner obtained by the toner production method of the present invention and a two-component developer containing a carrier comprising the toner and magnetic particles can be mounted on a process cartridge and used.
That is, at least the photosensitive member, a charging unit that charges the surface of the photosensitive member, an exposure unit that exposes the charged surface of the photosensitive member to form an electrostatic latent image, and toner or the toner on the formed electrostatic latent image One means selected from developing means for developing using a developer containing a carrier, transfer means for transferring the developed toner image to a recording medium, and cleaning means for removing toner remaining on the surface of the photoreceptor after transfer; , Can be mounted (loaded) as toner or developer used in a process cartridge that is detachable from the image forming apparatus main body.

  There are many shapes and the like of the process cartridge, but a general example is shown in FIG. That is, FIG. 1 is a schematic sectional view showing an example of the configuration of a process cartridge according to the present invention. An apparatus 14, a transfer device 16 that is a transfer means, a cleaning device 17 that is a cleaning means, and a charge removal device 1A that is a charge removal means are provided. In this case, the toner of the present invention is mounted on the developing device 14. Reference numeral 18 denotes an image receiving medium (for example, paper). Although the photoconductor (11) has a drum shape, it may be a sheet or an endless belt. Reference numeral 19 denotes fixing means.

In the following, maleic acid-modified rosin used for the synthesis of binder resins used in Examples and Comparative Examples was synthesized as follows.
(Synthesis Example 1)
<Purification of rosin>
1,000 g of tall rosin is added to a 2,000 mL distillation flask equipped with a fractionation tube, a reflux condenser, and a receiver, and distilled under a reduced pressure of 1 kPa to distill at 195 ° C. to 250 ° C. Collected as the main fraction. Hereinafter, tall rosin subjected to purification is referred to as unpurified rosin, and rosin collected as a main fraction is referred to as purified rosin.
20 g of each rosin was pulverized with a coffee mill (National MK-61M) for 5 seconds, and 0.5 g was measured in a headspace vial (20 mL) through a sieve having an opening of 1 mm. The headspace gas was sampled, and impurities in the unpurified rosin and the purified rosin were analyzed by the headspace GC-MS method as follows. The results are shown in Table 1.

<Measurement conditions of the headspace GC-MS method>
[A]: Headspace sampler (manufactured by Agilent, HP7694)
Sample temperature: 200 ° C
・ Loop temperature: 200 ℃
・ Transfer line temperature: 200 ℃
・ Sample heating equilibrium time: 30 min
・ Vial pressurized gas: Helium (He)
・ Bial pressurization time: 0.3 min
・ Loop filling time: 0.03 min
-Loop equilibration time: 0.3 min
・ Injection time: 1 min

[B]: GC (gas chromatography) (manufactured by Agilent, HP6890)
Analytical column: DB-1 (60 m-320 μm-5 μm)
・ Carrier: Helium (He)
・ Flow conditions: 1 mL / min
・ Inlet temperature: 210 ° C
Column head pressure: 34.2 kPa
Injection mode: split
Split ratio: 10: 1
-Oven temperature conditions: 45 ° C (3min) -10 ° C / min-280 ° C (15min)

[C]: MS (mass spectrometry) (manufactured by Agilent, HP5973)
-Ionization method: EI (electron impact) method-Interface temperature: 280 ° C
-Ion source temperature: 230 ° C
-Quadrupole temperature: 150 ° C
・ Detection mode: Scan 29-350m / s

<Measurement of saturation SP value of maleic acid-modified rosin using unpurified rosin>
In a 1,000 mL flask equipped with a fractionation tube, a reflux condenser, and a receiver, 332 g (1 mol) of unpurified rosin (SP value: 77.0 ° C.) and 98 g (1 mol) of maleic anhydride The temperature was raised from 160 ° C. to 230 ° C. over 8 hours, and after confirming that the SP value did not increase at 230 ° C., unreacted maleic anhydride and low-boiling substances under a reduced pressure of 5.3 kPa Was distilled off to obtain maleic acid-modified rosin. The SP value of the obtained maleic acid-modified rosin, that is, the saturated SP value of maleic acid-modified rosin using unpurified rosin was 116 ° C.

<Measurement of saturation SP value of maleic acid-modified rosin using purified rosin>
In a 1,000 mL flask equipped with a fractionation tube, a reflux condenser, and a receiver, 338 g (1 mol) of purified rosin (SP value: 76.8 ° C.) and 98 g (1 mol) of maleic anhydride were added. In addition, the temperature was increased from 160 ° C. to 230 ° C. over 8 hours, and after confirming that the SP value did not increase at 230 ° C., unreacted maleic anhydride and low-boiling substances were reduced under a reduced pressure of 5.3 kPa. Distillation was performed to obtain maleic acid-modified rosin. The SP value of the obtained maleic acid-modified rosin, that is, the saturated SP value of the maleic acid-modified rosin using purified rosin was 116 ° C.

(Synthesis Example 2)
<Synthesis of maleic acid-modified rosin A>
In a 10 L flask equipped with a fractionation tube, a reflux condenser, and a receiver, 6,084 g (18 mol) of purified rosin (SP value: 76.8 ° C.) and 1234.8 g (12. 6 mol), heated from 160 ° C. to 220 ° C. over 8 hours, reacted at 220 ° C. for 2 hours, and further distilled under reduced pressure of 5.3 kPa to obtain maleic acid-modified rosin A. It was. The resulting maleic acid-modified rosin A had an SP value of 116 ° C. and a maleic modification degree of 100.

(Synthesis Example 3)
<Synthesis of maleic acid-modified rosin B>
In a 10 L flask equipped with a fractionation tube, a reflux condenser and a receiver, 6,084 g (18 mol) of purified rosin (SP value: 76.8 ° C.) and 882 g (9 mol) of maleic anhydride were placed. In addition, the temperature was raised from 160 ° C. to 220 ° C. over 8 hours, reacted at 220 ° C. for 2 hours, and further distilled under a reduced pressure of 5.3 kPa to obtain maleic acid-modified rosin B. The obtained maleic acid-modified rosin B had an SP value of 106.2 ° C. and a maleic modification degree of 75.

(Synthesis Example 4)
<Synthesis of maleic acid-modified rosin C>
In a 10 L flask equipped with a fractionation tube, a reflux condenser, and a receiver, purified rosin (SP value: 76.8 ° C.) 6,084 g (18 mol) and maleic anhydride 529 g (5.4 mol) The mixture was heated from 160 ° C. to 220 ° C. over 8 hours, reacted at 220 ° C. for 2 hours, and then distilled under reduced pressure of 5.3 kPa to obtain maleic acid-modified rosin C. The resulting maleic acid-modified rosin C had an SP value of 96.4 ° C. and a maleic modification degree of 50.

(Synthesis Example 5)
<Synthesis of maleic acid-modified rosin D>
In a 10 L flask equipped with a fractionation tube, a reflux condenser, and a receiver, purified rosin (SP value: 76.8 ° C.) 6,084 g (18 mol), and maleic anhydride 352.8 g (3. 6 mol), heated from 160 ° C. to 220 ° C. over 8 hours, reacted at 220 ° C. for 2 hours, and further distilled under a reduced pressure of 5.3 kPa to obtain maleic acid-modified rosin D. It was. The resulting maleic acid-modified rosin D had an SP value of 88.6 ° C. and a maleic modification degree of 30.

(Synthesis Example 6)
<Synthesis of maleic acid-modified rosin E>
In a 10 L flask equipped with a fractionation tube, reflux condenser and receiver, 5,976 g (18 mol) of unpurified rosin (SP value: 77.0 ° C.) and 352.8 g (3 mol) of maleic anhydride .6 mol), heated from 160 ° C. to 220 ° C. over 8 hours, reacted at 250 ° C. for 2 hours, and further distilled under reduced pressure of 5.3 kPa to obtain maleic acid-modified rosin E. Obtained. The resulting maleic acid-modified rosin E had an SP value of 88.7 ° C. and a maleic modification degree of 30.

(Synthesis Example 7)
<Synthesis of maleic acid-modified rosin F>
In a 10 L flask equipped with a fractionation tube, reflux condenser and receiver, 5,976 g (18 mol) of unpurified rosin (SP value: 77.0 ° C.) and 352.8 g (3 mol) of maleic anhydride .6 mol), heated from 160 ° C. to 220 ° C. over 8 hours, reacted at 250 ° C. for 2 hours, and further distilled under reduced pressure of 5.3 kPa to obtain maleic acid-modified rosin F. Obtained. The resulting maleic acid-modified rosin F had an SP value of 83.8 ° C. and a maleic modification degree of 17.

  Next, a polyester-based binder resin (A) was synthesized using an alcohol component, a carboxylic acid component containing maleic acid-modified rosin synthesized above, and an esterification catalyst.

(Synthesis Examples 8 to 11)
<Synthesis of polyester binder resins A1 to A4>
Place the alcohol component shown in Table 2, the carboxylic acid component other than trimellitic anhydride, and the esterification catalyst into a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. Then, after a condensation polymerization reaction at 230 ° C. for 10 hours in a nitrogen atmosphere, the reaction was performed at 230 ° C. and 8 kPa for 1 hour. After cooling to 220 ° C., trimellitic anhydride shown in Table 2 below is added, and after reacting at normal pressure (101.3 kPa) for 1 hour, the reaction is performed at 220 ° C. and 20 kPa until the desired softening point is reached. The polyester-based binder resins A1 to A4 were synthesized.
In the polyester binder resins A1 to A4, the content of the divalent aliphatic alcohol having 2 to 6 carbon atoms was 100 mol% in the divalent alcohol component and 100 mol% in the alcohol component. .

(Synthesis Examples 12 to 13)
<Synthesis of polyester binder resins A5 to A6>
The alcohol component shown in Table 2, the carboxylic acid component containing maleic acid-modified rosin, and the esterification catalyst are placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. Then, after a polycondensation reaction was performed at 230 ° C. for 10 hours in a nitrogen atmosphere, the reaction was performed at 230 ° C. and 8 kPa until a desired softening point was reached, thereby synthesizing polyester-based binder resins A5 to A6.
In the polyester binder resin A5, the content of the divalent aliphatic alcohol having 2 to 6 carbon atoms was 74 mol% in the divalent alcohol component. In the polyester binder resin A6, the content of the divalent aliphatic alcohol having 2 to 6 carbon atoms was 69 mol% in the divalent alcohol component.

  Next, the polyester-type binder resin (B) was synthesize | combined using the alcohol component containing the alkylene oxide adduct of the bisphenol compound represented by the said General formula (1), and a carboxylic acid component.

(Synthesis Examples 14 to 20)
<Synthesis of polyester resins B1 to B7>
Place the alcohol component shown in Table 3 below, a carboxylic acid component other than trimellitic anhydride, and an esterification catalyst into a 5-liter four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple. Then, after a condensation polymerization reaction at 230 ° C. for 10 hours in a nitrogen atmosphere, the reaction was performed at 230 ° C. and 8 kPa for 1 hour. After cooling to 220 ° C., trimellitic anhydride shown in Table 3 below is added, and after reacting at normal pressure (101.3 kPa) for 1 hour, the reaction is performed at 220 ° C. and 20 kPa until the desired softening point is reached. And polyester resins B1 to B7 were obtained. The results are shown in Table 3 below for the softening point, glass transition temperature, and acid value of each resin.

  Next, a toner was prepared using the synthesized polyester resin (A), polyester resin (B), colorant, release agent, and the like.

(Examples 1-14, Comparative Examples 1-2)
<Production of toner>
After premixing the binder resin, release agent, and colorant combinations and prescription amounts shown in Table 4 below using a Henschel mixer (FM10B, manufactured by Mitsui Miike Chemical Co., Ltd.), biaxial The mixture was melted and kneaded at a temperature of 100 ° C. to 130 ° C. with a kneader (Ikegai, PCM-30).
The obtained kneaded product was cooled to room temperature and then coarsely pulverized to 200 μm to 300 μm with a hammer mill. Next, after finely pulverizing using a supersonic jet pulverizer, Labo Jet (manufactured by Nippon Pneumatic Industry Co., Ltd.), adjusting the pulverization air pressure appropriately so that the mass average particle diameter becomes 8.2 ± 0.3 μm. The louver opening is adjusted so that the mass average particle size is 9.0 ± 0.2 μm and the amount of fine powder of 4 μm or less is 10% by number or less with an airflow classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I). Classification was carried out with appropriate adjustment to obtain toner base particles. Next, 1.0 part by mass of an additive (HDK-2000, manufactured by Clariant Co., Ltd.) was stirred and mixed with a Henschel mixer with respect to 100 parts by mass of the toner base particles, thereby producing toners 1 to 16, respectively.

<Creation of carrier>
A coating material having the following composition is dispersed with a stirrer for 10 minutes to prepare a coating liquid, and 5,000 parts by mass of this coating liquid and a core material (Cu—Zn ferrite particles, mass average diameter = 80 μm) are rotated in a fluidized bed. The coating liquid was applied to the core material by applying it to a coating apparatus for coating while forming a swirling flow provided with a type bottom plate disk and stirring blades. The obtained coated material was baked in an electric furnace at 280 ° C. for 2 hours to prepare a carrier.
[Coating material composition]
Toluene: 450 parts by mass Silicone resin (SR2400, manufactured by Toray Dow Corning Silicone Co., Ltd., nonvolatile content 50% by mass): 450 parts by mass Aminosilane (SH6020, manufactured by Toray Dow Corning Silicone Co., Ltd.): 10 parts by mass Parts ・ Carbon black: 10 parts by mass

<Preparation of two-component developer>
Using a tumbler mixer (manufactured by Willy et Bacofen (WAB) Co., Ltd.) in which 5% by mass of the prepared toners 1 to 16 and 95% by mass of the prepared carrier are stirred by rolling the container. Were mixed and charged at 48 rpm for 5 minutes to prepare two-component developers 1-18.

[Performance evaluation]
Next, for the toners 1 to 16 of Examples and Comparative Examples, the pulverization property, antifouling property, surface friction coefficient of fixed image, cold offset resistance, hot offset resistance, and heat resistant storage stability were evaluated as follows. did. The results are shown in Table 6 below.
Note that the antifouling property, the cold offset resistance, and the hot offset resistance were evaluated by loading the developers 1 to 20 of each example and each comparative example in the image forming apparatus.
Here, as an image forming apparatus, a remodeling machine of an ultrahigh-speed digital laser printer IPSiO SP9500Pro adopting a two-component developing system, a direct transfer system, and a heating roller fixing system (manufactured by Ricoh Co., Ltd., printing speed 156 sheets / min (A4 size sideways) ))It was used.

<Crushability>
In Examples and Comparative Examples, 10.00 g of a raw material melt-kneaded product obtained at the time of toner production, coarsely pulverized to a particle size of 200 μm to 300 μm with a hammer mill, was precisely weighed, and mill and mixer type MM-I ( After crushing for 30 seconds with Hitachi Living Supply Co., Ltd., sieve through 30 mesh (opening: 500 μm), weigh accurately the mass (A) g of the resin that does not pass, and calculate the residual rate by the following formula (II) Asked. This operation was performed 3 times, and the average value of the average remaining rate was used as an index of grindability, and grindability was evaluated according to the following evaluation criteria. The smaller the average value of the residual rate, the better the grindability.
[Formula (II)]
Residual rate (%) = [(A) / toner mass before pulverization (10.00 g)] × 100
〔Evaluation criteria〕
◎: Residual rate is less than 3% ○: Residual rate is 3% or more and less than 8% △: Residual rate is 8% or more and less than 15% (same as conventional toner)
×: Residual rate is 15% or more and less than 20% XX: Residual rate is 20% or more

<Heat resistant storage stability>
The heat-resistant storage stability was measured using a penetration tester (manufactured by Nikka Engineering Co., Ltd.). Specifically, 10 g of each toner was weighed and placed in a 30 ml glass container (screw vial) in an environment of 20 to 25 ° C. and 40 to 60% RH, and the lid was closed. After tapping the glass container containing the toner 200 times, leaving it in a thermostat set at 50 ° C. for 48 hours, measuring the penetration with a penetration tester, and heat-resistant storage stability according to the following evaluation criteria Evaluated. The greater the penetration value, the better the heat resistant storage stability.
〔Evaluation criteria〕
◎: Needle penetration is 30 mm or more ○: Needle penetration is 20 mm to 29 mm
Δ: penetration is 15 mm to 19 mm (equivalent to conventional toner)
X: The penetration is 8 mm to 14 mm
XX: Needle penetration is 7mm or less

<Cold offset resistance>
Each developer is loaded into an ultrahigh-speed digital laser printer IPSiO SP9500Pro, and 1 cm of toner adhesion amount 0.20 ± 0.1 mg / cm ² on a thick paper transfer paper (manufactured by NBS Ricoh Co., Ltd., copy printing paper <135>). Create a square solid image, attach Scotch Mending Tape 810 (width 24 mm, manufactured by 3M) on the solid image, and apply a metal roller (φ50, manufactured by SUS) weighing 1 kg from the tape at a speed of 10 mm / s. 10 reciprocations were made while rolling. The tape was peeled off in a fixed direction at a speed of 10 mm / s, the image afterimage rate was determined from the image density before and after tape peeling using the following formula (III), and cold offset resistance was evaluated according to the following evaluation criteria.
[Formula (III)]
Image residual ratio (%) = (image density after peeling / image density before peeling) × 100
〔Evaluation criteria〕
A: Image remaining rate is 97% or more. B: Image remaining rate is 92% or more and less than 97%. Δ: Image remaining rate is 85% or more and less than 92%. X: Image remaining rate is 80% or more and less than 85%. )
XX: Image remaining rate is less than 80%

<Hot offset resistance>
Each developer is loaded into an ultrahigh-speed digital laser printer IPSiO SP9500Pro, and 1 cm of toner adhesion amount 0.40 ± 0.1 mg / cm ² on a thin paper transfer paper (manufactured by NBS Ricoh Co., Ltd., copy printing paper <55>). A square solid image was created, fixing was performed by changing the fixing roller temperature, the presence or absence of hot offset was visually evaluated, and the upper limit temperature at which hot offset did not occur was set as the upper limit fixing temperature, and the hot offset resistance was evaluated according to the following criteria. .
〔Evaluation criteria〕
A: The upper limit temperature of fixing is 240 ° C. or higher. O: The upper limit temperature of fixing is 220 ° C. or higher and lower than 240 ° C. Δ: The upper limit temperature of fixing is 180 ° C. or higher and lower than 220 ° C.
×: Fixing upper limit temperature is less than 180 ° C

<Development roller contamination resistance>
Each developer is loaded into an ultra-high-speed digital laser printer IPSiO SP9500Pro remodeling machine. After printing 100,000 sheets on a 5% image area chart, the developer and toner on the developing roller are removed, and the developing roller in the blank paper passing section The soil was visually evaluated to evaluate the stain resistance of the developing roller.
〔Evaluation criteria〕
◎: The developing roller is not soiled at all ○: The soiling is so small that it is hardly discernable by visual observation △: Slightly worrisome soiling occurs (same as conventional toner)
×: Dirt that is clearly problematic and difficult to use

<Toner Odor Evaluation Method>
20 g of each toner was weighed into an aluminum cup and allowed to stand on a hot plate heated to 150 ° C. for 30 minutes, and the odor generated from the toner was evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◎: Odor is not felt at all ○: Odor is hardly felt △: Odor is felt slightly, but there is no practical problem ×: Odor is felt strongly

From the results of Table 5 above, Examples 1 to 14 are compatible with low-temperature fixability, offset resistance, and heat-resistant storage stability at a level compatible with an ultrahigh-speed image forming system, as compared with Comparative Examples 1 and 2. It has been found that the generation of odor can be reduced, and further, it has a special effect on the antifouling property to the developing roller and the like, and is excellent in productivity.
The toner and developer of the present invention are compatible with ultra-high-speed image forming systems, and are compatible with low-temperature fixability, offset resistance, and heat-preserving stability, and can reduce odor generation. It has a special effect on the anti-contamination property and is excellent in productivity. For example, it can be suitably used for an ultra-high-speed printing system that can cope with the field of electrophotographic print on demand (POD). it can.

It is a schematic sectional drawing which shows the structural example of the process cartridge which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1A Static elimination apparatus 11 Photoconductor 12 Charging apparatus 13 Exposure apparatus 14 Developing apparatus 16 Transfer apparatus 17 Cleaning apparatus 18 Image receiving medium 19 Fixing apparatus

Claims (16)

A toner containing at least a binder resin and a colorant, wherein the binder resin contains 70 mol% or more of a divalent aliphatic alcohol having 2 to 6 carbon atoms in a divalent alcohol component as a main component. A polyester resin (A) obtained by polycondensation of an alcohol component containing, a carboxylic acid component containing a maleic acid-modified rosin, which is a reaction product of a rosin having a conjugated diene and maleic acid or a derivative thereof; A toner comprising a polyester resin (B) obtained by polycondensation of an alcohol component containing an alkylene oxide adduct of a bisphenol compound represented by 1) and a carboxylic acid component.

[In said general formula (1), R < ₁ > and R < ₂ > represents a C2-C4 alkylene group. R ₃ and R ₄ represent a hydrogen atom, a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group. x and y are integers greater than or equal to 0, and the sum is 1-16. ] 2. The toner according to claim 1, wherein the maleic acid-modified rosin has a maleic modification degree represented by the following formula (I) of 30 to 105.

[In the above formula (I), X ₁ is the SP value of maleic acid-modified rosin for calculating the degree of modification, X ₂ is a reaction of 1 mol of maleic acid or its derivative with 1 mol of rosin having a conjugated diene at 230 ° C. The saturated SP value of maleic acid-modified rosin obtained in this manner, Y represents the SP value of rosin having a conjugated diene, and each SP value is measured as follows. ]
<Measurement of SP value>
After each sample 2.1 g in a molten state is poured into a predetermined ring, the sample is cooled to room temperature and then measured under the following conditions based on JIS B7410.
Measuring machine: Ring and ball type automatic softening point tester (ASP-MGK2, manufactured by Meitec Co., Ltd.)
Temperature increase rate: 5 ° C / min
Temperature rising start temperature: 40 ° C
Measuring solvent: Glycerin   The toner according to claim 1, wherein the content of maleic acid-modified rosin in the carboxylic acid component in the polyester resin (A) is 15 to 85% by weight.   The toner according to claim 1, wherein the maleic acid-modified rosin in the polyester resin (A) is a rosin having a purified conjugated diene modified with maleic acid or a derivative thereof. .   The alcohol component and / or carboxylic acid component in the polyester resin (A) contains a trivalent or higher valent alcohol compound and / or a trivalent or higher carboxylic acid compound. The toner described.   The toner according to claim 1, wherein the content of the low molecular weight component having a molecular weight of 500 or less contained in the polyester resin (A) is 12% or less.   The polyester resin (A) is a main component of a divalent aliphatic alcohol having 2 to 6 carbon atoms in the presence of a titanium compound and / or a tin (II) compound having no Sn-C bond. The alcohol component contained in the divalent alcohol component in an amount of 70 mol% or more, and obtained by condensation polymerization of a rosin having a conjugated diene and maleic acid or a derivative thereof. The toner described in 1.   The polyester resin (B) is obtained by condensation polymerization of an alcohol component containing 80 mol% or more of an alkylene oxide adduct of a bisphenol compound represented by the general formula (1) in a divalent alcohol component and a carboxylic acid component. The toner according to claim 1, wherein the toner is obtained.   The toner according to claim 1, wherein a softening point Tm (B) of the polyester resin (B) is 90 ° C. or higher and 160 ° C. or lower.   The acid value of the polyester resin (A) is 25 to 70 mgKOH / g, and the acid value of the polyester resin (B) is 1 to 25 mgKOH / g. The toner described in 1.  The weight ratio [(B) / (A)] of the polyester resin (A) and the polyester resin (B) is 1/9 to 6/4. The toner described in 1.   A two-component developer comprising at least the toner according to claim 1 and a carrier comprising magnetic particles.   A step of charging at least the surface of the photosensitive member by a charging unit, a step of forming an electrostatic latent image on the surface of the photosensitive member by an exposure unit, and a step of developing the electrostatic latent image as a toner image using toner by a developing unit An image forming method comprising: a step of transferring the developed toner image onto a recording medium by a transfer unit; and a step of fixing the transferred toner image by a fixing unit, wherein the toner to be used is claimed. Item 12. An image forming method, which is the toner according to any one of Items 1 to 11.   A step of charging at least the surface of the photosensitive member with a charging unit; a step of forming an electrostatic latent image on the surface of the photosensitive member with an exposing unit; and a two-component development including a toner and a carrier on the electrostatic latent image with a developing unit An image forming method comprising: a step of developing a toner image using an agent; a step of transferring the developed toner image to a recording medium by a transfer unit; and a step of fixing the transferred toner image by a fixing unit. The image forming method according to claim 12, wherein the developer used is the two-component developer according to claim 12.   At least the photosensitive member, a charging unit that charges the surface of the photosensitive member, an exposure unit that exposes the charged surface of the photosensitive member to form an electrostatic latent image, and development that uses toner to develop the formed electrostatic latent image The image forming apparatus main body is detachable from the image forming apparatus main body, the transfer means for transferring the developed toner image to the recording medium, and the cleaning means for removing the toner remaining on the surface of the photoreceptor after the transfer. 12. A process cartridge according to claim 1, wherein the toner used is the toner according to claim 1.   At least a photosensitive member, a charging unit that charges the surface of the photosensitive member, an exposure unit that exposes the charged surface of the photosensitive member to form an electrostatic latent image, and a two-component that includes toner and a carrier in the formed electrostatic latent image One means selected from a developing means for developing using a developer of the system, a transferring means for transferring the developed toner image to a recording medium, and a cleaning means for removing the toner remaining on the surface of the photoreceptor after the transfer. 13. A process cartridge which is detachable from an integrated image forming apparatus main body, wherein the developer used is the two-component developer according to claim 12.

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