JP6987654B2 - toner - Google Patents

Description

The present invention relates to a toner used in an electrophotographic image forming method.

In recent years, with the development of image forming devices such as copiers and printers, there is a demand for toners capable of higher speed, higher image quality, longer life, and energy saving than before. In order to achieve energy saving, it is effective to lower the fixing temperature of the toner. As one of the means, it has been proposed to use a polyester resin having a low softening temperature. However, since the softening temperature is low, the toners may be fused to each other in a stationary state such as during storage or transportation. Therefore, as a means for achieving both low-temperature fixability and storage stability, a technique using a crystalline polyester resin having a sharp melt property in which the viscosity greatly decreases when the melting point is exceeded has been proposed (for example, Patent Documents 1 to 3).
On the other hand, crystalline polyester and amorphous polyester are also used in combination as a toner material (for example, Patent Documents 4 and 5). Further, the toner is held at a temperature close to the melting point of the crystalline polyester resin, and an annealing treatment is performed to promote the crystallization of the crystalline polyester (for example, Patent Document 6), or a nucleating agent that promotes the crystallization of the crystalline polyester is used. It has also been proposed to add (eg, Patent Documents 7 and 8).

Special Publication No. 56-13943 Special Publication No. 62-39428 Japanese Unexamined Patent Publication No. 4-120554 Japanese Unexamined Patent Publication No. 2002-318471 Japanese Unexamined Patent Publication No. 2007-41500 Japanese Unexamined Patent Publication No. 2012-93704 Japanese Unexamined Patent Publication No. 2006-11473 Japanese Unexamined Patent Publication No. 2007-033773

When crystalline polyester as described in Patent Documents 1 to 3 is used alone as a toner, the toner charge gradually escapes after triboelectric charging due to the low electrical resistance of the crystalline polyester. It was a big issue to get rid of it.
On the other hand, when crystalline polyester and amorphous polyester are used in combination as toner materials as in Patent Documents 4 and 5, the compatibility between crystalline polyester and amorphous polyester needs to be high in order to obtain low temperature fixability. be. However, when the compatibility between the two resins is high, the crystalline polyester and the amorphous polyester are compatible with each other during the toner production, and the glass transition temperature of the toner (hereinafter, also simply referred to as “Tg”) is lowered, which is excellent. Although low-temperature fixing property can be obtained, there is a problem that the charge retention property and the heat-resistant storage property of the toner are deteriorated.
Further, an annealing treatment for promoting crystallization of crystalline polyester as described in Patent Document 6 and a nucleating agent for promoting crystallization of crystalline polyester as described in Patent Documents 7 and 8 are added. Although it is possible to improve the charge retention property and the heat-resistant storage property, the Tg becomes high, so that the low-temperature fixing property may be deteriorated.
To solve such a problem, an object of the present invention is to provide a toner having excellent low temperature fixing property, charge retention property, and heat storage property.

As a result of diligent studies by the present inventors, in addition to the amorphous polyester having a specific acid value and hydroxyl value and the aliphatic crystalline polyester, a benzoic acid metal salt substituted with an alkyl group is used in combination. It was found that a toner having excellent low-temperature fixing property, charge retention property, and heat-resistant storage property can be obtained.
The benzoic acid metal salt substituted with an alkyl group has an aromatic ring and a carbonyl group having a high affinity with an amorphous polyester and an alkyl group having a high affinity with an aliphatic crystalline polyester. Therefore, the benzoic acid metal salt substituted with an alkyl group does not localize in the aliphatic crystalline polyester unlike the conventional nucleating agent, and tends to exist at the interface between the amorphous polyester and the aliphatic crystalline polyester. Seem. That is, as a result of not promoting the crystallization of the aliphatic crystalline polyester, constraining the motility, and losing the motility in the state where the aliphatic crystalline polyester is compatible with the amorphous polyester, the above-mentioned effect is exhibited. I think that the.
That is, the toner of the present invention is a toner having toner particles containing a resin component and a benzoic acid metal salt compound.
The resin component has an amorphous polyester and an aliphatic crystalline polyester, and the resin component has an amorphous polyester and an aliphatic crystalline polyester.
The content of the amorphous polyester in the resin component is 50% by mass or more, and the content is 50% by mass or more.
The total acid value of the amorphous polyester is 3 mgKOH / g or more and 10 mgKOH / g or less, and the total hydroxyl value is 40 mgKOH / g or more and 70 mgKOH / g or less.
The amorphous polyester has an amorphous polyester (A) and an amorphous polyester (B).
The weight average molecular weights of the amorphous polyester (A) and the amorphous polyester (B) are Ma and Mb, the acid values are Aa (mgKOH / g) and Ab (mgKOH / g), and the hydroxyl value is OHa ( mgKOH / g) and OHb (mgKOH / g)
When the mass ratios in the amorphous polyester are Wa (mass%) and Wb (mass%), respectively.
90 ≤ Wa + Wb ≤ 100,
Wa> Wb, Aa <Ab, OHa> OHb, Ma <Mb hold,
The benzoic acid metal salt compound is represented by the following formula (1), and is characterized by containing 0.1% by mass or more and 10% by mass or less with respect to the total mass of the resin component.

（式（１）中、Ｒ₁〜Ｒ₅はＨまたは炭素数３以上の直鎖状または分岐状のアルキル基である。Ｒ₁〜Ｒ₅の少なくとも１つは炭素数３以上の直鎖状または分岐状のアルキル基である。ｍは１〜３の整数、ｎは０〜２の整数である。ＭはＮａ、Ｋ、Ｃａ、Ｍｇ、Ｚｎ、Ａｌのいずれかを表す。）

(In the formula (1), R _{1 to} R ₅ are H or a linear or branched alkyl group having 3 or more carbon atoms. At least one of _{R 1 to} R _{5 is a linear chain having 3 or more carbon atoms.} Alternatively, it is a branched alkyl group. M is an integer of 1 to 3 and n is an integer of 0 to 2. M represents any of Na, K, Ca, Mg, Zn, and Al.)

According to the present invention, it is possible to provide a toner having excellent low temperature fixing property, charge retention property, and heat storage property.

The toner in the present invention contains a resin component and a benzoic acid metal salt compound. In the present invention, the resin component mainly refers to a polymer component that contributes to fixing performance. The resin component includes an amorphous polyester and an aliphatic crystalline polyester.

Amorphous polyester is a non-crystalline polyester resin. The amorphous polyester needs to be contained in the resin component in an amount of 50% by mass or more.

The amorphous polyester is composed of a plurality of resins and includes an amorphous polyester (A) and an amorphous polyester (B). The mass ratio Wa (mass%), acid value Aa (mgKOH / g), hydroxyl value OHa (mgKOH / g), and weight average molecular weight Ma of the amorphous polyester (A) in the amorphous polyester are not the same. Between the mass ratio Wb (mass%), acid value Ab (mgKOH / g), hydroxyl value OHb (mgKOH / g), and weight average molecular weight Mb of the crystalline polyester (B) in the aromatic amorphous polyester. The following relationship holds.
Wa> Wb, Aa <Ab, OHa> OHb, Ma <Mb

When the above relationship is established, the low temperature fixing property, charge retention property, and heat storage property of the toner are improved. By containing a large amount of low acid value and high hydroxyl value low molecular weight components in the amorphous polyester, the benzoic acid metal salt compound described later easily interacts with the highly motile low molecular weight components, and as a result, the non-crystalline polyester is described above. It seems that it became easier to distribute at the interface between the crystalline polyester and the aliphatic crystalline polyester described later.

The acid value is the number of mg of potassium hydroxide required to neutralize an acid component such as free fatty acid and resin acid contained in 1 g of a sample. The measuring method was measured according to JIS-K0070. The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to the hydroxyl group when 1 g of the sample is acetylated. The measuring method was measured according to JIS-K0070.

From the viewpoint of low temperature fixability, the mass ratio Wa (mass%) of the amorphous polyester (A) and the mass ratio Wb (mass%) of the amorphous polyester (B) are 90 ≦ Wa + Wb ≦ 100. It is necessary, and more preferably 95 ≦ Wa + Wb ≦ 100. Further, 60 ≦ Wa / (Wa + Wb) ≦ 90 is necessary from the viewpoint of low temperature fixing property and heat-resistant storage property, and 70 ≦ Wa / (Wa + Wb) ≦ 90 is more preferable.

The acid value Aa of the amorphous polyester (A) is preferably 0 mgKOH / g ≦ Aa ≦ 7 mgKOH / g from the viewpoint of low temperature fixability. The hydroxyl value OHa of the amorphous polyester (A) is preferably 45 mgKOH / g ≦ OHa ≦ 65 mgKOH / g from the viewpoint of low temperature fixability.

The acid value Ab of the amorphous polyester (B) is preferably 5 mgKOH / g ≦ Aa ≦ 30 mgKOH / g from the viewpoint of low temperature fixability and charge retention. The hydroxyl value OHb of the amorphous polyester (B) is preferably 0 mgKOH / g ≦ OHa ≦ 55 mgKOH / g from the viewpoint of low temperature fixability.

Further, it is preferable and more preferably that the difference in acid value between the amorphous polyester (A) and the amorphous polyester (B) is 5 or more and 30 or less from the viewpoint of low temperature fixability and heat storage stability. Is 5 or more and 20 or less. The difference in hydroxyl value between the amorphous polyester (A) and the amorphous polyester (B) OHa-OHb is preferably 5 or more and 65 or less from the viewpoint of low temperature fixability and heat storage stability, and more preferably 5. More than 60 and less.

The weight average molecular weight Ma of the amorphous polyester (A) is preferably 3000 ≦ Ma ≦ 10000, and more preferably 3000 ≦ Ma ≦ 8000 from the viewpoint of low temperature fixability. Further, the ratio (Ma / Mb) of the weight average molecular weight of the amorphous polyester (A) to the amorphous polyester (B) is 0.001 or more and 0.1 or less, that is, low temperature fixing property and heat storage property. It is preferable from the viewpoint of.

Among the dicarboxylic acid-derived units contained in the amorphous polyester (A) and the amorphous polyester (B), the proportions of the terephthalic acid-derived units represented by the formula (2) Ta (mol%) and Tb ( Mol%) is preferably 70 ≦ Ta ≦ 100 and Ta> Tb from the viewpoint of low temperature fixability. The proportion of units derived from terephthalic acid can be measured by a known method, for example, by NMR.

It is preferable that the glass transition point of the amorphous polyester (A) and the amorphous polyester (B) is 50 ° C. or higher and 80 ° C. or lower from the viewpoint of low temperature fixability and heat storage stability, and more preferably 50 ° C. or higher and 70 ° C. or higher. It is below ° C.

The total acid value of the amorphous polyester needs to be 3 mgKOH / g or more and 10 mgKOH / g or less. The total acid value is a weighted average calculated from the acid value and mass ratio of a plurality of resins contained in the amorphous polyester. Further, the total hydroxyl value of the amorphous polyester needs to be 40 mgKOH / g or more and 70 mgKOH / g or less (preferably 40 mgKOH / g or more and 60 mgKOH / g or less). The total hydroxyl value is a weighted average calculated from the hydroxyl values and mass ratios of a plurality of resins contained in the amorphous polyester.

The resin component in the present invention includes an aliphatic crystalline polyester. The aliphatic crystalline polyester is a polyester resin having crystallization, and is a unit Y1 derived from an aliphatic dicarboxylic acid represented by the following formula (3) and a unit Y2 derived from an aliphatic dialcohol represented by the following formula (4). And have. One or more aliphatic crystalline polyesters may be contained.

（式中、ｐは４以上１２以下の整数であり、ｑは４以上１２以下の整数である。）

(In the formula, p is an integer of 4 or more and 12 or less, and q is an integer of 4 or more and 12 or less.)

The content of the aliphatic crystalline polyester is preferably 5% by mass or more and 30% by mass or less with respect to the total mass of the resin component from the viewpoint of low temperature fixability and charge retention, and more preferably 5% by mass. It is 20% by mass or less.

The melting point of the aliphatic crystalline polyester is preferably 50 ° C. or higher and 90 ° C. or lower, preferably 60 ° C. or higher and 80 ° C. or lower, from the viewpoint of low temperature fixability and charge retention. The melting point of the aliphatic crystalline polyester can be measured using a differential scanning calorimeter (DSC). Specifically, 0.01 to 0.02 g of a sample is precisely weighed in an aluminum pan and heated from 0 ° C. to 200 ° C. at a heating rate of 10 ° C./min to obtain a DSC curve. From the obtained DSC curve, the peak temperature of the endothermic peak is defined as the melting point.

In the toner of the present invention, other polymers may be used in combination as the resin component in addition to the amorphous polyester and the aliphatic crystalline polyester. Specifically, the following polymers and the like can be used. Monopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and its substitutions; styrene-p-chlorstyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene -Styrene-based copolymers such as acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers; polyvinyl chloride, phenolic resin, naturally modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, poly Examples thereof include vinyl acetate, silicone resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyethylene resin and polypropylene resin.

The toner in the present invention contains a benzoic acid metal salt compound. The benzoic acid metal salt compound is a compound represented by the formula (1), has an aromatic ring and a carbonyl group having a high affinity with an amorphous polysell, and has a high affinity with an aliphatic crystalline polyester. It has a linear or / and branched alkyl group.

（式（１）中、Ｒ₁〜Ｒ₅はＨまたは炭素数３以上の直鎖状または分岐状のアルキル基である。Ｒ₁〜Ｒ₅の少なくとも１つは炭素数３以上の直鎖状または分岐状のアルキル基である。ｍは１〜３の整数、ｎは０〜２の整数である。ＭはＮａ、Ｋ、Ｃａ、Ｍｇ、Ｚｎ、Ａｌのいずれかを表す。）

(In the formula (1), R _{1 to} R ₅ are H or a linear or branched alkyl group having 3 or more carbon atoms. At least one of _{R 1 to} R _{5 is a linear chain having 3 or more carbon atoms.} Alternatively, it is a branched alkyl group. M is an integer of 1 to 3 and n is an integer of 0 to 2. M represents any of Na, K, Ca, Mg, Zn, and Al.)

The content of the benzoic acid metal salt compound is preferably 0.1% by mass or more and 10% by mass or less with respect to the total mass of the resin component from the viewpoint of low temperature fixing property, charge retention property and heat storage property. More preferably, it is 0.5% by mass or more and 5% by mass or less.

The toner of the present invention may contain a colorant. Examples of the colorant include the following.

Examples of the black colorant include carbon black; a color toned black using a yellow colorant, a magenta colorant, and a cyan colorant. The pigment may be used alone as the colorant, but it is more preferable to improve the sharpness by using the dye and the pigment in combination from the viewpoint of the image quality of the full-color image.

Examples of the magenta toner pigment include the following. C. 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: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; C.I. I. Pigment Violet 19; C.I. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. Disperse thread 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the cyan toner pigment include the following. C. I. Pigment Blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid blue 45, a copper phthalocyanine pigment in which one or more and five or less phthalocyanine methyl groups are substituted in the phthalocyanine skeleton.

As the dye for cyan toner, C.I. I. There is Solvent Blue 70.

Examples of the pigment for yellow toner include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C.I. I. Bat Yellow 1, 3, 20.
Examples of the dye for yellow toner include C.I. I. There is Solvent Yellow 162.

These colorants can be used alone or in admixture, and even in the form of a solid solution. The colorant is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner.

In the present invention, the content of the colorant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component.

The toner of the present invention may contain a mold release agent, and examples thereof include the following.

Low molecular weight polyolefins such as polyethylene; Silicones having a melting point (softening point) by heating; Fatty acid amides such as oleic acid amide, erucic acid amide, lysinolic acid amide, stearic acid amide; Esther such as stearyl stearate Waxes; Carnauba wax, Rice wax, Candelilla wax, Wood wax, Plant wax such as jojoba oil; Animal wax such as Mitsurou; Montan wax, Ozokerite, Celesin, Paraffin wax, Microcrystalin wax, Fisher tropsch wax , Mineral and petroleum waxes such as ester waxes; and their modifications.

The content of the release agent is preferably 1 to 25 parts by mass with respect to 100 parts by mass of the resin component constituting the toner.

From the viewpoint of obtaining a high-definition image, the toner of the present invention preferably has a volume-based median diameter of 3.0 μm or more and 10.0 μm or less, and more preferably 4.0 or more and 7.0 μm or less.

As a method for producing the toner particles of the present invention, a known method can be used. Hereinafter, the toner manufacturing procedure by the pulverization method will be described as an example.

In the raw material mixing step, as materials constituting the toner particles, for example, a binder resin, a fatty acid metal salt, and other components such as a mold release agent, a colorant, and a charge control agent, if necessary, are weighed and blended in a predetermined amount. And mix. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industries, Ltd.) and the like.

Next, the mixed materials are melt-kneaded. In the melt-kneading process, batch-type kneaders such as pressurized kneaders and Bambary mixers and continuous-type kneaders can be used, and single-screw or twin-screw extruders have become the mainstream because of the advantage of continuous production. There is. For example, KTK type twin-screw extruder (manufactured by Kobe Steel), TEM type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Iron Works), twin-screw extruder (manufactured by Kay-Cee). ), Co-kneader (manufactured by Bus Co., Ltd.), Kneedex (manufactured by Nippon Coke Industries Co., Ltd.), etc. Further, the resin composition obtained by melt-kneading is rolled with two rolls or the like, and is rapidly cooled with water or the like in the cooling step.

Then, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the crushing process, after coarse crushing with a crusher such as a crusher, a hammer mill, or a feather mill, further, for example, a cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo mill. (Made by Turbo Industries) or a fine crusher using the air jet method.

After that, if necessary, classification such as inertial classification type elbow jet (manufactured by Nittetsu Mining Co., Ltd.), centrifugal force classification method turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), faculty (manufactured by Hosokawa Micron) Classify using a machine or a sieving machine to obtain a classified product (toner particles).

Further, if necessary, an external additive is applied to the surface of the toner particles. As a method of externally adding an external additive, a predetermined amount of classified toner and various known external additives are mixed, and a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a henschel mixer, a nautamixer, and a mechano are used. Examples thereof include a method of stirring and mixing using a mixing device such as a hybrid (manufactured by Nippon Coke Industries Co., Ltd.) and Nobilta (manufactured by Hosokawa Micron Co., Ltd.) as an external mixer.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the embodiments of the present invention are not limited thereto.

<Example 1>
Acrylic polyester A1 67.5 parts by mass [Composition (mol%) [Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: Polyoxyethylene (2.2) -2 , 2-Bis (4-hydroxyphenyl) propane: terephthalic acid = 80:20: 100], weight average molecular weight (Mw) = 7,000, acid value = 4 mgKOH / g, hydroxyl value = 55 mgKOH / g, glass transition point = 52 ° C]
Aspherical polyester B1 22.5 parts by mass [Composition (mol%) [Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: Polyoxyethylene (2.2) -2 , 2-bis (4-hydroxyphenyl) propane: fumaric acid: trimellitic acid = 60: 40: 80: 20], weight average molecular weight (Mw) = 150,000, acid value = 10 mgKOH / g, hydroxyl value = 50 mgKOH / G, glass transition point = 55 ° C]
Crystalline polyester 10 parts by mass [composition (molar ratio) [1,9-nonanediol: sebacic acid = 100: 100], weight average molecular weight (Mw) = 15,500, melting point = 72 ° C.]
・ Fischer-Tropschwax (peak temperature of maximum endothermic peak 78 ° C) 5 parts by mass ・ Copper phthalocyanine (CI Pigment Blue 15: 3) 7 parts by mass ・ Benzoic acid metal salt compound 1 1 part by mass [in formula (1) , R ₁ = R ₂ = R ₄ = R ₅ = H, R ₃ = C (CH ₃ ) ₃ , M = Al, m = 2, n = 1]
The above materials were mixed using a Henshell mixer (FM-75 type, manufactured by Mitsui Mine Co., Ltd.) at a rotation speed of 20 s ^-1 and a rotation time of 5 min, and then a twin-screw kneader (PCM-30) set at a temperature of 130 ° C. Kneaded with a mold (manufactured by Ikekai Co., Ltd.). The obtained kneaded product was cooled to 25 ° C. and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed product. The obtained coarse crushed product was finely pulverized with a mechanical crusher (T-250, manufactured by Turbo Industries, Ltd.). Further, classification was performed using Faculty F-300 (manufactured by Hosokawa Micron Co., Ltd.) to obtain toner 1.

Table 1 shows the constituent conditions of the obtained toner 1.

<Example 2>
Acrylic polyester B1 to amorphous polyester B2 [Composition (mol%) [Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: Polyoxyethylene (2.2) -2 , 2-Bis (4-hydroxyphenyl) propane: terephthalic acid: fumaric acid: trimellitic acid = 80: 20: 40: 30: 30], weight average molecular weight (Mw) = 760,000, acid value = 20 mgKOH / g , Hydroxy group value = 35 mgKOH / g, glass transition point = 55 ° C.], and the toner 2 having the constitution shown in Table 1 was obtained in the same manner as in Example 1.

<Example 3>
Toner 3 having the constitution shown in Table 1 was obtained in the same manner as in Example 1 except that the amorphous polyester A1 was changed to 49.5 parts by mass and the amorphous polyester B1 was changed to 40.5 parts by mass.

<Example 4>
Toner 4 having the constitution shown in Table 1 was obtained in the same manner as in Example 1 except that the amorphous polyester A1 was changed to 85.5 parts by mass and the amorphous polyester B1 was changed to 4.5 parts by mass.

<Example 5>
Amorphous polyester A1 to amorphous polyester A2 [Composition (mol%) [Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: Polyoxyethylene (2.2) -2 , 2-Bis (4-hydroxyphenyl) propane: terephthalic acid = 80:20: 100], weight average molecular weight (Mw) = 6,900, acid value = 1 mgKOH / g, hydroxyl value = 62 mgKOH / g, glass transition point = 53 ° C.], the toner 5 having the configuration shown in Table 1 was obtained in the same manner as in Example 1.

<Example 6>
Amorphous polyester A1 to amorphous polyester A3 [composition (mol%) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.2) -2 , 2-Bis (4-hydroxyphenyl) propane: terephthalic acid = 80:20: 100], weight average molecular weight (Mw) = 7,500, acid value = 9 mgKOH / g, hydroxyl value = 52 mgKOH / g, glass transition point = 54 ° C.] was obtained in the same manner as in Example 1 to obtain the toner 6 having the configuration shown in Table 1.

<Example 7>
Acrylic polyester A1 to amorphous polyester A4 [Composition (mol%) [Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: Polyoxyethylene (2.2) -2 , 2-Bis (4-hydroxyphenyl) propane: terephthalic acid = 80:20: 100], weight average molecular weight (Mw) = 7,500, acid value = 7 mgKOH / g, hydroxyl value = 42 mgKOH / g, glass transition point = 57 ° C.], and the amorphous polyester B1 was replaced with the amorphous polyester B3 [composition (mol%) [composition (mol%)] polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl). Propane: Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) Propane: Fumaric acid: Trimellitic acid = 60: 40: 80: 20], Weight average molecular weight (Mw) = 160,000 , Acid value = 15 mgKOH / g, hydroxyl value = 35 mgKOH / g, glass transition point = 56 ° C.], and the same as in Example 1, the toner 7 having the constitution shown in Table 1 was obtained.

<Example 8>
Acrylic polyester B1 to amorphous polyester B4 [composition (mol%) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.2) -2 , 2-bis (4-hydroxyphenyl) propane: fumaric acid: trimellitic acid = 80:20:90:10], weight average molecular weight (Mw) = 25,000, acid value = 16 mgKOH / g, hydroxyl value = 47 mgKOH A toner 8 having the configuration shown in Table 1 was obtained in the same manner as in Example 1 except that / g and the glass transition point = 53 ° C.].

<Example 9>
Acrylic polyester A1 to amorphous polyester A5 [Composition (mol%) [Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: Polyoxyethylene (2.2) -2 , 2-Bis (4-hydroxyphenyl) propane: terephthalic acid: fumaric acid = 80: 20: 60: 40], weight average molecular weight (Mw) = 7,300, acid value = 6 mgKOH / g, hydroxyl value = 53 mgKOH / The toner 9 having the configuration shown in Table 1 was obtained in the same manner as in Example 1 except that g, the glass transition point = 51 ° C.].

<Example 10>
The configurations shown in Table 1 are the same as in Example 1 except that the amorphous polyester A1 is changed to 52.5 parts by mass, the amorphous polyester B1 is changed to 17.5 parts by mass, and the crystalline polyester is changed to 30 parts by mass. Toner 10 was obtained.

<Example 11>
Toner 11 having the constitution shown in Table 1 was obtained in the same manner as in Example 1 except that the benzoic acid metal salt compound 1 was changed to 0.5 parts by mass.

<Example 12>
Toner 12 having the constitution shown in Table 1 was obtained in the same manner as in Example 1 except that the benzoic acid metal salt compound 1 was changed to 5 parts by mass.

<Example 13>
Benzoic acid metal salt compound 1 is changed to benzoic acid metal salt compound 2 [in formula (1), R ₁ = R ₂ = R ₄ = R ₅ = H, R ₃ = C (CH ₃ ) ₃ , M = Zn, m = 2, n = 0], the toner 13 having the configuration shown in Table 1 was obtained in the same manner as in Example 1.

<Example 14>
Benzoic acid metal salt compound 1 is changed to benzoic acid metal salt compound 3 [in formula (1), R ₁ = R ₂ = R ₄ = R ₅ = H, R ₃ = CH ₃ , M = Zn, m = 2, n = A toner 14 having the configuration shown in Table 1 was obtained in the same manner as in Example 1 except that it was changed to 0].

<Example 15>
Benzoic acid metal salt compound 1 is changed to benzoic acid metal salt compound 4 [in formula (1), R ₁ = R ₂ = R ₄ = R ₅ = H, R ₃ = C (CH ₃ ) ₃ , M = Na, m = 1, n = 0], the toner 15 having the configuration shown in Table 1 was obtained in the same manner as in Example 1.

<Comparative Example 1>
Toner 16 having the constitution shown in Table 1 was obtained in the same manner as in Example 1 except that the benzoic acid metal salt compound 1 was changed to 0.05 parts by mass.

<Comparative Example 2>
Toner 17 having the constitution shown in Table 1 was obtained in the same manner as in Example 1 except that the benzoic acid metal salt compound 1 was changed to 15 parts by mass.

<Comparative Example 3>
Amorphous polyester A1 to amorphous polyester A6 [composition (mol%) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.2) -2 , 2-Bis (4-hydroxyphenyl) propane: terephthalic acid = 80:20: 100], weight average molecular weight (Mw) = 7,400, acid value = 16 mgKOH / g, hydroxyl value = 35 mgKOH / g, glass transition point = 55 ° C.] was obtained in the same manner as in Example 1 except that the toner 18 having the configuration shown in Table 1 was obtained.

<Comparative Example 4>
Toner 19 having the constitution shown in Table 1 was obtained in the same manner as in Example 1 except that the amorphous polyester A1 was changed to 36 parts by mass and the amorphous polyester B1 was changed to 54 parts by mass.

<Comparative Example 5>
The toner 20 having the configuration shown in Table 1 was used in the same manner as in Example 1 except that the amorphous polyester A1 was changed to 75 parts by mass, the amorphous polyester B1 to 25 parts by mass, and the crystalline polyester to 0 parts by mass. Obtained.

<Comparative Example 6>
A toner 21 having the composition shown in Table 1 was obtained in the same manner as in Example 1 except that the benzoic acid metal salt compound 1 was changed to aluminum tribenzoate.

<Comparative Example 7>
Toner 22 having the composition shown in Table 1 was obtained in the same manner as in Example 1 except that the benzoic acid metal salt compound 1 was changed to 4-tert-butylbenzoic acid.

The following evaluation test was performed using each of the above toners. The evaluation results are shown in Table 2.

[Evaluation of charge retention]
0.01 g of toner was weighed in an aluminum pan and charged to −600 V using a strocon charging device. Subsequently, the change behavior of the surface potential was measured for 30 minutes using a surface electrometer (model 347 manufactured by Trek Japan) in an atmosphere of a temperature of 30 ° C. and a humidity of 80%. From the measurement results, the charge retention rate was calculated from the following formula.
Charge retention after 30 minutes (%) = (surface potential after 30 minutes / initial surface potential) × 100
A: Charge retention rate is 90% or more B: Charge retention rate is 50% or more and less than 90% C: Charge retention rate is 10% or more and less than 50% D: Charge retention rate is less than 10%

[Evaluation of low temperature fixability]
A two-component developer was prepared by mixing the toner and a ferrite carrier (average particle size 42 μm) surface-coated with a silicone resin so that the toner concentration was 8% by mass. The two-component developer was filled in a commercially available full-color digital copying machine (CLC1100, manufactured by Canon Inc.) to form an unfixed toner image (0.6 mg / cm ^{2 ) on a receiving paper (64 g / m 2).} The fixing unit removed from a commercially available full-color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon) was modified so that the fixing temperature could be adjusted, and a fixing test of an unfixed toner image was performed using this. The process speed was set to 246 mm / sec under normal temperature and humidity, and the state when the unfixed toner image was fixed was visually evaluated.

(Evaluation criteria)
A: Can be fixed in a temperature range of 130 ° C or lower B: Can be fixed in a temperature range higher than 130 ° C and 140 ° C or lower C: Can be fixed in a temperature range higher than 140 ° C and 150 ° C or lower C: 150 ° C There is a fixable area only in the higher temperature range

[Evaluation of heat storage resistance]
The toner was allowed to stand in a constant temperature and humidity chamber at 40 ° C. and a humidity of 95% for 2 weeks, and the degree of blocking was visually evaluated.
A: Blocking does not occur B: Even if blocking occurs, it is easily dispersed by light vibration.
C: Blocking occurs, but it disperses when it continues to vibrate.
D: Blocking occurs and does not disperse even when force is applied.

Claims (7)

A toner having toner particles containing a resin component and a benzoic acid metal salt compound.
The resin component has an amorphous polyester and an aliphatic crystalline polyester, and the resin component has an amorphous polyester and an aliphatic crystalline polyester.
The content of the amorphous polyester in the resin component is 50% by mass or more, and the content is 50% by mass or more.
The total acid value of the amorphous polyester is 3 mgKOH / g or more and 10 mgKOH / g or less, and the total hydroxyl value is 40 mgKOH / g or more and 70 mgKOH / g or less.
The amorphous polyester has an amorphous polyester (A) and an amorphous polyester (B).
The weight average molecular weights of the amorphous polyester (A) and the amorphous polyester (B) are Ma and Mb, the acid values are Aa (mgKOH / g) and Ab (mgKOH / g), and the hydroxyl value is OHa ( When the mass ratios in the amorphous polyester are Wa (mass%) and Wb (mass%), respectively, when mgKOH / g) and OHb (mgKOH / g) are used.
90 ≤ Wa + Wb ≤ 100,
Wa> Wb, Aa <Ab, OHa> OHb, Ma <Mb hold,
The benzoic acid metal salt compound is represented by the following formula (1), and is a toner characterized by containing 0.1% by mass or more and 10% by mass or less with respect to the total mass of the resin component.

(In the formula (1), R _{1 to} R ₅ are H or a linear or branched alkyl group having 3 or more carbon atoms. At least one of _{R 1 to} R _{5 is a linear chain having 3 or more carbon atoms.} Alternatively, it is a branched alkyl group. M is an integer of 1 to 3 and n is an integer of 0 to 2. M represents any of Na, K, Ca, Mg, Zn, and Al.) The mass ratio Wa (mass%) of the amorphous polyester (A) and the mass ratio Wb (mass%) of the amorphous polyester (B) are 0.6 ≦ Wa / (Wa + Wb) ≦ 0.9.
The toner according to claim 1. The toner according to claim 1 or 2, wherein the acid value Aa of the amorphous polyester (A) is 0 mgKOH / g or more and 7 mgKOH / g or less, and the hydroxyl value OHa is 45 mgKOH / g or more and 65 mgKOH / g or less. The item according to any one of claims 1 to 3, wherein the ratio (Ma / Mb) of the weight average molecular weight of the amorphous polyester (A) to the amorphous polyester (B) is 0.001 or more and 0.1 or less. The toner described. Among the dicarboxylic acid-derived units contained in the amorphous polyester (A) and the amorphous polyester (B), the proportions of the units derived from terephthalic acid represented by the formula (2) Ta (mol%) and Tb ( The toner according to any one of claims 1 to 4, wherein (mol%) is 70 ≦ Ta ≦ 100 and Ta> Tb.

The toner according to any one of claims 1 to 5, wherein the content of the aliphatic crystalline polyester in the resin component is 5% by mass or more and 30% by mass or less. In the above formula (1), R ₃ is a linear or branched alkyl group having 3 or more carbon atoms, R ₁ , R ₂ , R ₄ and R ₅ are H, and M is Zn and Al. The toner according to any one of claims 1 to 6.