WO2019124334A1

WO2019124334A1 - Toner

Info

Publication number: WO2019124334A1
Application number: PCT/JP2018/046451
Authority: WO
Inventors: 裕也千本; 紅一郎越智; 智代宮階; 崇平佐
Original assignee: キヤノン株式会社
Priority date: 2017-12-20
Filing date: 2018-12-18
Publication date: 2019-06-27

Abstract

Provided is a toner with excellent metallic gloss and bending resistance of images. The toner has a toner particle comprising a resin having an acid group, an aluminum pigment, and a fatty acid metal salt, wherein the acid value of the resin having an acid group is 5-25 mg KOH/g, the amount of the resin having an acid group is 50% by mass or more, the amount of the aluminum pigment is 10-40% by mass, the fatty acid metal salt is represented by the following formula (1), and the amount thereof is 1-10 parts by mass with respect to 100% by mass of the aluminum pigment. (In the formula (1), R is each independently a linear or branched alkyl or hydroxyalkyl group having 8-30 carbon atoms, M is Al, Zn, Mg, Ca, Sr, K, or Na, p is an integer of 1-3, and q is an integer of 0-2.)

Description

toner

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

In recent years, with the development of image forming apparatuses such as copying machines and printers, toners capable of coping with higher speed, higher image quality, longer life, and energy saving than ever before are required. In order to achieve high image quality, special color toners have been developed that cover colors that can not be expressed by conventional YMCK. One example is a toner that emits metallic gloss color (metallic color). For example, toners using metallic aluminum pigments have been developed to emit metallic gloss colors. (For example, Patent Document 1)

JP, 2014-157188, A

In order to enhance the metallic luster color, there is a means for containing a large amount of aluminum pigment in the toner. However, as a result, it was found that the bending resistance of the fixed image is lowered due to the decrease of the resin component.
In order to solve this problem, the bending resistance can be improved by using a high molecular weight resin having a large amount of crosslinking components. However, it has been found that the toner is difficult to be crushed, so that the aluminum pigment is hardly oriented, and the metallic gloss of the image is lowered.
To such a problem, an object of the present invention is to provide a toner excellent in the metallic gloss of an image and bending resistance.

As a result of intensive studies by the present inventors, it was found that the above problems can be solved by containing a resin having a specific acid value, an aluminum pigment, and a fatty acid metal salt in toner particles.
Fatty acid metal salts consist of carboxylic acid metal salt sites and long chain alkyl sites. Due to the presence of the fatty acid metal salt in the toner particles, the metal carboxylate metal salt portion of the fatty acid metal salt is an acid group of a resin having an acid group (for example, a carboxy group), and an alumina-derived hydroxyl group present on the surface of an aluminum pigment. It is thought that the interaction between the resin having an acid group and the aluminum pigment is intensified as a result.
Furthermore, it is speculated that the presence of a flexible long-chain alkyl moiety can relieve stress even if it is applied. It is considered that the above-described interaction is maintained even after the fixing step in the electrophotographic process, and as a result, the bending resistance of the image is improved.

That is, the toner of the present invention is
A toner comprising toner particles comprising a resin having an acid group, an aluminum pigment, and a fatty acid metal salt,
The acid value of the resin having the acid group is 5 mgKOH / g or more and 25 mgKOH / g or less, and the content of the resin having the acid group in the toner particle is 50% by mass or more.
The content of the aluminum pigment in the toner particles is 10% by mass to 40% by mass,
The fatty acid metal salt is represented by the following formula (1):
The toner is characterized in that the content of the fatty acid metal salt in the toner particles is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the aluminum pigment.

(In formula (1), each R independently represents a linear or branched alkyl group having 8 to 30 carbon atoms, or a linear or branched hydroxyalkyl having 8 to 30 carbon atoms M is a group represented by Al, Zn, Mg, Ca, Sr, K, or Na, p is an integer of 1 or more and 3 or less, and q is an integer of 0 or more and 2 or less.)

According to the present invention, it is possible to provide a toner excellent in the metallic glossiness and the bending resistance of an image.

In the present invention, the descriptions of “more than or equal to or less than xxx” or “○ to xxx” representing a numerical range mean a numerical range including the lower limit and the upper limit which are endpoints, unless otherwise noted.
The toner in the present invention contains a resin having an acid group in toner particles, an aluminum pigment, and a fatty acid metal salt.
The resin having an acid group used in the present invention means a resin having an acid group such as a carboxyl group or a sulfo group at an end or a side chain of a molecular chain. Specifically, acrylic resins, methacrylic resins, styrene-acrylic copolymers, styrene-methacrylic copolymers, polyester resins and the like can be suitably exemplified. Among these, it is preferable to use a polyester resin from the viewpoint of easily realizing the present embodiment.
In the present invention, the content of the resin having an acid group in toner particles is required to be 50% by mass or more. The resin having an acid group is composed of one or more resins. It is considered that the bendability is improved because the strength of the image is improved if the above range is satisfied.
The content of the resin having an acid group in toner particles is preferably 60% by mass or more. The upper limit is not particularly limited, but is preferably 85% by mass or less, more preferably 80% by mass or less.

The acid value of the resin having an acid group is required to be 5 mg KOH / g or more and 25 mg KOH / g or less from the viewpoint of bending resistance, and is preferably 7 mg KOH / g or more and 20 mg KOH / g or less. It is thought that the fatty acid metal salt described later interacts in a well-balanced manner with the resin having an acid group and the aluminum pigment described later within the above range, and the bending resistance is improved.
The acid value is the number of mg of potassium hydroxide required to neutralize the acid component such as free fatty acid and resin acid contained in 1 g of the sample. The measuring method is measured according to JIS-K 0070.

The polyester resin preferably contains a monomer unit derived from an alcohol component and a monomer unit derived from an acid component. In addition, a monomer unit means the form which the monomer substance in a polymer reacted. The following compounds are mentioned as a monomer which produces | generates a polyester resin.
Examples of the alcohol component include the following dihydric alcohols.
Ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol And 2-ethyl-1,3-hexanediol, hydrogenated Bisphenol A, bisphenols represented by the following formula (I) and derivatives thereof, and diols represented by the following formula (II).
As the alcohol component, as a polyhydric alcohol having a valence of 3 or more, 1,2,3-propanetriol, trimethylolpropane, hexanetriol, pentaerythritol or the like may be used.

(In the formula, R represents an ethylene group or a propylene group, X and Y each represent an integer of 0 or more, and the average value of X + Y is 0 or more and 10 or less.)

Examples of the acid component include the following divalent carboxylic acids.
Phthalic acid, terephthalic acid, isophthalic acid, benzenedicarboxylic acids such as phthalic anhydride, or anhydrides thereof; succinic acids, adipic acid, sebacic acid, alkyl dicarboxylic acids such as azelaic acid or anhydrides thereof; The following alkyl group or succinic acid or anhydride thereof substituted with an alkenyl group having 6 to 18 carbon atoms; fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acid such as itaconic acid or anhydride thereof.

It is also preferable to use a trivalent or higher polyvalent carboxylic acid as the acid component. For example, 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid and their acid anhydrides or lower alkyl esters Can be mentioned.
Among the above, aromatic compounds having high stability due to environmental changes are preferable, and examples thereof include 1,2,4-benzenetricarboxylic acid and its anhydride.

As the alcohol component, bisphenol represented by the formula (I) is preferable, and polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2, 2-Bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-) Hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4) More preferred are alkylene oxide adducts of bisphenol A, such as -hydroxyphenyl) propane. That is, the polyester resin preferably contains a monomer unit derived from an alkylene oxide adduct of bisphenol A. More preferably, it is a propylene oxide adduct of bisphenol A.
From the viewpoint of bending resistance, the content ratio of the monomer unit derived from the propylene oxide adduct of bisphenol A is preferably 70 mol% or more and 100 mol% or less among the monomer units derived from the alcohol component contained in the polyester resin, and 80 mol% It is more preferable that it is 100 mol% or less.
Although the ratio of the unit derived from the propylene oxide adduct of bisphenol A can be measured by a known method, for example, it can be measured by NMR.

The weight average molecular weight Mw of the polyester resin is preferably 50000 or more and 500000 or less, more preferably 80000 or more and 300000 or less, and still more preferably 100000 or more and 250,000 or less.

The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the polyester resin is preferably 10 or more from the viewpoint of metallic gloss and bending resistance, and more preferably 20 or more. On the other hand, the upper limit is not particularly limited, but is preferably 80 or less, more preferably 50 or less.

From the viewpoint of metallic gloss and bending resistance, the content ratio of the component having a molecular weight of 100 or more and 5000 or less measured by GPC of the tetrahydrofuran-soluble component of the polyester resin is based on the total mass of the tetrahydrofuran-soluble component of the polyester resin. It is preferable that it is 10 to 50 mass%, and it is more preferable that it is 20 to 40 mass%. The content ratio of the component having a molecular weight of 100 or more and 5,000 or less can be controlled, for example, by adjusting the polymerization conditions of the polyester resin, or by mixing a plurality of resins.

In the present invention, in addition to the resin having an acid group, other polymers may be used in combination as long as the effects of the present invention are not impaired. Specifically, homopolymers of styrene and its substitution products such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene, etc .; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinyl naphthalene Copolymers, Styrene copolymers such as styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer; polyvinyl chloride, phenolic resin, natural resin modified phenolic resin, natural resin modified maleic acid resin, acrylic Resin, methacrylic resin, polyvinyl acetate, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyethylene resin, polypropylene resin, etc. may be mentioned.

In the present invention, the aluminum pigment is a luster pigment used to develop a metallic feeling, and is a flat or scaly pigment having metal aluminum powder as a main component. The aluminum pigment may be subjected to a surface treatment with an inorganic oxide such as silica or a resin, if necessary. A commercially available thing can also be used for an aluminum pigment, For example, PCS900 (made by Eckart) etc. are mentioned.
The content of the aluminum pigment in the toner particles is required to be 10% by mass or more and 40% by mass or less from the viewpoint of metallic gloss. The content of the aluminum pigment is preferably 15% by mass or more and 35% by mass or less.

The volume average particle diameter of the aluminum pigment is preferably 0.5 μm to 30 μm from the viewpoint of metallic gloss, and more preferably 1.0 μm to 20 μm.

In the present invention, a fatty acid metal salt refers to a compound represented by the following formula (1).

In the formula (1), each R independently represents a linear or branched alkyl group having 8 to 30 carbon atoms (preferably 9 to 25 carbon atoms), or 8 to 30 carbon atoms (preferably 9 carbon atoms). A linear or branched hydroxyalkyl group, wherein M is Al, Zn, Mg, Ca, Sr, K, or Na, and p is 1 or more and 3 or less (preferably 2 or more and 3 or less). The following integer), q represents an integer of 0 or more and 2 or less (preferably 0 or more and 1 or less). The metal M is preferably Al, Zn, Mg, Ca or Sr.

The fatty acid metal salt is contained in the toner particles, and is preferably present inside the toner particles. The content of the fatty acid metal salt in the toner particles is required to be 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the aluminum pigment from the viewpoint of bending resistance. Preferably, it is 1 to 5 parts by mass.

An endothermic peak area at melting point T (° C.) of a fatty acid metal salt alone measured by a differential scanning calorimeter (DSC) using 0.01 g of fatty acid metal salt alone is S1 (J), and a difference is made using 0.01 g of toner The peak area of the maximum endothermic peak in a temperature range of T-10 (° C.) or more and T + 10 (° C.) or less measured by a scanning calorimeter (DSC) is S2 (J), and fatty acid metal salt contained in 0.01 g of toner When the mass is W (g), it is preferable that 0 ≦ (S2 / W) / (S1 / 0.01) ≦ 0.5. More preferably, 0 ≦ (S2 / W) / (S1 / 0.01) ≦ 0.3, and still more preferably 0 ≦ (S2 / W) / (S1 / 0.01) ≦ 0.2. is there.
Within the above range, the proportion of the fatty acid metal salt compatible with the toner particles is appropriate, which is preferable from the viewpoint of bending resistance. S2 can be controlled, for example, by means such as selection of resin type and adjustment of production conditions (for example, kneading and cooling conditions in the pulverization method).
In addition, the specific measuring method of a differential scanning calorimeter (DSC) is as follows. The measuring device uses a differential scanning calorimeter “Q2000” manufactured by TA Instruments. A 0.01 g 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.
In the measurement from the toner, the fatty acid metal salt can be separated and measured by the following method.

(Separation of fatty acid metal salt from toner)
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water, and dissolved while heating in water to prepare a sucrose concentrate. In a tube for centrifugation, 31 g of the above sucrose concentrate, and Contaminone N (a 10% by weight aqueous solution of a neutral detergent for cleaning a pH 7 precision measuring instrument consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, 6 mL of Wako Pure Chemical Industries, Ltd. is added to prepare a dispersion. To this dispersion is added 1.0 g of toner, and the toner is loosened with a spatula or the like. Next, shake the centrifuge tube with a shaker. After shaking, the solution is replaced with a glass tube for swing rotor (50 mL), and separated with a centrifuge under conditions of 3500 rpm and 30 minutes.
By this operation, the toner particles and the detached external additive are separated. The toner particles are visually observed to be sufficiently separated from each other, and the toner particles are collected, filtered by a vacuum filter, and then dried by a drier for 1 hour or more, and the external additive is separated. Get
Further, the obtained toner particles are separated by dissolving soluble components other than aluminum pigment and fatty acid metal salt with a solvent such as tetrahydrofuran, toluene and hexane, and further fatty acid metal salt is extracted with a heated solvent such as xylene or toluene The fatty acid metal salt is separated by concentrating and drying the filtrate.

The acid value of the resin having an acid group is A (mg KOH / g), the content of the resin having an acid group contained in 1 g of toner particles is a (g), and the fatty acid metal salt contained in 1 g of toner particles From the viewpoint of bending resistance that [A × a / (56.1 × 1000)] / b is 0.10 or more and 0.50 or less, where b (mol) is the content of the metal M contained preferable. More preferably, it is 0.20 or more and 0.40 or less.
[A × a / (56.1 × 1000)] / b indicates the molar ratio of the acid group of the resin having an acid group to the metal of the fatty acid metal salt. The interaction between the fatty acid metal salt becomes moderate, and as a result, the interaction between the three substances including the aluminum pigment works effectively, so the bending resistance becomes better.

The detected amount of metal atom contained in fatty acid metal salt measured by surface analysis of toner by X-ray photoelectron spectroscopy (ESCA) is c [atom%], and metal M contained in fatty acid metal salt contained in 100 g of toner It is preferable that c and d satisfy c / d ≦ 1 where d [mol] is the content of More preferably, 0 ≦ c / d ≦ 0.5 is satisfied.
c / d is an index indicating how much fatty acid metal salt contained in the toner is present on the outermost surface of the toner particle. When c / d is in the above range, the fatty acid metal salt is present inside the toner particles, and as a result, the resin having an acid group and the aluminum pigment easily interact with the fatty acid metal salt, so that the bending resistance is improved. Sex is good.

The specific measurement method of X-ray photoelectron spectroscopy (ESCA) is as follows. The apparatus is performed using an X-ray photoelectron spectroscopy analyzer (PHI (registered trademark) 5000 VERSAP ROBE II, manufactured by ULVAC-PHI, Inc.).
The toner is placed in a recess of a sample table, pressed and scraped, introduced into a chamber, and X-Raysetting is measured under the conditions of 100 μm (beam diameter) 25 W 15 kV, Pass Energy 58.7 eV, and Step 0.125 eV. The measurement result is analyzed, and c [atom%] is calculated from the peak intensity of the metal contained in the fatty acid metal salt.

The toner may contain a release agent. As a mold release agent, the following are mentioned, for example.
Low molecular weight polyolefins such as polyethylene; silicones having a melting point (softening point) upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide and stearic acid amide; esters such as stearyl stearate Waxes; plant-based waxes such as carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil; animal-based waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax And mineral and petroleum waxes such as ester waxes; and modified products thereof.
The content of the release agent is preferably 1 part by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the resin having an acid group.
The melting point of the release agent is preferably 50 ° C. or more and 100 ° C. or less, and more preferably 70 ° C. or more and 100 ° C. or less.

A publicly known method can be used as a method of producing toner particles. It is preferable to have the process of mixing and heat-kneading the resin which has an acidic radical, fatty acid metal salt, and an aluminum pigment. That is, the toner particles are preferably pulverized toner particles.
Hereinafter, a toner manufacturing procedure in the pulverizing method will be described as an example.
In the raw material mixing step, for example, a predetermined amount of a resin having an acid group, a fatty acid metal salt, an aluminum pigment, and other components such as a releasing agent and a charge control agent are weighed as materials constituting toner particles. Mix and mix. Examples of the mixing apparatus include a double con mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano hybrid (manufactured by Nippon Coke Industry Co., Ltd.).

Next, the mixed materials are melt-kneaded. In the melt-kneading step, a batch-type kneader such as a pressure kneader or a Banbury mixer, or a continuous-type kneader can be used, and a single-screw or twin-screw extruder is preferable from the viewpoint of continuous production. The temperature for melt kneading is preferably about 100 to 200 ° C.
For example, a KTK type twin screw extruder (made by Kobe Steel, Ltd.), a TEM type twin screw extruder (made by Toshiba Machine Co., Ltd.), a PCM kneader (made by Ikegai Iron Works), a twin screw extruder (made by Kay C.K.) And Ko Kneader (manufactured by Bus Co., Ltd.) and Niedex (manufactured by Japan Coke Industry Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading is rolled by two rolls etc., and it quenches with water etc. at a cooling process.

The cooled resin composition is then ground to the desired particle size in the grinding step. In the grinding process, for example, after coarsely grinding with a grinder such as crusher, hammer mill, feather mill, etc., for example, Cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), superrotor (manufactured by Nisshin Engineering), turbo, Milled with a mill (manufactured by Turbo Kogyo Co., Ltd.) or an air jet type pulverizer.
After that, if necessary, inertial classification type elbow jet (made by Nittetsu Mining Co., Ltd.), centrifugal force classification type Turboplex (made by Hosokawa Micron), TSP separator (made by Hosokawa Micron), Faculty (made by Hosokawa Micron) Classification is performed using a classifier or a sieving machine to obtain a classified product (toner particles).

The obtained toner particles may be used as a toner as it is. If necessary, an external additive may be externally added to the surface of the toner particles to form a toner. As a method of adding external additives, toner particles and various known external additives are compounded in predetermined amounts, and double con mixer, V type mixer, drum type mixer, super mixer, Henschel mixer, Nauta mixer, mechano hybrid ( The method of stirring and mixing using mixing apparatuses, such as Nippon Coke Kogyo Co., Ltd.) and Nobilta (made by Hosokawa Micron Corporation), is used as an external adder.
The toner of the present invention preferably has a volume-based median diameter of 3.0 μm or more and 30.0 μm or less, and more preferably 4.0 or more and 20.0 μm or less.

Hereinafter, the measuring method of the physical property relevant to this invention is described.
<Measurement of Content of Resin Having Acid Groups in Toner Particles>
From the toner particles from which the external additive has been separated by the above-mentioned method, a resin having an acid group is dissolved with a solvent such as tetrahydrofuran and filtered to extract a filtrate. After centrifuging the filtrate, the content of the resin having an acid group is measured by concentrating and drying.

<Measurement of Aluminum Pigment Content in Toner Particles>
The aluminum pigment and the fatty acid metal salt are separated from the toner particles from which the external additive has been separated by the above-described method, and the fatty acid metal salt is extracted with a heated solvent such as xylene or toluene, and the amount of the remaining aluminum pigment is measured.

<Measurement of Fatty Acid Metal Salt Content in Toner Particles>
The fatty acid metal salt is extracted and measured in the manner described above. The structure of the residual fatty acid metal salt is determined using nuclear magnetic resonance spectroscopy (NMR), infrared spectroscopy (IR), and fluorescent X-ray measurement.

<Measurement of Metal M Content Contained in Fatty Acid Metal Salt in Toner Particles>
After fatty acid metal salts are extracted by the above-mentioned method, quantification is carried out using fluorescent X-ray measurement or ICP emission analysis.

<Measurement of Number Average Molecular Weight (Mn) and Weight Average Molecular Weight (Mw) of Resin Having Acid Group>
The number average molecular weight (Mn) and the weight average molecular weight (Mw) are measured by gel permeation chromatography (GPC) as follows.
First, the sample (resin) is dissolved in tetrahydrofuran (THF) for 24 hours at room temperature. Then, the resulting solution is filtered through a solvent-resistant membrane filter "Maechoridisc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. It measures on condition of the following using this sample solution.
Device: HLC8120 GPC (detector: RI) (made by Tosoh Corporation)
Column: 7 series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (made by Showa Denko)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- 10, use a molecular weight calibration curve prepared using F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500, manufactured by Tosoh Corporation).

<Method of measuring acid number>
The acid value is the number of mg of potassium hydroxide necessary to neutralize the acid contained in 1 g of the sample. The acid value of a material such as a resin having an acid group is measured according to JIS K 0070-1992, and specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95% by volume), ion-exchanged water is added to make it 100 ml, and a phenolphthalein solution is obtained.
7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 volume%) is added to make 1 liter. After being placed in an alkali resistant container and allowed to stand for 3 days so as not to touch carbon dioxide gas etc., filtration is performed to obtain a potassium hydroxide solution. The resulting potassium hydroxide solution is stored in an alkali resistant container. The factor of the potassium hydroxide solution is as follows: 25 ml of 0.1 mol / l hydrochloric acid is taken in an Erlenmeyer flask, several drops of the phenolphthalein solution are added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization Determine from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main Test A 2.0 g sample is precisely weighed in a 200 ml Erlenmeyer flask, 100 ml of a mixed solution of toluene / ethanol (2: 1) is added, and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is assumed to be when the pale pink color of the indicator lasts for about 30 seconds.
(B) Blank test The same titration as in the above operation is performed except that no sample is used (ie, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The obtained result is substituted into the following equation to calculate the acid value.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mg KOH / g), B: addition amount of potassium hydroxide solution of blank test (ml), C: addition amount of potassium hydroxide solution of this test (ml), f: potassium hydroxide Solution factor, S: mass of sample (g).
(When measuring from toner)
From the toner particles from which the external additive has been separated by the above-mentioned method, a resin having an acid group is dissolved with a solvent such as tetrahydrofuran and filtered to extract a filtrate. After centrifuging the filtrate, the acid value of the resin having an acid group obtained by concentration and drying is measured.

<A measurement of the content ratio of a component having a molecular weight of 100 or more and 5000 or less measured by GPC of the THF soluble portion of the resin having an acid group>
From the integrated molecular weight distribution curve obtained by GPC measurement, the integrated concentration of molecular weight in the range of 100 to 5,000 is determined, and the content ratio is calculated.

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples, but the embodiments of the present invention are not limited thereto. In addition, the number of parts and% of an Example and a comparative example are all mass references | standards unless there is particular notice. The constitution conditions of each toner particle are shown in Table 1.

Example 1
・ Polyester resin 1: 64 parts [composition (mol%) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: terephthalic acid: dodecyl succinic acid: trimellitic acid = 80: 20: 75: 10: 15], Mw = 152,000, Mw / Mn = 32, the amount of components having a molecular weight of 100 to 5,000 = 25% by mass, acid value = 12 mg KOH / g]
Aluminum pigment (PCS 900, silica treated metal aluminum pigment, manufactured by Eckart): 30 parts Fischer Tropsch wax (melting point 78 ° C.): 5 parts Calcium distearate: 1 part [in the formula (1), R = C ₁₇ H ₃₅ , M = Ca, p = 2, q = 0]
A two-shaft kneader (PCM-30) set to a temperature of 130 ° C. after mixing the above materials using a Henschel mixer (type FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s ⁻¹ for 5 minutes. Kneaded in a mold, manufactured by Ikegai Co., Ltd.). The resulting kneaded product was cooled to 25 ° C., and roughly crushed to 1 mm or less with a hammer mill to obtain a coarse product. The obtained crude material was finely pulverized by a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles 1.
To 100 parts of the obtained toner particles, 1.5 parts of hydrophobized silica fine powder having a primary particle diameter of 10 nm and 2.5 parts of hydrophobized silica fine powder having a primary particle diameter of 100 nm are used. Dry mixing was carried out with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain Toner 1. The volume-based median diameter of Toner 1 was 9.3 μm.

Example 2
Toner 2 was obtained in the same manner as in Example 1 except that 84 parts of polyester resin 1 and 10 parts of aluminum pigment were used. The volume-based median diameter of Toner 2 was 9.3 μm.

Example 3
Toner 3 was obtained in the same manner as in Example 1 except that 54 parts of polyester resin 1 and 40 parts of aluminum pigment were used. The volume-based median diameter of Toner 3 was 9.5 μm.

Example 4
Polyester resin 1 to polyester resin 2 [composition (mol%) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: fumaric acid: trimellitic acid = 72: 28: 90: 10], Mw = 91,000, Mw / Mn = 25, amount of components having a molecular weight of 100 or more and 5000 or less = 31% by mass, acid Toner 4 was obtained in the same manner as in Example 1 except that the pigment amount was changed to 7 mg KOH / g]. The volume-based median diameter of Toner 4 was 9.0 μm.

Example 5
Polyester resin 1 is polyester resin 3 [composition (mol%) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: fumaric acid: dodecyl succinic acid: trimellitic acid = 77: 23: 65: 5:30], Mw = 121,000, Mw / Mn = 35, the amount of components having a molecular weight of 100 to 5000 Toner 5 was obtained in the same manner as in Example 1 except that the acid content was changed to 32% by mass, and the acid value was 21 mgKOH / g. The volume-based median diameter of the toner 5 was 9.3 μm.

Example 6
Toner 6 was obtained in the same manner as in Example 1 except that 64.5 parts of polyester resin 1 and 0.5 parts of calcium distearate were changed. The volume-based median diameter of Toner 6 was 9.2 μm.

Example 7
Toner 7 was obtained in the same manner as in Example 1 except that 63 parts of polyester resin 1 and 2 parts of calcium distearate were changed. The volume-based median diameter of Toner 7 was 9.1 μm.

Example 8
Toner 8 in the same manner as in Example 1 except that calcium distearate was changed to aluminum tristearate [in formula (1), R = C ₁₇ H ₃₅ , M = Al, p = 3, q = 0]. I got The volume-based median diameter of the toner 8 was 9.3 μm.
As described above, the silica fine powder and the polyester resin are removed from the toner 8, and aluminum tristearate is extracted using xylene heated to 110 ° C., and after drying, the aluminum tristearate is fluorescent X-ray It quantified by measurement.
The remaining aluminum pigment was dried and weighed. The content of the aluminum pigment in the toner particles obtained by the above method was 30% by mass, and the content of aluminum tristearate relative to the aluminum pigment was 3.3% by mass.

Example 9
Except changing calcium distearate to sodium stearate [in formula (1), R = C ₁₇ H ₃₅ , M = Na, p = 1, q = 0] and the temperature of the twin-screw kneader to 180 ° C. In the same manner as in Example 1, a toner 9 was obtained. The volume-based median diameter of Toner 9 was 9.4 μm.

Example 10
Calcium distearate is biaxially converted to calcium 12-hydroxy distearate [in the formula (1), R = C ₆ H ₁₃ -CH (OH) -C ₁₀ H ₂₀ , M = Ca, p = 2, q = 0]. A toner 10 was obtained in the same manner as in Example 1 except that the temperature of the kneader was changed to 160 ° C. The volume-based median diameter of the toner 10 was 8.9 μm.

Example 11
Except that calcium distearate was changed to calcium behenate [in formula (1), R = C ₂₁ H ₄₃ , M = Ca, p = 2, q = 0] and the temperature of the twin-screw kneader to 140 ° C. In the same manner as in Example 1, a toner 11 was obtained. The volume-based median diameter of the toner 11 was 9.3 μm.

Example 12
Toner 12 is prepared in the same manner as in Example 1 except that calcium distearate is changed to calcium decanoate [in formula (1), R = C ₉ H ₁₉ , M = Ca, p = 2, q = 0]. Obtained. The volume-based median diameter of the toner 12 was 9.1 μm.

Example 13
Polyester resin 1 to polyester resin 4 [composition (mol%) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: fumaric acid: trimellitic acid = 55: 45: 85: 15], Mw = 132,000, Mw / Mn = 36, component amount of molecular weight 100 or more and 5000 or less = 33% by mass, acid The toner 13 was obtained in the same manner as in Example 1 except that the toner amount was changed to 11 mg KOH / g. The volume-based median diameter of the toner 13 was 9.2 μm.

Example 14
Polyester resin 1 to polyester resin 5 [composition (mol%) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: fumaric acid: trimellitic acid = 74: 26: 95: 5], Mw = 52,000, Mw / Mn = 12, amount of components having a molecular weight of 100 or more and 5000 or less = 29% by mass, acid Toner 14 was obtained in the same manner as in Example 1 except that the pigment amount was changed to 14 mg KOH / g]. The volume-based median diameter of the toner 14 was 9.2 μm.

Example 15
Polyester resin 1 to polyester resin 6 [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: 35: 55: 10], Mw = 110,000, Mw / Mn = 11, the amount of components having a molecular weight of 100 to 5000, = A toner 15 was obtained in the same manner as in Example 1 except that the amount was changed to 18% by mass, and the acid value = 15 mg KOH / g. The volume-based median diameter of the toner 15 was 9.0 μm.

Example 16
A toner 16 was obtained in the same manner as in Example 1 except that the temperature of the twin-screw kneader was changed to 100 ° C. The volume-based median diameter of the toner 16 was 9.3 μm.

Example 17
Toner 17 was obtained in the same manner as in Example 1 except that 64.6 parts of polyester resin 1 and 0.4 parts of calcium distearate were changed. The volume-based median diameter of the toner 17 was 9.3 μm.

Example 18
Toner 18 was obtained in the same manner as in Example 1 except that 61.5 parts of polyester resin 1 and 3.5 parts of calcium distearate were changed. The volume-based median diameter of the toner 18 was 9.1 μm.

Example 19
Toner 19 is prepared in the same manner as in Example 1 except that calcium distearate is changed to zinc distearate [in formula (1), R = C ₁₇ H ₃₅ , M = Zn, p = 2, q = 0]. Obtained. The volume-based median diameter of the toner 19 was 9.2 μm.

Example 20
Polyester resin 1 is a styrene acrylic resin S1 [composition (mol%) styrene: n butyl acrylate: acrylic acid = 76: 22: 2], Mw = 51,000, Mw / Mn = 3, the amount of components having a molecular weight of 100 or more and 5000 or less A toner 20 was obtained in the same manner as in Example 1, except that the acid value was changed to 10% by mass and the acid value was 9 mgKOH / g. The volume-based median diameter of the toner 20 was 9.4 μm.

Comparative Example 1
A toner 21 was obtained in the same manner as in Example 1, except that 89.8 parts of polyester resin 1, 5 parts of aluminum pigment, and 0.2 parts of calcium distearate were changed. The volume-based median diameter of the toner 21 was 9.0 μm.

Comparative Example 2
A toner 22 was obtained in the same manner as in Example 1, except that 44 parts of polyester resin 1, 50 parts of aluminum pigment, and 1 part of calcium distearate were changed. The volume-based median diameter of the toner 22 was 9.6 μm.

Comparative Example 3
A toner 23 was obtained in the same manner as in Example 1, except that 64.8 parts of polyester resin 1 and 0.2 parts of calcium distearate were changed. The volume-based median diameter of the toner 23 was 9.1 μm.

Comparative Example 4
A toner 24 was obtained in the same manner as in Example 1, except that 60 parts of polyester resin 1 and 5 parts of calcium distearate were changed. The volume-based median diameter of the toner 24 was 9.4 μm.

Comparative Example 5
Polyester resin 1 was polyester resin 7 [composition (mol%) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: terephthalic acid: trimellitic acid = 100: 90: 10], Toner 25 is obtained in the same manner as in Example 1, except that Mw = 185,000, Mw / Mn = 36, the amount of components having a molecular weight of 100 to 5,000 = 27% by mass, and the acid value = 3 mg KOH / g]. The The volume-based median diameter of the toner 25 was 9.2 μm.

Comparative Example 6
Polyester resin 1 to polyester resin 8 [composition (mol%) [polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: fumaric acid: trimellitic acid = 75: 25: 80: 20], Mw = 154,000, Mw / Mn = 39, component amount of molecular weight 100 or more and 5000 or less = 28% by mass, acid Toner 26 was obtained in the same manner as in Example 1 except that the pigment amount was changed to 27 mg KOH / g]. The volume-based median diameter of the toner 26 was 9.0 μm.

Comparative Example 7
Toner 27 was obtained in the same manner as in Example 1 except that calcium benzoate was changed to calcium benzoate. The volume-based median diameter of the toner 27 was 9.2 μm.

Comparative Example 8
Toner 28 was obtained in the same manner as in Example 1 except that calcium distearate was changed to calcium propionate. The volume-based median diameter of the toner 28 was 9.3 μm.

Comparative Example 9
Toner particles 27 were obtained in the same manner as in Example 1 except that 65 parts of polyester resin 1 and 0 parts of calcium distearate were changed, to 100 parts of the obtained toner particles, and the primary particle diameter was 10 nm. 1.5 parts of hydrophobized silica fine powder and 2.5 parts of hydrophobized silica fine powder having a primary particle diameter of 100 nm and 1 part of calcium stearate are dry mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) Toner 29 was obtained. The volume-based median diameter of the toner 29 was 10.1 μm.

The following evaluation test was performed using each of the above toners. The evaluation results are shown in Table 1.
<Metal gloss>
Each of the above toners and a ferrite carrier (average particle diameter 42 μm) surface-coated with a silicone resin were mixed so that the toner concentration was 8% by mass, to prepare a two-component developer. Using a commercially available full color digital copier (CLC1100, manufactured by Canon Inc.), an unfixed toner image (0.9 mg / cm ² ) on coated paper (OK Top Coat +, Oji Paper, 127 g / m ² ) It formed.
The fixing unit removed from a commercially available full-color digital copier (imageRUNNER ADVANCE C5051, manufactured by Canon) is modified so that the fixing temperature can be adjusted, and the process speed is set to 357 mm / sec under room temperature 15 ° C, humidity 10%, The unfixed image was fixed. The specular reflectance of the image of the fixed material at the highest fixable temperature is measured with a variable angle photometer GH-100S (incident angle 45 °, light receiving angle 315 °) manufactured by Asahi Spectroscope, and the metal is combined with visual observation and metal The gloss was evaluated.
(Evaluation criteria)
A: The specular reflectance is 1% or more, and the metallic gloss is high visually B: the specular reflectance is 0.5% or more and less than 1%, the metallic gloss is visually observed C: positive The reflectance is less than 0.5%, and there is almost no metallic luster visually

<Bending resistance>
The two-component developer obtained above was used with a commercially available full color digital copier (CLC1100, manufactured by Canon Inc.) to obtain an unfixed toner image (0.9 mg / cm ² ) on an image receiving paper (64 g / m ² ). Formed. The fixing unit removed from a commercially available full-color digital copier (imageRUNNER ADVANCE C5051, manufactured by Canon) is modified so that the fixing temperature can be adjusted, and the process speed is set to 357 mm / sec under room temperature 15 ° C, humidity 10%, The unfixed image was fixed.
The fixed image at the maximum fixable temperature was folded in a cross, and rubbed five times with a soft thin paper (trade name "Dasper", manufactured by Ozu Sangyo Co., Ltd.) while applying a load of 4.9 kPa. Next, an area of 512 pixels square of the cross portion with a resolution of 800 pixels / inch was photographed with a CCD camera. The threshold value was set to 60%, the image was binarized, and the area ratio of the white part which was the part where the toner peeled was measured. The smaller the area ratio of the white part, the better the bending resistance. (Evaluation criteria)
A: Area ratio of white part is less than 2.0% B: Area ratio of white part is 2.0% or more and less than 4.0% C: Area ratio of white part is 4.0% or more and less than 6.0% D : Area ratio of white part is 6.0% or more

In the table, A is a value of “[A × a / (56.1 × 1000)] / b”, B is “(S2 / W) / (S1 / 0.01)”, and C is It is the value of c / d. The content of the resin having an acid group and the aluminum pigment is the content in the toner particles, and the content of the fatty acid metal salt indicates the number of parts by mass with respect to 100 parts by mass of the aluminum pigment. The “PO ratio” indicates the content ratio of monomer units derived from a propylene oxide adduct of bisphenol A among monomer units derived from an alcohol component. The “low molecular weight component amount” indicates the content ratio of a component having a molecular weight of 100 or more and 5,000 or less measured by GPC of the THF soluble portion of the polyester resin. The unit of acid value is mg KOH / g.
The present invention is not limited to the above embodiment, and various changes and modifications can be made without departing from the spirit and scope of the present invention. Accordingly, the following claims are attached to disclose the scope of the present invention.
The present application claims priority based on Japanese Patent Application No. 2017-243768 filed on Dec. 20, 2017 and Japanese Patent Application No. 2018-208435 submitted on November 5, 2018, The entire contents of the description are incorporated herein.

Claims

A toner comprising toner particles comprising a resin having an acid group, an aluminum pigment, and a fatty acid metal salt,
The acid value of the resin having the acid group is 5 mgKOH / g or more and 25 mgKOH / g or less, and the content of the resin having the acid group in the toner particle is 50% by mass or more.
The content of the aluminum pigment in the toner particles is 10% by mass to 40% by mass,
The fatty acid metal salt is represented by the following formula (1):
The toner according to claim 1, wherein the content of the fatty acid metal salt in the toner particles is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the aluminum pigment.

(In formula (1), each R independently represents a linear or branched alkyl group having 8 to 30 carbon atoms, or a linear or branched hydroxyalkyl having 8 to 30 carbon atoms M is a group represented by Al, Zn, Mg, Ca, Sr, K, or Na, p is an integer of 1 or more and 3 or less, and q is an integer of 0 or more and 2 or less.)
The acid value of the resin having the acid group is A (mg KOH / g),
The content of the resin having the acid group contained in 1 g of the toner particles is a (g),
When the content of the metal M contained in the fatty acid metal salt contained in 1 g of the toner particles is b (mol), [A × a / (56.1 × 1000)] / b is 0.10 or more and 0 The toner according to claim 1, which is not more than 50.
The toner according to claim 1, wherein the metal M contained in the fatty acid metal salt is Al, Zn, Mg, Ca, or Sr.
The toner according to any one of claims 1 to 3, wherein the resin having an acid group is a polyester resin.
The toner according to claim 4, wherein the polyester resin contains a monomer unit derived from an alkylene oxide adduct of bisphenol A.
6. The toner according to claim 4, wherein a content ratio of a monomer unit derived from a propylene oxide adduct of bisphenol A is 70 mol% or more and 100 mol% or less among monomer units derived from an alcohol component contained in the polyester resin.
The weight average molecular weight Mw of the polyester resin is 50000 or more and 500000 or less,
The toner according to any one of claims 4 to 6, wherein a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the polyester resin is 20 or more.
The content ratio of the component having a molecular weight of 100 to 5,000 measured by gel permeation chromatography of the tetrahydrofuran soluble component of the polyester resin is 20% by mass or more based on the total mass of the tetrahydrofuran soluble component of the polyester resin The toner according to any one of claims 4 to 7.
An endothermic peak area at the melting point T (° C.) of the fatty acid metal salt alone measured by a differential scanning calorimeter (DSC) using 0.01 g of the fatty acid metal salt alone is S1 (J),
The peak area of the maximum endothermic peak in a temperature range of T-10 (° C.) or more and T + 10 (° C.) or less measured by a differential scanning calorimeter (DSC) using 0.01 g of the toner is S2 (J)
When the mass of the fatty acid metal salt contained in 0.01 g of the toner is W (g),
9. The toner according to any one of claims 1 to 8, wherein 0 ≦ (S2 / W) / (S1 / 0.01) ≦ 0.3.
The detected amount of metal atoms contained in the fatty acid metal salt measured by surface analysis of the toner by X-ray photoelectron spectroscopy (ESCA) is c [atom%], and the fatty acid metal salt contained in 100 g of the toner 10. The toner according to any one of claims 1 to 9, wherein c and d satisfy the relationship of c / d ≦ 1 where d (mol) is the content of the metal M contained.
The toner according to any one of claims 1 to 10, wherein the toner particles are pulverized toner particles.