JP7451166B2 - toner - Google Patents

Description

The present invention relates to a toner for developing electrostatic images used in electrophotography, electrostatic recording, and the like.

As copying machines and printers have become more widespread, the performance required of toner has also become more sophisticated. In recent years, a digital printing technology called print-on-demand (POD), which directly prints without going through a plate-making process, has been attracting attention. In the POD market, while supporting a wide range of media (paper types), it is possible to stably obtain print products with higher image quality than before, even when outputting at high speed and in large quantities over a long period of time. Desired. Therefore, in addition to having a wide fixing area and high charge maintenance properties, toners are required to maintain stable fluidity over a long period of time.

Patent Document 1 discloses a toner that has excellent charging stability and blocking resistance by using a toner containing a composite polyester in which silicone oil is bonded to polyester.

Further, Patent Document 2 proposes to maintain the fluidity of toner by adding large-diameter silica particles formed by a sol-gel method to toner particles.

Japanese Patent Application Publication No. 2002-12657 JP2012-163623A

The toner disclosed in Patent Document 1 has good toner fixability and charging stability, but a portion derived from the silicone oil and a portion derived from the functional group of the polyester resin exist unevenly on the surface, and one toner particle There were variations in the adhesion distribution on the surface layer. Therefore, when viewed in a minute area, there is a difference in fluidity between the toners, and a slight disturbance of dots occurs during transfer, which tends to cause roughness in the image. Such a phenomenon is particularly noticeable in a low-humidity environment that is easily affected by charging. Furthermore, since the adhesive force distribution on the surface layer of a single toner particle becomes non-uniform, a phenomenon called fixing explosion, in which the toner image on the image is disturbed by the influence of the fixing member during fixing, tends to occur. As a result, an image problem called trailing occurs in the image.

On the other hand, in the invention of Patent Document 2, the fluidity of the toner is improved by using large-sized silica particles. However, when used for a long period of time, the silica particles migrate from the toner particle surface to the carrier or become embedded in the toner, resulting in the binding resin part of the toner matrix being exposed to the surface layer, Affected by the fluidity of origin. As a result, there is room for improvement when considering obtaining high-quality images over a long period of time.

The present invention has been made to solve the above-mentioned problems, and its purpose is to have a wide fixing area and suppress roughness and trailing even when used for a long period of time in a low humidity environment. An object of the present invention is to provide a toner capable of printing high-quality images.

The present invention provides a toner containing toner particles having a binder resin and a polar group-containing olefin copolymer, the binder resin comprising a modified polyester having a silicone unit represented by the following general formula [1]. and the content of the modified polyester is 50.0% by mass or more in the binder resin, and the modified polyester contains the silicone unit at 0.5% by mass or more and 5.0% by mass or less, The polar group-containing olefin copolymer is a polymer having a polar unit and a polyolefin unit, and the polar unit is an α,β-unsaturated carboxylic acid and a derivative thereof, an unsaturated nitrile and a derivative thereof. The present invention relates to a toner characterized in that the unit is derived from any compound selected from the group consisting of.

（式中、Ｒ_１およびＲ_２は、それぞれ独立して、水素、メチル基またはフェニル基を表し、ｎは、１０～８０の数を表す。）

(In the formula, R ₁ and R ₂ each independently represent hydrogen, a methyl group, or a phenyl group, and n represents a number from 10 to 80.)

According to the present invention, it is possible to provide a toner that has a wide fixing area and is capable of printing high-quality images with suppressed roughness and trailing even when used for a long period of time in a low-humidity environment. I can do it.

In the present invention, the descriptions such as "from XX to XX" and "XX to XX" indicating a numerical range mean a numerical range including the lower limit and upper limit, which are the endpoints, unless otherwise specified.

The present inventors conducted extensive studies with the aim of providing a wide fixing area and further improving the uniformity of the adhesive force distribution on the surface layer of each particle of the toner. As a result, a structure containing a modified polyester having a silicone unit represented by the following general formula [1] and a polar group-containing olefin copolymer was reached. By using such toner, it is possible to obtain an excellent fixing area, and furthermore, it is possible to obtain images with less roughness and trailing even when used for a long period of time in a low humidity environment. I found out.

（式中、Ｒ_１およびＲ_２は、それぞれ独立して、水素、メチル基またはフェニル基を表し、ｎは、１０～８０の整数を表す。）

(In the formula, R ₁ and R ₂ each independently represent hydrogen, a methyl group, or a phenyl group, and n represents an integer of 10 to 80.)

The reason why the effects of the present invention were obtained is considered as follows.

The modified polyester in the present invention is a polymer having a polar unit and a polyolefin unit. Since the polyester unit has high polarity and the silicone unit has low polarity, it is a resin in which a highly polar unit and a low polar unit are chemically bonded.

By including a silicone unit with low polarity, the surface free energy of the binder resin can be effectively lowered, and high temperature separability during fixing is improved. However, studies by the present inventors have revealed that when a resin having a silicone unit is used, the roughness of the image is reduced, especially in a low-humidity environment. This is because the presence of polyester units with high polarity and silicone units with low polarity on the surface layer of the toner makes the adhesive force distribution of each particle of the toner uneven on the surface layer, resulting in slight dot disturbances during transfer. It is thought that this caused the roughness to decrease as a result. Further, since the adhesive force distribution of each toner particle on the surface layer becomes non-uniform, a phenomenon called trailing, in which the toner image on the image is disturbed by the influence of the fixing member during fixing, tends to occur. As a result, an image problem called trailing occurs.

On the other hand, the polar group-containing olefin copolymer is characterized in that the polar unit is a unit derived from at least one of α,β-unsaturated carboxylic acid and its derivatives, unsaturated nitrile and its derivatives. shall be.

As a result of extensive studies, the inventors of the present invention found that by using a toner containing a modified polyester and a polar group-containing olefin copolymer, a toner with high temperature separation properties and suppressed image roughness and trailing in a low humidity environment was created. Obtainable.

I think the reason for this is as follows.

The olefin unit of the polar group-containing olefin copolymer does not have a bulky portion in the molecule, so it can move relatively freely in the toner, and also has low polarity, so it tends to exist on the surface layer of the toner. Furthermore, since the silicone unit of modified polyester also has low polarity, it tends to exist on the surface layer of the toner. Furthermore, since the olefin unit with high affinity is present in the toner surface layer, the modified polyester can be more stably present in the toner surface layer.

On the other hand, since the polar group of the polar group-containing olefin copolymer has high polarity, it tends to exist inside the toner. At this time, by interacting with the highly polar polyester unit in the modified polyester, it is possible to suppress the highly polar polyester unit from appearing on the toner surface layer.

As a result, the surface layer of each toner particle has a uniform presence of low-polarity silicone units, resulting in a uniform and low adhesive force distribution, which reduces roughness and trailing of images in low-humidity environments. It is possible to obtain a toner with good suppression of

From the above, by using a toner containing a modified polyester and a polar group-containing olefin copolymer, good high-temperature separation properties can be obtained, and roughness and trailing of images can be suppressed in a low-humidity environment.

Each component will be described in detail below.

[Polar group-containing olefin copolymer]
The polar group-containing olefin copolymer in the present invention preferably contains 2.0% by mass or more and 60.0% by mass or less, and preferably 5.0% by mass or more and 50.0% by mass or less of units having polarity. is more preferable, and it is even more preferable that the content is 10.0% by mass or more and 20.0% by mass or less. When the content of the polar unit is within the above range, the polar unit does not appear on the surface layer of the toner and tends to exist stably inside the toner. Therefore, the polyester unit in the modified polyester having high affinity can be more stably present inside the toner. As a result, the adhesion force distribution on the surface layer of each toner particle is uniform and low, which effectively suppresses image roughness and trailing in low-humidity environments, and has excellent high-temperature separation properties. You can get toner.

The polar group-containing olefin copolymer in the present invention preferably has a weight average molecular weight (Mw) of 5.0 x 10 ³ or more and 7.0 x 10 ⁴ or less, and 1.0 x 10 More preferably, it is ⁴ or more and 5.0×10 ⁴ or less. When the weight average molecular weight of the polar group-containing olefin copolymer is within the above range, the polar group-containing olefin copolymer can stably exist near the surface layer of the toner in the toner. Therefore, the silicone unit in the modified polyester can be more uniformly present on the surface layer of each particle of the toner. As a result, the adhesion force distribution on the surface layer of each toner particle is uniform and low, which effectively suppresses image roughness and trailing in low-humidity environments, and has excellent high-temperature separation properties. You can get toner.

The polar group-containing olefin copolymer in the present invention preferably contains 0.10 parts by mass or more and 20.0 parts by mass or less, and 0.50 parts by mass or more and 10.0 parts by mass or less, per 100 parts by mass of the binder resin. It is more preferable to contain it. When the content of the polar group-containing olefin copolymer is within the above range, the polar group-containing olefin copolymer can stably exist near the surface layer of the toner in the toner. Therefore, the silicone unit in the modified polyester can be more uniformly present on the surface layer of each particle of the toner. As a result, the adhesion force distribution on the surface layer of each toner particle is uniform and low, which effectively suppresses image roughness and trailing in low-humidity environments, and has excellent high-temperature separation properties. You can get toner.

The components constituting the polar group-containing olefin copolymer will be explained in detail.

The polar group-containing olefin copolymer is a copolymer having both a polar unit and an olefin unit.

Polar units include α,β-unsaturated carboxylic acids (compounds with a reactive carbon-carbon double bond and a carboxy group) and their derivatives, and unsaturated nitriles (compounds with a reactive carbon-carbon double bond and a carboxy group). It has a unit derived from any compound selected from the group consisting of compounds having a cyano group) and derivatives thereof.

The term “derived unit” refers to a unit in which a reactive carbon-carbon double bond, which is formed when the above compound is polymerized, becomes a single bond.

Examples of unsaturated nitriles include (meth)acrylonitrile and cyanostyrene.

Examples of the α,β-unsaturated carboxylic acid include (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid and anhydrides thereof, monomethyl maleate, monobutyl maleate, monomethyl itaconate, and the like.

The polar group-containing olefin copolymer contains a unit derived from at least one of α,β-unsaturated carboxylic acids and derivatives thereof, unsaturated nitriles and derivatives thereof, and a copolymer with other monomers (a) in addition to a polyolefin. It may also be a polymer.

Other monomers (a) include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, Styrenic monomers such as benzylstyrene; vinyl ester monomers such as vinyl acetate; vinyl ether monomers such as vinyl methyl ether; halogen-containing vinyl monomers such as vinyl chloride; diene monomers such as butadiene and isobutylene; Can be used in combination.

Further, in the case of a binder resin containing polyester as a main component, the polar group-containing olefin copolymer may be a compound having a structure in which a polyester component and a polyolefin have reacted.

Examples of the olefin unit include low molecular weight polyethylene and low molecular weight polypropylene.

In the olefin unit, the peak temperature of the maximum endothermic peak measured using a differential scanning calorimeter (DSC) is preferably 60°C or more and 110°C or less, more preferably 70°C or more and 80°C or less. Further, the olefin unit preferably has a weight average molecular weight (Mw) of 900 or more and 50,000 or less.

Further, from the viewpoint of reactivity during production of the polar group-containing olefin copolymer, it is preferable to have a branched structure like polypropylene.

The content of the olefin unit is preferably 5.0% by mass or more and 30.0% by mass or less, and 10.0% by mass or more and 20.0% by mass or less, based on the total amount of the polar group-containing olefin copolymer. It is more preferable that

In the present invention, the method for producing the polar group-containing olefin copolymer is not particularly limited, and conventionally known methods can be used.

In the case of the above-mentioned polar group-containing olefin copolymer, the polar unit, which is a polyester affinity site, and the polypropylene unit, which is a silicone unit affinity site, are each optimal for a modified polyester having a silicone unit. be converted into As a result, the silicone unit in the modified polyester can be more uniformly present on the surface layer of each particle of the toner. As a result, the adhesion force distribution on the surface layer of each toner particle is uniform and the adhesion force is low, which effectively suppresses roughness and trailing of images in low-humidity environments, and provides a toner with excellent high-temperature separation properties. can be obtained.

[Modified polyester]
The content of the modified polyester in the binder resin is preferably 50.0% by mass or more. Since the modified polyester having silicone units is the main component of the binder resin, the silicone units in the modified polyester can be more uniformly present on the surface layer of each particle of the toner. As a result, the uniformity of the adhesive force distribution on the surface layer of each particle of the toner is further improved, and it is possible to obtain a toner that has excellent high-temperature separation properties and that suppresses roughness and trailing of images in a low-humidity environment. I can do it.

The components constituting the polyester unit of the modified polyester will be explained in detail. Note that one or more of various components can be used as the following components depending on the type and use.

Examples of the divalent acid component constituting the polyester unit include the following dicarboxylic acids or derivatives thereof. Benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride or their anhydrides or lower alkyl esters; Alkyldicarboxylic acids or their anhydrides or their anhydrides such as succinic acid, adipic acid, sebacic acid, and azelaic acid; Lower alkyl esters thereof; alkenylsuccinic acids or alkylsuccinic acids having an average carbon number of 1 or more and 50 or less, or anhydrides or lower alkyl esters thereof; unsaturated such as fumaric acid, maleic acid, citraconic acid, and itaconic acid Dicarboxylic acids or their anhydrides or their lower alkyl esters.

On the other hand, examples of the dihydric alcohol component constituting the polyester unit include the following. Ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5 -Pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanedimethanol (CHDM), hydrogenated Bisphenol A, bisphenol represented by formula (I-1) and its derivatives:

（式中、Ｒはエチレン又はプロピレン基であり、ｘ、ｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０以上１０以下である。）
及び式（Ｉ－２）で示されるジオール類。

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x+y is 0 or more and 10 or less.)
and diols represented by formula (I-2).

（式中、Ｒ’はエチレン又はプロピレン基であり、ｘ’、ｙ’はそれぞれ０以上の整数であり、かつ、ｘ’＋ｙ’の平均値は０以上１０以下である。）

(In the formula, R' is an ethylene or propylene group, x' and y' are each an integer of 0 or more, and the average value of x'+y' is 0 or more and 10 or less.)

The constituent components of the polyester unit used in the present invention include trivalent or higher carboxylic acid compounds and trivalent or higher alcohol compounds in addition to the above-mentioned divalent carboxylic acid compounds and divalent alcohol compounds. You may.

Examples of trivalent or higher carboxylic acid compounds include, but are not particularly limited to, trimellitic acid, trimellitic anhydride, pyromellitic acid, and the like. Further, examples of trivalent or higher alcohol compounds include trimethylolpropane, pentaerythritol, glycerin, and the like.

The constituent components of the polyester unit used in the present invention may contain a monovalent carboxylic acid compound and a monovalent alcohol compound in addition to the above-mentioned compounds. Specifically, monovalent carboxylic acid compounds include palmitic acid, stearic acid, arachidic acid, behenic acid, and cerotic acid, heptacanoic acid, montanic acid, melisic acid, lactacic acid, and tetracontanoic acid. , pentacontanoic acid, etc.

Further, examples of the monohydric alcohol compound include behenyl alcohol, ceryl alcohol, mericyl alcohol, and tetracontanol.

The components constituting the silicone unit of the modified polyester will be explained in detail. Note that one or more of various components can be used as the following components depending on the type and use.

The silicone unit has a silicone unit represented by the following general formula [1].

（式中、Ｒ_１およびＲ_２は、それぞれ独立して、水素、メチル基またはフェニル基を表し、ｎは、１０～８０の整数を表す。）

(In the formula, R ₁ and R ₂ each independently represent hydrogen, a methyl group, or a phenyl group, and n represents an integer of 10 to 80.)

As a component used to constitute the silicone unit, a silicone oil having a functional group chemically reacting with polyester at the end of general formula [1] can be used. Examples of functional groups that react with polyester include hydroxy groups, carboxyl groups, epoxy groups, and amino groups.

The terminal functional group of the silicone oil is preferably a hydroxy group or a carboxyl group from the viewpoint of controlling reactivity with polyester.

The valency of the functional groups of silicone oil is not particularly limited. However, when a silicone unit is introduced into the main skeleton of polyester, the silicone unit can be more uniformly present on the surface layer of each particle of the toner. It is preferable to use

Moreover, it is preferable that the modified polyester contains silicone units in an amount of 0.5% by mass or more and 5.0% by mass or less.

The method for producing the modified polyester is not particularly limited, and any known method can be used. For example, a polyester resin is produced by polymerizing the aforementioned divalent carboxylic acid compound, divalent alcohol compound, and silicone oil having a functional group through an esterification reaction or transesterification reaction, and a condensation reaction. The polymerization temperature is not particularly limited, but is preferably in the range of 180°C or higher and 290°C or lower. When polymerizing the polyester resin, for example, a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, germanium dioxide, or other polymerization catalyst can be used.

The softening point of the modified polyester is preferably 85°C or higher and 150°C or lower, more preferably 100°C or higher and 150°C or lower. When the softening point of the modified polyester is within the above range, the silicone unit in the modified polyester can be more uniformly present on the surface layer of each particle of the toner. As a result, the uniformity of the adhesive force distribution on the surface layer of each particle of the toner described above has been improved, and roughness and trailing of images in low humidity environments are better suppressed, and the toner has excellent high-temperature separation properties. can be obtained.

Note that the softening point is measured as follows. The softening point of the resin is measured using a constant load extrusion type capillary rheometer "Flow Characteristic Evaluation Device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, a constant load is applied from the top of the measurement sample by a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve can be obtained that shows the relationship between temperature and temperature.

In the present invention, the "melting temperature in the 1/2 method" described in the manual attached to the "Flow Tester CFT-500D" is defined as the softening point. Note that the melting temperature in the 1/2 method is calculated as follows. First, find 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time the outflow starts (this is set as X. X = (Smax - Smin) / 2). The temperature of the flow curve when the amount of descent of the piston becomes the sum of X and Smin in the flow curve is the melting temperature Tm in the 1/2 method.

The measurement sample was obtained by compression molding approximately 1.3 g of sample at approximately 10 MPa for approximately 60 seconds using a tablet compression machine (for example, NT-100H, manufactured by NP System Co., Ltd.) in an environment of 25 ° C. A cylinder with a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Heating method Starting temperature: 50℃
Achieved temperature: 200℃
Measurement interval: 1.0℃
Temperature increase rate: 4.0℃/min
Piston cross-sectional area: 1.000cm ²
Test load (piston load): 10.0kgf (0.9807MPa)
Preheating time: 300 seconds Die hole diameter: 1.0mm
Die length: 1.0mm

[toner]
The toner of the present invention can be used as any of a magnetic one-component toner, a non-magnetic one-component toner, and a non-magnetic toner for two-component developers.

When used as a magnetic one-component toner, magnetic iron oxide particles are preferably used as the colorant. The magnetic iron oxide particles contained in the magnetic one-component toner include magnetic iron oxides such as magnetite, maghemite, and ferrite, and magnetic iron oxides containing other metal oxides; metals such as Fe, Co, and Ni; Alloys of these metals with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, and V; Mixtures may be mentioned.

The content of the magnetic iron oxide particles is preferably 30 parts by mass or more and 150 parts by mass or less based on 100 parts by mass of the binder resin.

Examples of colorants used as non-magnetic one-component toners and non-magnetic toners for two-component developers include the following.

As the black pigment, carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black, etc. is used.

Pigments or dyes can be used as coloring agents suitable for yellow color. As a pigment, C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, C. I. Bat Yellow 1, 3, and 20 are listed. As a dye, C. I. Examples include Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, and the like. These materials may be used alone or in combination of two or more.

Pigments or dyes can be used as colorants suitable for cyan color. As a pigment, C. I. Pigment Blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66, etc., C.I. I. Bat Blue 6, C. I. Acid Blue 45 is mentioned. As a dye, C. I. Examples include Solvent Blue 25, 36, 60, 70, 93, and 95. These materials may be used alone or in combination of two or more.

Pigments or dyes can be used as colorants suitable for magenta color. As a pigment, 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, 48; 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, etc., C. I. Pigment Violet 19; C. I. Bat Red 1, 2, 10, 13, 15, 23, 29, and 35 are mentioned. As magenta dye, C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc., C.I. I. Disperse Red 9, C. I. Solvent Violet 8, 13, 14, 21, 27 etc., C.I. I. Oil-soluble dyes such as Disperse 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, etc., C. I. Examples include basic dyes such as basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28. These materials may be used alone or in combination of two or more.

The content of the colorant other than the magnetic material is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

A release agent (wax) may be used to impart release properties to the toner. Examples of waxes used in the present invention include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, olefin copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; Oxidized waxes of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; Carnauba wax waxes containing fatty acid esters as a main component, such as behenyl behenate, and montanate wax; and waxes that are partially or completely deoxidized from fatty acid esters such as deoxidized carnauba wax. In addition, saturated straight chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol, and seryl alcohol. , saturated alcohols such as mericyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide Acid amide, saturated fatty acid bisamides such as hexamethylene bisstearic acid amide; ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyladipic acid amide, N,N'-dioleylsebacic acid amide unsaturated fatty acid amides such as m-xylene bisstearamide, aromatic bisamides such as N,N'-distearyl isophthalic acid amide; fats such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate, etc. group metal salts (generally called metal soaps); waxes made by grafting aliphatic hydrocarbon waxes with vinyl copolymer monomers such as styrene and acrylic acid; Partial esterification products of alcohols; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils and the like can be mentioned.

The mold release agent particularly preferably used in the present invention is an aliphatic hydrocarbon wax. For example, low molecular weight hydrocarbons obtained by radical polymerization of alkylene under high pressure or polymerization under low pressure with Ziegler catalyst or metallocene catalyst; Fischer-Tropsch wax synthesized from coal or natural gas; and obtained by thermally decomposing high molecular weight olefin polymers. A synthetic hydrocarbon wax obtained from the distillation residue of hydrocarbons obtained by the Age method from synthesis gas containing carbon monoxide and hydrogen, or a synthetic hydrocarbon wax obtained by hydrogenating these is preferable. Furthermore, those obtained by fractionating the hydrocarbon wax by using a press perspiration method, a solvent method, a vacuum distillation method, or a fractional crystallization method are more preferably used. In particular, wax synthesized by a method that does not involve polymerization of alkylene is preferred from the viewpoint of its molecular weight distribution.

The wax may be added at the time of producing the toner or during the production of the binder resin. Further, these waxes may be used alone or in combination of two or more. The wax is preferably added in an amount of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

In the toner of the present invention, a known charge control agent can be used as the charge control agent. Specifically, azo iron compounds, azo chromium compounds, azo manganese compounds, azo cobalt compounds, azo zirconium compounds, carboxylic acid derivative chromium compounds, carboxylic acid derivative zinc compounds, and carboxylic acid derivative aluminum compounds. , zirconium compounds of carboxylic acid derivatives. As the carboxylic acid derivative, aromatic hydroxycarboxylic acids are preferred. Further, a charge control resin can also be used. If necessary, one type or two or more types of charge control agents may be used in combination. The charge control agent is preferably added in an amount of 0.1 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the binder resin.

Note that the average circularity of the toner is preferably 0.960 or more and 0.980 or less from the viewpoint of chargeability of the toner.

In the toner of the present invention, it is preferable to externally add silica fine powder to the toner particles in order to improve charging stability, developability, fluidity, and durability. The silica fine powder preferably has a specific surface area of 30 m ² /g or more and 500 m 2 /g or less, more preferably 50 ^{m 2 /} g or more and 400 m ² /g or less, as measured by the BET method using nitrogen adsorption. Further, it is preferable to use 0.01 parts by mass or more and 8.00 parts by mass or less of silica fine powder, and more preferably 0.10 parts by mass or more and 5.00 parts by mass or less, based on 100 parts by mass of toner particles.

The BET specific surface area of silica fine powder can be measured using, for example, a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics), GEMINI2360/2375 (manufactured by Micrometic Co., Ltd.), or Tristar 3000 (manufactured by Micrometic Co., Ltd.). It can be calculated by adsorbing nitrogen gas on the surface of the body and using the BET multipoint method.

The silica fine powder contains unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane coupling agents, and functional groups for the purpose of hydrophobization and triboelectricity control, as necessary. It is also preferable that the material be treated with a treatment agent such as a silane compound or other organosilicon compound, or a combination of various treatment agents.

Furthermore, other external additives may be added to the toner of the present invention as required. Examples of such external additives include fine resin particles that function as charging aids, conductivity imparting agents, fluidity imparting agents, anti-caking agents, release agents during hot roller fixing, lubricants, abrasives, etc. Examples include inorganic fine powder. Examples of the charging aid include metal oxides such as titanium oxide, zinc oxide, and alumina. Examples of the lubricant include polyfluoroethylene powder, zinc stearate powder, and polyvinylidene fluoride powder. Examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder.

The method for producing toner particles in the present invention is not particularly limited, and any known method can be used. Examples include a pulverization method, an emulsion aggregation method, a suspension polymerization method, a dissolution suspension method, and the like.

Toner particles produced by the pulverization method are produced, for example, as follows. The modified polyester, the polar group-containing olefin copolymer, and other additives as necessary are sufficiently mixed using a mixer such as a Henschel mixer or a ball mill. The mixture is melt-kneaded using a heat kneader such as a twin-screw extruder, heated roll, kneader, or extruder. At that time, wax, magnetic iron oxide particles, and metal-containing compounds can also be added. After the melt-kneaded product is cooled and solidified, it is pulverized and classified to obtain toner particles. At this time, the average circularity of the toner particles can be controlled by adjusting the exhaust temperature during pulverization. Further, if necessary, toner particles and external additives are mixed using a mixer such as a Henschel mixer to obtain a toner.

Examples of mixers include: Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); Super mixer (manufactured by Kawata Co., Ltd.); Ribocone (manufactured by Okawara Seisakusho Co., Ltd.); Nauta mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron Co., Ltd.); Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.) ; Loedige mixer (manufactured by Matsubo).

Examples of the kneading machine include the following. KRC kneader (manufactured by Kurimoto Iron Works); Bussco kneader (manufactured by Buss); TEM extruder (manufactured by Toshiba Machinery Co., Ltd.); TEX twin-screw kneader (manufactured by Japan Steel Works, Ltd.); PCM kneader (manufactured by Ikegai) (manufactured by Tekkosho Co., Ltd.); Three-roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho Co., Ltd.); Kneedex (manufactured by Mitsui Mining Co., Ltd.); MS-type pressure kneader, nidaruder (manufactured by Moriyama Seisakusho Co., Ltd.); Banbury mixer (manufactured by Kobe Steel Co., Ltd.) (manufactured by Shosha).

Examples of the crusher include the following: Counter jet mill, Micron jet, Innomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industries); Cross jet mill (manufactured by Kurimoto Iron Works); Ulmax (manufactured by Nisso Engineering) ); SK Jet-O-Mill (manufactured by Seishin Enterprises); Kryptron (manufactured by Kawasaki Heavy Industries); Turbo Mill (manufactured by Turboe Industries); Super Rotor (manufactured by Nisshin Engineering).

In addition, after crushing, if necessary, hybridization system (manufactured by Nara Kikai Seisakusho), Nobilta (manufactured by Hosokawa Micron), Mechano Fusion System (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron), Innomizer (manufactured by Hosokawa Micron), , Theta Composer (manufactured by Tokuju Kosho Co., Ltd.), Mechano Mill (manufactured by Okada Seiko Co., Ltd.), and Meteor Rainbow MR Type (manufactured by Nippon Pneumatic Co., Ltd.) are used to perform surface treatment on toner particles and control the average circularity of toner particles. You can also.

After that, if necessary, classification is performed using an inertial classification method Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.), a centrifugal force classification method Turboplex (manufactured by Hosokawa Micron Corporation), a TSP separator (manufactured by Hosokawa Micron Corporation), or a Faculty (manufactured by Hosokawa Micron Corporation). Classify using a machine or sieve. Thereafter, a desired amount of external additive is externally added to the surfaces of the obtained heat-treated toner particles having a desired particle size. External addition treatment methods include double con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, Mechano Hybrid (manufactured by Nippon Coke Industries Co., Ltd.), Nobilta (manufactured by Hosokawa Micron Co., Ltd.), etc. An example is a method of stirring and mixing using a mixing device as an external addition device. At that time, if necessary, an external additive such as a fluidizing agent may be added externally.

When the toner of the present invention is used as a nonmagnetic toner for a two-component developer, common carriers such as ferrite and magnetite carriers and resin-coated carriers can be used as carriers used in combination. Furthermore, a binder type carrier core in which magnetic powder is dispersed in a resin can also be used.

The resin-coated carrier consists of carrier core particles and a coating material that is a resin that covers (coats) the surface of the carrier core particles. Resins used for the coating include styrene-acrylic resins such as styrene-acrylic ester copolymers and styrene-methacrylic ester copolymers; acrylic resins such as acrylic ester copolymers and methacrylic ester copolymers. System resins; fluorine-containing resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymers, and polyvinylidene fluoride; silicone resins; polyester resins; polyamide resins; polyvinyl butyral; and aminoacrylate resins. Other examples include iomonomer resin and polyphenylene sulfide resin. These resins can be used alone or in combination.

Next, a method for measuring the particle size distribution of toner particles according to the present invention will be described.

On the "Change standard measurement method (SOM) screen" of the dedicated software, set the total count in control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter) Set the value obtained using By pressing the threshold/noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the aperture tube flush after measurement.

On the "pulse to particle size conversion setting screen" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Approximately 200 ml of the above electrolyte aqueous solution is placed in a 250 ml round-bottom glass beaker exclusively for Multisizer 3, set on a sample stand, and stirred with a stirrer rod counterclockwise at 24 revolutions/second. Then, use the special software's ``aperture flush'' function to remove dirt and air bubbles from inside the aperture tube.
(2) Pour about 30 ml of the above electrolytic aqueous solution into a 100 ml glass flat-bottomed beaker, and add "Contaminon N" as a dispersant (precision measurement of pH 7 consisting of nonionic surfactant, anionic surfactant, and organic builder). Approximately 0.3 ml of a diluted solution prepared by diluting a 10% by mass aqueous solution of a neutral detergent for cleaning utensils (manufactured by Wako Pure Chemical Industries, Ltd.) by 3 times by mass with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with their phases shifted by 180 degrees, and are placed in the water tank of an ultrasonic dispersion device "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is poured into the water tank, and approximately 2 ml of the contaminon N is added to the water tank.
(4) Set the beaker of (2) above in the beaker fixing hole of the ultrasonic disperser, and operate the ultrasonic disperser. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner particles are added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In addition, in the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10° C. or more and 40° C. or less.
(6) Using a pipette, drop the electrolytic aqueous solution (5) in which toner particles are dispersed into the round-bottomed beaker (1) placed in the sample stand, and adjust the measured concentration to about 5%. Then, the measurement is continued until the number of particles to be measured reaches 50,000.
(7) Analyze the measurement data using the dedicated software attached to the device and calculate the weight average particle diameter (D4). Note that when the dedicated software is set to graph/volume %, the "average diameter" on the analysis/volume statistics (arithmetic mean) screen is the weight average particle diameter (D4).

The basic configuration and features of the present invention have been described above, and the present invention will be specifically described below based on examples. However, the present invention is not limited to this in any way. Note that unless otherwise specified, "parts" and "%" are based on mass.

<Production of binder resin 1>
・Bisphenol A ethylene oxide (2.2 mol adduct): 50.0 mol parts ・Bisphenol A propylene oxide (2.2 mol adduct): 50.0 mol parts ・Terephthalic acid: 90.0 mol parts ・Trianhydride Mellitic acid: 10.0 mole parts 97 parts by mass of the monomer constituting the above polyester unit and 3 parts of silicone oil having hydroxyl groups at both ends (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd.), together with 500 ppm of titanium tetrabutoxide. Mixed in a 5 liter autoclave.

The autoclave was equipped with a reflux condenser, a water separator, a N ₂ gas introduction pipe, a thermometer, and a stirring device, and a polycondensation reaction was carried out at 230° C. while introducing N ₂ gas into the autoclave. The reaction time was adjusted to reach the desired softening point, and after the reaction was completed, the mixture was taken out of the container, cooled, and crushed to obtain a binder resin 1. Binder Resin 1 had a Tm of 130°C and a Tg of 55°C.

<Production of binder resins 2 to 8>
Binder Resins 2 to 8 were obtained in the same manner as Binder Resin 1, except that the amount of silicone oil added was changed, the reaction time was adjusted, and Tm and Tg were changed.

<Production of polar group-containing olefin copolymer 1>
In an autoclave reaction tank equipped with a thermometer and a stirrer, 300.0 parts of xylene and 10.0 parts of polypropylene (melting point 90°C) were thoroughly dissolved, and after purging with nitrogen, 68.0 parts of styrene and 10.0 parts of methacrylic acid were added. 12.0 parts of butyl acrylate, and 250.0 parts of xylene were added dropwise at 180° C. for 3 hours to polymerize. This temperature was further maintained for 30 minutes to remove the solvent, thereby obtaining polar group-containing olefin copolymer 1. Table 2 shows the composition of the obtained polar group-containing olefin copolymer 1.

<Production of polar group-containing olefin copolymers 2 to 12>
In the production of polar group-containing olefin copolymer 1, conditions were changed as appropriate so that the types and contents of olefins, the types and contents of polar group-containing units, and the types and contents of other monomers were as shown in Table 2. . Other than that, the same operations as in the production example of polar group-containing olefin copolymer 1 were performed to obtain polar group-containing olefin copolymers 2 to 12. Table 2 shows the composition of the obtained polar group-containing olefin copolymer.

(Manufacture of toner 1)
- Binder resin 1 100.0 parts - Polar group-containing olefin copolymer 1 5.0 parts - C.I. I. Pigment Blue 15:3 4.0 parts

The above materials were premixed using a Henschel mixer, and then melt-kneaded at 160°C using a twin-screw kneading extruder.

The obtained kneaded product was cooled, coarsely pulverized with a hammer mill, and then finely pulverized with a turbo mill.

The obtained finely pulverized product was classified using a multi-division classifier utilizing the Coanda effect to obtain negatively triboelectrically charged toner particles having a weight average particle diameter (D4) of 6.0 μm.

To 100 parts of the toner particles, 2.0 parts of hydrophobized silica fine particles (specific surface area due to nitrogen adsorption measured by BET method: 140 m ² /g) were externally added and mixed, and the mixture was sieved through a mesh with an opening of 150 μm. Toner 1 was obtained.

[Manufacture of carrier]
(Manufacture of magnetic core particles)
- 62.7 parts of Fe ₂ O ₃ - 29.5 parts of MnCO ₃ - 6.8 parts of Mg(OH) _{2 -} 1.0 part of SrCO ₃ The ferrite raw materials were weighed so that the above materials had the above composition ratios.

Thereafter, the mixture was ground and mixed for 5 hours in a dry vibration mill using stainless steel beads with a diameter of 1/8 inch. The obtained pulverized material was made into pellets of approximately 1 mm square using a roller compactor.

Coarse powder was removed from the pellets using a vibrating sieve with an opening of 3 mm, then fine powder was removed using a vibrating sieve with an opening of 0.5 mm, and then the pellets were heated in a burner-type firing furnace under a nitrogen atmosphere (oxygen concentration 0. 01% by volume) at a temperature of 1000° C. for 4 hours to produce calcined ferrite. The composition of the obtained calcined ferrite was as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe2O3) _d

In the above formula, a=0.257, b=0.117, c=0.007, d=0.393
After the calcined ferrite was crushed to about 0.3 mm with a crusher, 30 parts of water was added to 100 parts of the calcined ferrite using zirconia beads having a diameter of 1/8 inch, and the mixture was crushed with a wet ball mill for 1 hour. Furthermore, the obtained slurry was pulverized for 4 hours in a wet ball mill using alumina beads having a diameter of 1/16 inch to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).

To 100 parts of calcined ferrite, 1.0 part of ammonium polycarboxylate as a dispersant and 2.0 parts of polyvinyl alcohol as a binder were added to the ferrite slurry, and the mixture was dried using a spray dryer (manufacturer: Okawara Kakoki). Then, it was granulated into spherical particles. After adjusting the particle size of the obtained particles, they were heated at 650° C. for 2 hours using a rotary kiln to remove the organic components of the dispersant and binder.

In order to control the firing atmosphere, the temperature was raised from room temperature to 1300°C in 2 hours in an electric furnace under a nitrogen atmosphere (oxygen concentration 1.00% by volume), and then fired at a temperature of 1150°C for 4 hours. Thereafter, the temperature was lowered to 60° C. over a period of 4 hours, the temperature was returned to the atmosphere from the nitrogen atmosphere, and the sample was taken out at a temperature of 40° C. or lower.

After crushing the agglomerated particles, the low-magnetic products are cut by magnetic separation, and coarse particles are removed by sieving with a sieve with an opening of 250 μm, and the 50% particle size (D50) based on volume distribution is 37.0 μm. magnetic core particles were obtained.

(Manufacture of coating resin)
・Cyclohexyl methacrylate monomer 26.8%
・Methyl methacrylate monomer 0.2%
・Methyl methacrylate macromonomer 8.4%
(Macromonomer with a weight average molecular weight of 5000 having a methacryloyl group at one end)
・Toluene 31.3%
・Methyl ethyl ketone 31.3%
・Azobisisobutyronitrile 2.0%

Of the above materials, cyclohexyl methacrylate monomer, methyl methacrylate monomer, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were placed in a four-necked separable flask equipped with a reflux condenser, thermometer, nitrogen inlet tube, and stirring device. . After nitrogen gas was introduced into the separable flask to create a sufficient nitrogen atmosphere, the mixture was heated to 80° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization.

Hexane was injected into the obtained reaction product to precipitate the copolymer. The obtained precipitate was filtered and dried under vacuum to obtain a resin.

30 parts of the resin was dissolved in a mixed solvent of 40 parts of toluene and 30 parts of methyl ethyl ketone to obtain a resin solution (solid content concentration 30%).

(Preparation of coating resin solution)
・Resin solution (solid content concentration 30%) 33.3%
・Toluene 66.4%
・Carbon black (Regal330; manufactured by Cabot) 0.3%
(Number average particle diameter of primary particles: 25 nm, nitrogen adsorption specific surface area: 94 m ² /g, DBP oil absorption: 75 ml/100 g)

The above materials were placed in a paint shaker and dispersed for 1 hour using zirconia beads with a diameter of 0.5 mm. The obtained dispersion liquid was filtered through a 5.0 μm membrane filter to obtain a coating resin solution.

(Coat of coating resin)
The coating resin solution and the magnetic core particles were charged into a vacuum degassing kneader maintained at room temperature (the amount of the coating resin solution added was 2.5 parts as a resin component per 100 parts of the magnetic core particles).

After the addition, the mixture was stirred at a rotational speed of 30 rpm for 15 minutes, and after a certain amount (80%) of the solvent had evaporated, the temperature was raised to 80° C. while mixing under reduced pressure, and the toluene was distilled off over 2 hours, followed by cooling.

The obtained magnetic carrier was separated into low-magnetic products by magnetic separation, passed through a sieve with an opening of 70 μm, and then classified with an air classifier to obtain magnetic carriers with a 50% particle size (D50) based on volume distribution of 38.2 μm. I got a career.

[Preparation of two-component developer 1]
Toner 1 and magnetic carrier were mixed at 0.5 s ⁻¹ using a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) such that toner 1 was 10 parts to 90 parts of magnetic carrier. Two-component developer 1 was prepared by mixing under the condition that the rotation time was 5 minutes.

The following evaluations were performed using the obtained two-component developer 1.

<Example 1>
The following evaluations were conducted using a Canon full-color copying machine imagePRESS C800 or a modified version thereof.

The image forming apparatus has a photoconductor as an image carrier on which an electrostatic latent image is formed, and has a developing step of developing the electrostatic latent image on the photoconductor into a toner image using a two-component developer.

The method further includes a transfer step of transferring the developed toner image to an intermediate transfer member, and then transferring the toner image of the intermediate transfer member to paper, and a fixing step of fixing the toner image on the paper by heat.

Two-component developer 1 was put into the developing device of the cyan station of this image forming apparatus, and the following evaluation was performed.

<Evaluation of hot offset resistance>
The fixing device of a Canon full color copier imagePRESS C800 was taken out and an external fixing device was used which was modified so that it could operate outside the copier and the fixing temperature and process speed could be set arbitrarily. Using this external fixing device, paper was passed under an N/L environment.

Hot offset resistance was evaluated by using 50 g/m ² paper and passing an unfixed image on A4 paper in landscape orientation, with a halftone image density of 0.5 over the entire area within 5 cm from the leading edge, and a solid white image on the rest of the paper. did. The unfixed image created by the above method was placed on an A4 sheet of paper, with the temperature of the heating element of the fixing device adjusted at 5°C intervals in the temperature range of 210 to 240°C, the process speed set to 50 mm/sec, and the nip width set to 13 mm. After passing 100 sheets, the above A4 landscape image was passed through and fixed. At this time, the level of offset appearing in the white background area was visually confirmed.
A: No offset occurs at all.
B: At a fixing temperature of 240° C., a slight offset occurred at the edges other than the portion where the A4 sheet was passed in portrait orientation.
C: At a fixing temperature of 230° C., a slight offset occurred at the edges other than the portion where the A4 sheet was passed in portrait orientation.
D: A noticeable offset occurred, or a faint offset occurred at a fixing temperature of 220° C. or lower.

<Evaluation of roughness>
Roughness was evaluated by dot reproducibility. After continuously printing up to 10,000 sheets of test charts with a print ratio of 5% in a low temperature, low humidity environment (5°C, 5% RH), a halftone (30H) image is formed, and the dot reproducibility of this image is based on the following standards. Evaluation was made based on.

High white paper GF-C081 (81.4 g/m ² , manufactured by Canon Marketing Japan Inc.) was used as the recording medium. Note that the 30H image is a value expressed in hexadecimal 256 gradations, and is a halftone image when 00H is a solid white (non-image) and FFH is a solid image (full image).

The image was obtained by measuring the area of 1000 dots using a digital microscope VHX-500 (lens wide range zoom lens VH-Z100 manufactured by Keyence Corporation).

The number average (S) of the dot area and the standard deviation (σ) of the dot area were calculated, and the dot reproducibility index was calculated using the following formula.

Then, evaluation was made using the dot reproducibility index (I) of the halftone image. The smaller the value of the dot reproducibility index (I), the better the dot reproducibility.

Dot reproducibility index (I)=σ/S×100
(Evaluation criteria)
A: I is less than 1.0 B: I is 1.0 or more and less than 1.5 C: I is 1.5 or more and less than 2.0 D: I is 2.0 or more and less than 4.0 E: I is 4. 0 or more and less than 6.0 F: I is 6.0 or more

<Evaluation of tailing>
GF-R070 (67.0 g/m2, Canon Marketing Japan Inc.) was used as the recording medium. In addition, it was left to stand in a low-temperature, low-humidity environment (5° C., 5% RH) for 48 hours or more to fully dry (moisture content less than 3%).

Under a low temperature, low humidity environment (5° C., 5% RH), a horizontal line image chart with 4 dot lines arranged at 20 dot spaces was used, and trailing generated from the horizontal lines on the image was counted and judged according to the following criteria.
A: No tailing occurred.
B: Less than one tailing occurs per horizontal line.
C: Two or fewer tails occur per horizontal line.
D: Three or less tailings occur per horizontal line.
E: Four or more tailings occur per horizontal line.

In each of the above evaluation items, the two-component developer 1 was evaluated as A in all cases.

(Manufacture of toners 2 to 16)
Toners 2 to 16 were obtained in the same manner as Toner 1 except that the types and amounts of the binder resin and polar group-containing olefin copolymer were changed as shown in Table 3.

(Preparation of two-component developers 2 to 16)
Two-component developers 2 to 13 were prepared in the same manner as in the production of two-component developer 1, except that the toners were changed as shown in Table 4.

<Examples 2 to 13, Comparative Examples 1 to 3>
Evaluations were conducted in the same manner as for Two-Component Developer 1, except that Two-Component Developers 2 to 16 were used. The evaluation results are shown in Table 4.
Note that Examples 7 to 13 are described as reference examples.

Claims (6)

A toner having toner particles containing a binder resin and a polar group-containing olefin copolymer,
The binder resin contains a modified polyester having a silicone unit represented by the following general formula [1],
The content of the modified polyester is 50.0% by mass or more in the binder resin,
The modified polyester contains the silicone unit in an amount of 0.5% by mass or more and 5.0% by mass or less,
The polar group-containing olefin copolymer is a polymer having a polar unit and a polyolefin unit,
A toner characterized in that the polar unit is a unit derived from any compound selected from the group consisting of α,β-unsaturated carboxylic acids and derivatives thereof, unsaturated nitriles and derivatives thereof.

(In the formula, R ₁ and R ₂ each independently represent hydrogen, a methyl group, or a phenyl group, and n represents an integer of 10 to 80.) The toner according to claim 1, wherein the polar group-containing olefin copolymer contains the polar unit in an amount of 2.0% by mass or more and 60.0% by mass or less. 3. The toner according to claim 1, wherein the polar group-containing olefin copolymer has a weight average molecular weight (Mw) of 5.0×10 ³ or more and 7.0×10 ^{4 or} less in molecular weight distribution determined by GPC. The toner according to any one of claims 1 to 3, wherein the toner particles contain 0.10 parts by mass or more and 20.0 parts by mass or less of the polar group-containing olefin copolymer per 100 parts by mass of the binder resin. . 5. The toner according to claim 1, wherein in the silicone unit, R ₁ and R ₂ in the general formula [1] are both methyl groups. The toner according to any one of claims 1 to 5, wherein the polyolefin unit contained in the polar group-containing olefin copolymer is a polypropylene unit.