JP2018105951A - Image forming method, image forming apparatus, and toner kit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that can be adapted to a high-speed developing system, and is excellent in development stability, low-temperature fixability, and hot offset resistance.SOLUTION: The present image forming method is an image forming method including: forming a color toner image by combining a transparent toner and one or more colored toners selected from the group consisting of a yellow toner, a magenta toner, a cyan toner, and a black toner; and forming a transparent toner image on a top layer of a transfer material. The colored toners and transparent toner are a toner containing a binder resin and a mold release agent; the storage elastic modulus at 90°C of the colored toners is G'(90) and the storage elastic modulus at 90°C of the transparent toner G'(90) satisfy a specific relationship.SELECTED DRAWING: None

Description

  The present invention relates to an image forming method, an image forming apparatus, and a toner kit used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system.

2. Description of the Related Art Conventionally, an image forming apparatus using electrophotography uses not only colored toners (hereinafter referred to as color toners) such as yellow, magenta, cyan, and black but also transparent toners that are colorless and transparent to transfer toner images onto transfer materials. An image forming apparatus to be formed has been proposed. In this way, various expressions can be made by using the transparent toner. For example, there is a method in which gloss is uniformly imparted to the entire image surface of a sheet with a transparent toner. In this method, the image surface of the transfer material and the white background where no color toner is placed are covered with transparent toner to give gloss.
However, in the image forming method using these transparent toners, a color toner image and a transparent toner image must be sequentially formed and fixed on a transfer material, so that the amount of toner that must be fixed at a time increases. For this reason, the fixing device requires a large number of heating temperatures and pressures, and accordingly, problems are likely to occur in the offset phenomenon and separation between the fixing member and the transfer material after fixing.
In contrast to this, only the color toner image is first formed and fixed on the transfer material, and then the transparent toner image is formed and fixed thereon, and the fixing temperature and pressure necessary for only the transparent toner are adjusted. Thus, proposals have also been made to improve offset resistance and separability.
However, in either method, the amount of toner applied to the transfer material changes between the image portion and the white background portion of the transparent toner, so that the amount of heat received by the toner changes and affects the surface state of the toner after fixing. As a result, it is difficult to maintain the gloss uniformity of the image. Especially in the white background where the amount of toner loaded is small, the transparent toner penetrates excessively into the transfer material and the texture of the transfer material shows through. Occurred, and the decrease in glossiness was remarkable.
As an image forming method using a transparent toner, there is a method of forming a mark such as a gloss mark, a watermark, a security mark, or the like on a sheet using the transparent toner. Specifically, there is a method in which a mark such as the logo is formed on a white background portion of a sheet and used like a watermark. Alternatively, there is a method in which, in the image portion of the sheet, an image is formed with a color toner, and then a mark such as the above logo is formed to make the mark stand out by gloss difference.
The transparent toner used to form such a mark is preferably different in glossiness from the color toner, unlike the transparent toner used for glossing as described above.
For example, Patent Documents 1 and 2 propose to secure glossiness and suppress toner blister phenomenon by adjusting the storage elastic modulus of color toner and transparent toner. However, it is insufficient in terms of gloss uniformity in the white background and the image area, and on the other hand, in the image formation such as “watermark” mark, the difference in gloss between the color image and the transparent image is insufficient, which is an improvement. There was room.

JP 2010-79106 A JP 2010-237240 A

An object of the present invention is an image forming method using a color toner and a transparent toner, which has solved the above-mentioned problems, and has an excellent fixing property and high-temperature offset resistance, and an excellent gloss uniformity. An image forming apparatus and a toner kit are provided.
It is another object of the present invention to provide an image forming method, an image forming apparatus, and a toner kit that satisfy a sufficient recognition performance even when an image such as a “watermark” mark is output.

The above problem can be solved by the toner having the following configuration.
That is, the present invention provides a charging step of charging the electrostatic latent image carrier by a charging means,
An exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image;
A developing step of developing the electrostatic latent image with a developer containing toner and a magnetic carrier to form a toner image using a developing device;
In an image forming method comprising a transfer step of transferring the toner image to a transfer material with or without an intermediate transfer member, and a fixing step of fixing the transferred toner image to the transfer material.
The image forming method forms a color toner image by combining one or more color toners selected from the group consisting of yellow toner, magenta toner, cyan toner, and black toner and a transparent toner, on the transfer material. An image forming method for forming a transparent toner image on the uppermost layer;
The colored toner and the transparent toner are toners containing a binder resin and a release agent,
The storage elastic modulus G ′ _Cl (90) of the colored toner at 90 ° C. and the storage elastic modulus G ′ _Tr (90) of the transparent toner at 90 ° C. satisfy the following formulas (1) to (3). The present invention relates to an image forming method.
3.0 × 10 ⁵ ≦ G ′ _Tr (90) ≦ 1.0 × 10 ⁷ (1)
5.0 × 10 ⁴ ≦ G ′ _Cl (90) ≦ 1.0 × 10 ⁶ (2)
7.0 ≦ G ′ _Tr (90) / G ′ _Cl (90) ≦ 100.0 (3)
The present invention also provides a charging means for charging the electrostatic latent image carrier.
Exposure means for exposing the charged electrostatic latent image carrier to form an electrostatic latent image;
A developing unit having a developer containing toner and a magnetic carrier, and developing the electrostatic latent image with the developer to form a toner image;
In an image forming apparatus having a transfer unit for transferring the toner image to a transfer material with or without an intermediate transfer member, and a fixing unit for fixing the transferred toner image to the transfer material,
The image forming apparatus forms a color toner image by combining one or more color toners selected from the group consisting of yellow toner, magenta toner, cyan toner, and black toner and a transparent toner, on the transfer material. An image forming apparatus for forming a transparent toner image on the uppermost layer;
The colored toner and the transparent toner are toners containing a binder resin and a release agent,
The storage elastic modulus at 90 ° C. of the colored toner is G ′ _Cl (90) and the storage elastic modulus G ′ _Tr (90) of the transparent toner at 90 ° C. satisfies the following formulas (1) to (3). The present invention relates to an image forming apparatus.
3.0 × 10 ⁵ ≦ G ′ _Tr (90) ≦ 1.0 × 10 ⁷ (1)
5.0 × 10 ⁴ ≦ G ′ _Cl (90) ≦ 1.0 × 10 ⁶ (2)
7.0 ≦ G ′ _Tr (90) / G ′ _Cl (90) ≦ 100.0 (3)
Furthermore, the present invention provides a charging step of charging the electrostatic latent image carrier by a charging means,
An exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image;
A developing step of developing the electrostatic latent image with a developer containing toner and a magnetic carrier using a developing device to form a toner image;
In a toner kit used in an image forming method including a transfer step of transferring the toner image to a transfer material with or without an intermediate transfer member, and a fixing step of fixing the transferred toner image to the transfer material,
The image forming method forms a color toner image by combining one or more color toners selected from the group consisting of yellow toner, magenta toner, cyan toner, and black toner and a transparent toner, on the transfer material. An image forming method for forming a transparent toner image on the uppermost layer;
The colored toner and the transparent toner are toners containing a binder resin and a release agent,
The storage elastic modulus at 90 ° C. of the colored toner satisfies G ′ _Cl (90), and the storage elastic modulus G ′ _Tr (90) of the transparent toner at 90 ° C. satisfies the following formulas (1) to (3). And a toner kit for use in an image forming method.
3.0 × 10 ⁵ ≦ G ′ _Tr (90) ≦ 1.0 × 10 ⁷ (1)
5.0 × 10 ⁴ ≦ G ′ _Cl (90) ≦ 1.0 × 10 ⁶ (2)
7.0 ≦ G ′ _Tr (90) / G ′ _Cl (90) ≦ 100.0 (3)

  According to the present invention, in an image forming method using colored (color) toner and transparent toner, excellent fixability, high-temperature offset resistance, gloss uniformity, and recognition ability such as “watermark” mark can be satisfied. .

It is a figure which shows the sample image for evaluation used for this invention.

  Hereinafter, embodiments for carrying out the image forming method, the image forming apparatus, and the toner kit of the present invention will be described in detail.

The basic configuration of the image forming method on which the present invention is premised is that a charging step of charging the electrostatic latent image carrier with a charging means, and exposing the charged electrostatic latent image carrier to form an electrostatic latent image. The electrostatic latent image is developed with a developer containing toner and a magnetic carrier using an exposure process and a developing device, and a developing process for forming a toner image, with or without an intermediate transfer member. One or more selected from the group consisting of yellow toner, magenta toner, cyan toner, and black toner, having a transfer step of transferring to a transfer material and a fixing step of fixing the transferred toner image to the transfer material The color toner and the transparent toner are combined to form a color toner image, and the transparent toner image is formed on the uppermost layer on the transfer material. The colored toner and the transparent toner are toners containing a binder resin and a releasing agent, and the storage elastic modulus of the colored toner at 90 ° C. is G ′ _Cl (90) and the transparent toner at 90 ° C. The storage elastic modulus G ′ _Tr (90) satisfies the following formula.
3.0 × 10 ⁵ ≦ G ′ _Tr (90) ≦ 1.0 × 10 ⁷ (1)
5.0 × 10 ⁴ ≦ G ′ _Cl (90) ≦ 1.0 × 10 ⁶ (2)
7.0 ≦ G ′ _Tr (90) / G ′ _Cl (90) ≦ 100.0 (3)

  That is, the inventors of the present invention, in an image forming method using color toner and transparent toner, control the storage elastic modulus of each toner, thereby improving the adhesion between the toners and peeling off the uppermost transparent toner. It has been found that fixing failure can be suppressed, and excessive penetration into the transfer material is suppressed even in a white background where the amount of toner is small, thereby maintaining gloss. Further, since there is a sufficient gloss difference between the transparent toner and the color toner, it has been found that the “watermark” image using the transparent toner has excellent recognizability.

  The present inventors consider the following effects of using the toner of the present invention having such a configuration.

The transparent toner according to the present invention is characterized in that the storage elastic modulus at 90 ° C. is such that G ′ _Tr (90) is 3.0 × 10 ⁵ (Pa) or more and 1.0 × 10 ⁷ (Pa) or less. . By having a storage elastic modulus in the above range, it melts sufficiently at the time of fixing, maintains the smoothness of the transparent toner surface layer, and satisfies the gloss uniformity of the image without excessively penetrating the transfer material.

When the storage elastic modulus G ′ _Tr (90) at 90 ° C. of the transparent toner is less than 3.0 × 10 ⁵ (Pa), the penetration into the transfer material progresses and the texture of the transfer material becomes transparent, resulting in a decrease in glossiness. cause. When G ′ _Tr (90) is more than 1.0 × 10 ⁷ (Pa), the transparent toner on the color toner upper layer is peeled off, and the glossiness is lowered.

The color toner according to the present invention is characterized in that the storage elastic modulus at 90 ° C. is such that G ′ _Cl (90) is 5.0 × 10 ⁴ (Pa) or more and 1.0 × 10 ⁶ (Pa) or less. To do. By having the storage elastic modulus in the above range, sufficient color mixing can be achieved, and high-temperature offset resistance and separability can be satisfied.

When the color toner has a storage elastic modulus at 90 ° C. of G ′ _Cl (90) of less than 5.0 × 10 ⁴ (Pa), a high temperature offset occurs when the color toner and the transparent toner are fixed separately. As a result, the separability to the fixing member becomes insufficient, causing problems such as winding. When G ′ _Cl (90) is more than 1.0 × 10 ⁶ (Pa), the adhesion with the transparent toner becomes insufficient, the glossiness is lowered due to the peeling of the transparent toner, and the color mixture is insufficient. Thus, sufficient color development becomes difficult.

The one feature of the present invention, the ratio G _'Tr storage modulus G 90 ° C. of the transparent toner' _Tr (90) and the storage modulus G at 90 ° C. of the color toner _'Cl (90) (90) / G ′ _Cl (90) is 7.0 or more and 100.0 or less. By maintaining the above relationship between the storage elastic modulus of the transparent toner and the color toner, the adhesion between the transparent toner and the color toner is maintained, and even when creating a mark with the transparent toner, a sufficient gloss difference from the color toner is obtained and recognized. Excellent in properties.

When G ′ _Tr (90) / G ′ _Cl (90) is less than 7.0, it is difficult to obtain a gloss difference between the color toner and the transparent toner, and a “watermark” image such as a logo mark is printed on the color image. It becomes difficult to recognize in the case of. When G ′ _Tr (90) / G ′ _Cl (90) exceeds 100.0, the adhesion between the color toner and the transparent toner becomes insufficient, and the transparent toner as the uppermost layer peels off from the color toner, and the surface of the image Smoothness is disturbed and glossiness is reduced.

Further, in the present invention, the storage elastic modulus G ′ _Cl (130) at 130 ° C. of the color toner is 1.0 × 10 ³ or more and 1.0 × 10 ⁵ or less. This is preferable when the transparent toner and the color toner are fixed together in a high-speed printing system in which the toner is required.

When G ′ _Cl (130) is 1.0 × 10 ³ or more, high-temperature offset is unlikely to occur when a color toner is used alone, and image disturbance and fouling of the fixing member are difficult to occur. When G ′ _Cl (130) is 1.0 × 10 ⁵ or less, the adhesion between the color toner and the transparent toner is enhanced, and the glossiness is hardly lowered due to the peeling of the transparent toner.

Further, the present invention provides a ratio G ′ _Tr (130) / G ′ _Cl (130) between the storage elastic modulus G ′ _Tr (130) of the transparent toner at 130 ° C. and the storage elastic modulus G ′ _Cl (130) of the color toner at 130 ° C. ) Is preferably 0.5 or more and 5.0 or less when the transparent toner and the color toner that require fixing under higher temperature / high pressure conditions are fixed together.

When G ′ _Tr (130) / G ′ _Cl (130) is 0.5 or more, the storage elastic modulus of the transparent toner increases and high temperature offset hardly occurs, and excessive penetration of the toner into the transfer material. It is difficult for the glossiness of the image to decrease due to the exposure of the texture. When G ′ _Tr (130) / G ′ _Cl (130) is 5.0 or less, the adhesion between the color toner and the transparent toner is enhanced, and the glossiness is not easily lowered due to peeling of the transparent toner.

  The components contained in the color toner and the transparent toner of the present invention will be described in detail.

[Binder resin]
The binder resin used in the toner of the present invention is not particularly limited, and the following polymers or resins can be used.

  For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer , Styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrenic copolymers such as ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, Acrylic resin, meta Lil resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone - indene resins, and petroleum resins.

  Among these, it is preferable to use a polyester resin or a hybrid resin of a polyester resin and a vinyl resin from the viewpoint of low-temperature fixability and chargeability control.

  The polyester resin preferably used in the present invention is a resin having a “polyester unit” in the binder resin chain. Specifically, the component constituting the polyester unit is a dihydric or higher alcohol. And monomer components and acid monomer components such as divalent or higher carboxylic acids, divalent or higher carboxylic acid anhydrides, and divalent or higher carboxylic acid esters.

  For example, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4) can be used as the divalent or higher alcohol monomer component. -Hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2- Alkylene oxide adducts of bisphenol A such as bis (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2 -Propylene glycol, 1,3-propylene glycol, 1,4-butanedio , Neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, Examples include 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like.

  Of these, the alcohol monomer component preferably used is an aromatic diol. In the alcohol monomer component constituting the polyester resin, the aromatic diol is preferably contained in a proportion of 80 mol% or more.

  On the other hand, the acid monomer component such as the divalent or higher carboxylic acid, the divalent or higher carboxylic acid anhydride, and the divalent or higher carboxylic acid ester includes aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or the like. Anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; succinic acid substituted with alkyl groups or alkenyl groups having 6 to 18 carbon atoms or anhydrides thereof; fumaric acid, maleic acid Unsaturated dicarboxylic acids such as acids and citraconic acid or anhydrides thereof.

  Of these, the acid monomer component preferably used is a polyvalent carboxylic acid such as terephthalic acid, succinic acid, adipic acid, fumaric acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, or an anhydride thereof.

  Further, the acid value of the polyester resin is preferably 1 mgKOH / g or more and 20 mgKOH / g or less from the viewpoint of the stability of the triboelectric charge amount.

  In addition, this acid value can be made the said range by adjusting the kind and compounding quantity of the monomer used for resin. Specifically, it can be controlled by adjusting the alcohol monomer component ratio / acid monomer component ratio and molecular weight during resin production. Moreover, it can control to make terminal alcohol react with a polyvalent acid monomer (for example, trimellitic acid) after ester condensation polymerization.

  Moreover, the hybrid resin containing the other resin component which has a polyester resin as a main component may be sufficient. For example, a hybrid resin of a polyester resin and a vinyl resin can be given. As a method of obtaining a reaction product of a vinyl resin or a vinyl copolymer unit and a polyester resin, such as a hybrid resin, a monomer component capable of reacting with each of the vinyl resin, the vinyl copolymer unit and the polyester resin is included. Where a polymer is present, a method of performing a polymerization reaction of one or both resins is preferable.

[Release agent (wax)]
Although it does not specifically limit as a wax as a mold release agent used for the toner of this invention, The following are mentioned. Low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymer, hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of hydrocarbon wax such as oxidized polyethylene wax or block copolymer thereof; Waxes mainly composed of fatty acid esters such as carnauba wax; those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax. Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Saturated alcohols such as sil alcohols; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Esters with alcohols such as sil alcohols; Fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Methylene bis stearic acid amide, ethylene biscapric acid Saturated fatty acid bisamides such as amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; Of unsaturated fatty acid amides such as sebacic acid amide; aromatic bisamides such as m-xylene bis stearic acid amide, N, N ′ distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate Aliphatic metal salts such as those commonly referred to as metal soaps; waxes grafted to aliphatic hydrocarbon waxes using vinylic monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides Alcohol Partial ester; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils.

  Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are preferable from the viewpoint of improving low-temperature fixability and fixing wrapping resistance.

  The wax content is preferably 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin. Further, from the viewpoint of achieving both the storage stability of the toner and the high temperature offset resistance, in the endothermic curve at the time of temperature rise measured by a differential scanning calorimeter (DSC), the maximum existing in the temperature range of 30 ° C. to 200 ° C. The peak temperature of the endothermic peak is preferably 50 ° C. or higher and 110 ° C. or lower.

[Colorant]
Examples of the colorant that can be contained in the colored toner of the present invention include the following.

  Examples of the black colorant include carbon black; those prepared by using a yellow colorant, a magenta colorant, and a cyan colorant and adjusting the color to black. As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.

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

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

  The following are mentioned as a cyan coloring pigment. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of cyan coloring dyes include C.I. I. There is Solvent Blue 70.

  The following are mentioned as a yellow coloring pigment. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20

  Examples of yellow coloring dyes include C.I. I. There is Solvent Yellow 162.

  The amount of the colorant used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the binder resin.

[Charge control agent]
The toner of the present invention may contain a charge control agent as necessary. As the charge control agent contained in the toner, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.

  Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymeric compounds having sulfonic acid or carboxylic acid in the side chain, sulfonates or sulfonated compounds in the side chain. Examples thereof include a polymer compound, a polymer compound having a carboxylate or a carboxylic acid ester in the side chain, a boron compound, a urea compound, a silicon compound, and calixarene. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

[External additive]
In the present invention, an external additive may be further added as necessary to improve fluidity and adjust the triboelectric charge amount.

  As the external additive, inorganic fine particles such as silica, titanium oxide, aluminum oxide, and strontium titanate are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

As the specific surface area of the external additive used, inorganic fine particles having a specific surface area of 10 m ² / g or more and 50 m ² / g or less are preferable from the viewpoint of suppressing embedding of the external additive.

  The external additive is preferably used in an amount of 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the toner particles.

[Career]
The toner of the present invention is preferably mixed with a magnetic carrier and used as a two-component developer in that a stable image can be obtained over a long period of time.

  Examples of the magnetic carrier include iron powder whose surface is oxidized or non-oxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, rare earth, and alloys thereof. Generally known materials such as magnetic materials such as particles, oxide particles and ferrite, and magnetic material-dispersed resin carriers (so-called resin carriers) containing magnetic materials and binder resins that hold the magnetic materials in a dispersed state. Can be used.

[Production method]
The toner production method of the present invention is not particularly limited as long as it is a conventionally known toner production method such as an emulsion aggregation method, a melt kneading method, or a dissolution suspension method, but the melt kneading method is preferable from the viewpoint of the dispersibility of raw materials.

  The melt-kneading method is characterized in that a toner composition that is a raw material of toner particles is melt-kneaded, and the obtained kneaded product is pulverized. An example of the manufacturing method will be described.

  In the raw material mixing step, components such as a binder resin, a wax, a colorant, and a charge control agent are weighed and mixed in a predetermined amount as materials constituting the toner particles and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano-hybrid (manufactured by Nippon Coke Industries, Ltd.).

  Next, the mixed material is melt-kneaded to disperse other raw materials and the like in the binder resin. In the melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. From the advantage that continuous production is possible, a single-screw or twin-screw extruder has become the mainstream. Yes. For example, KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Tekko), twin screw extruder (manufactured by K.C. ), Co-kneader (manufactured by Buss), kneedex (manufactured by Nippon Coke Industries Co., Ltd.), and the like. Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

  Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization step, for example, after coarse pulverization with a pulverizer such as a crusher, a hammer mill, or a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill Finely pulverize with a turbomill (made by Turbo Industries) or air jet type fine pulverizer.

  Then, if necessary, classification such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) The toner particles are obtained by classification using a machine or a sieving machine.

  Thereafter, external additives such as inorganic fine powder and resin particles selected as necessary may be added to externally add other inorganic fine particles to improve fluidity and charge stability. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano-hybrid (manufactured by Nippon Coke Industries, Ltd.).

  Next, methods for measuring physical properties related to the present invention will be described.

<Measuring method of viscoelasticity of toner>
As a measuring apparatus, a rotating plate type rheometer “ARES” (manufactured by TA INSTRUMENTS) is used. As a measurement sample, a sample obtained by press molding a toner into a disk shape having a diameter of 7.9 mm and a thickness of 2.0 ± 0.3 mm using a tablet molding machine in an environment of 25 ° C. is used. The sample is mounted on a parallel plate, heated from room temperature (25 ° C.) to 100 ° C. over 15 minutes to adjust the shape of the sample, then cooled to the measurement start temperature of viscoelasticity, and measurement is started. At this time, it is important to set the sample so that the initial normal force becomes zero. Further, as described below, in the subsequent measurement, the effect of normal force can be canceled by performing automatic tension adjustment (Auto Tension Adjustment ON).

The measurement is performed under the following conditions (1) to (10).
(1) A parallel plate having a diameter of 7.9 mm is used.
(2) The frequency (Frequency) is 6.28 rad / sec (1.0 Hz).
(3) The applied strain initial value (Strain) is set to 0.1%.
(4) Measure between 30 and 200 ° C. at a ramp rate of 2.0 ° C./min. In the measurement, the following automatic adjustment mode setting conditions are used. Measurement is performed in an automatic strain adjustment mode (Auto Strain).
(5) The maximum applied strain (Max Applied Strain) is set to 20.0%.
(6) The maximum torque (Max Allowed Torque) is set to 200.0 g · cm, and the minimum torque (Min Allowed Torque) is set to 0.2 g · cm.
(7) The distortion adjustment (Strain Adjustment) is set to “20.0% of Current Strain”. In the measurement, an automatic tension adjustment mode (Auto Tension) is adopted.
(8) Set automatic tension direction (Auto Tension Direction) as compression (Compression).
(9) An initial static force (Initial Static Force) is set to 10.0 g, and an automatic tension sensitivity (Auto Tension Sensitivity) is set to 40.0 g.
(10) The operating condition of the automatic tension (Sample Tension) is 1.0 × 10 ³ Pa or more.

<Measurement method of softening point (Tm) of binder resin>
The softening point of the resin is measured by 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, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). Then, the temperature of the flow curve when the piston descending amount is X in the flow curve is the melting temperature in the 1/2 method.

  As a measurement sample, about 1.0 g of resin is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.

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

<Measurement of glass transition temperature (Tg) of binder resin>
The glass transition temperature of the resin is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 5 mg of resin is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature rising rate is 10 ° C./min between a measurement range of 30 to 200 ° C. Measure with. The temperature is raised to 180 ° C. and held for 10 minutes, then the temperature is lowered to 30 ° C., and then the temperature is raised again. In the second temperature raising process, a specific heat change is obtained in the temperature range of 30 to 100 ° C. At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature (Tg) of the resin.

<Measurement of weight average molecular weight of binder resin>
The molecular weight distribution of the THF soluble part of the resin is measured by gel permeation chromatography (GPC) as follows.

The column is stabilized in a 40 ° C. heat chamber, and tetrahydrofuran (THF) is allowed to flow through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count value. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is suitably used. The detector uses an RI (refractive index) detector. In addition, as a column, it is good to combine several commercially available polystyrene gel columns, for example, the following combinations are mentioned. Combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P made by Showa Denko KK, TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ) made by Tosoh Corporation , G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), TSKgourd column combination.

  Moreover, a sample is produced as follows.

  Place 50 mg of the sample in 10 ml of THF, leave it at 25 ° C. for several hours, shake well, mix well with THF (until the sample is no longer integrated), and let stand for more than 12 hours. Note that the total standing time in THF is 24 hours. Then, a sample processing filter (pore size of 0.2 μm or more and 0.5 μm or less, for example, Myssho Disc H-25-2 (manufactured by Tosoh Corporation)) can be used as a GPC sample.

<Measurement of melting point of wax>
The melting point of the wax is the peak temperature of the maximum endothermic peak in the DSC curve measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 2 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The maximum endothermic peak temperature of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the melting point.

<Measurement of weight average particle diameter (D4) of toner>
The weight average particle diameter (D4) of the toner is determined based on the precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting and analyzing the measurement data, the measurement data is measured with 25,000 effective channels. Analyze and calculate. As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in deionized water to a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software is set as follows.

  In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked. In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

Specific measurement methods are as follows (1) to (7).
(1) About 200 ml of the electrolytic solution is placed in a 250 ml round bottom beaker made exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. The dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is placed in a glass 100 ml flat bottom beaker, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder having a pH of 7 is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for cleaning precision instruments (made by Wako Pure Chemical Industries, Ltd.) 3 times by weight with deionized water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkiki Bios) with an electrical output of 120 W. A fixed amount of deionized water is added, and about 2 ml of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) In the round bottom beaker (1) installed in the sample stand, the electrolyte aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

  Hereinafter, the present invention will be described with reference to production examples and examples.

<Production example of polyester resin for color toner>
(Production Example 1 of Low Molecular Weight Polyester Resin L)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 72.0 parts by mass Terephthalic acid: 28.0 parts by mass Tin 2-ethylhexanoate (esterification catalyst): 0.5 parts by mass The above materials were weighed into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, then cooled to 180 ° C. and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 3 parts by mass Tert-butylcatechol (polymerization inhibitor): 0.1 part by mass Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, and the temperature was maintained at 180 ° C. The reaction was continued for 1 hour. After confirming that the softening point measured according to ASTM D36-86 reached 94 ° C., the reaction was stopped by lowering the temperature (second reaction step) to obtain a low molecular weight polyester resin L-1. The resulting low molecular weight polyester resin L-1 had a softening point (Tm) of 96 ° C. and a glass transition temperature (Tg) of 57 ° C.

(Production Examples 2 to 8 of Low Molecular Weight Polyester Resin L)
In the production example 1 of the low molecular weight polyester resin L, while adjusting the reaction conditions, the low molecular weight polyester resins L-2 to L are adjusted while adjusting the reaction conditions so as to be the molecular weight, glass transition point, and softening point shown in Table 1. -8 was produced. Table 1 shows the physical properties of the obtained low molecular weight polyester resin L.

(Production Example 1 of high molecular weight polyester resin H)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane: 72.3 parts by mass Terephthalic acid: 18.3 parts by mass Fumaric acid: 2.9 parts by mass 2-ethyl Tin hexanoate (esterification catalyst): 0.5 part by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 6.5 parts by mass Tert-butylcatechol (polymerization inhibitor): 0.1 parts by mass Thereafter, the above materials are added, the pressure in the reaction vessel is lowered to 8.3 kPa, and the temperature is increased to 160 ° C. The reaction was allowed to proceed for 15 hours while maintaining. After confirming that the softening point measured according to ASTM D36-86 reached 132 ° C., the reaction was stopped by lowering the temperature (second reaction step) to obtain a high molecular weight polyester resin A (H) -1. The obtained high molecular weight polyester resin A (H) -1 had a softening point (Tm) of 132 ° C. and a glass transition temperature (Tg) of 61 ° C.

(Production Examples 2 to 7 of high molecular weight polyester resin H)
In the production example 1 of the high molecular weight polyester resin H, while adjusting the reaction conditions, adjusting the reaction conditions so as to be the molecular weight, glass transition point, and softening point shown in Table 2, the high molecular weight polyester resins H-2 to H-7 was produced. The physical properties of the obtained high molecular weight polyester resin H are shown in Table 2.

<Example of production of hybrid resin for transparent toner>
(Production example 1 of hybrid resin M)
· Dicumyl peroxide was placed in a dropping funnel in 10 parts by mass of styrene, 5 parts by mass of 2-ethylhexyl acrylate, 2 parts by mass of fumaric acid, and 5 parts by mass of a dimer of α-methylstyrene.

In addition, as a material of the polyester resin unit,
25 parts by mass of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 15 parts by mass of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Terephthalic acid 9 parts by weight trimellitic anhydride 5 parts by weight fumaric acid 24 parts by weight,
-Tin 2-ethylhexanoate (esterification catalyst): 0.5 part by mass is placed in a 4-liter four-necked flask made of glass, and a thermometer, stirring rod, condenser and nitrogen inlet tube are attached to the four-necked flask. This four-necked flask was placed in a mantle heater. Next, after the inside of the four-necked flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and while stirring at a temperature of 130 ° C., the monomer and the polymerization of the vinyl copolymer from the previous dropping funnel The initiator was added dropwise over about 4 hours. Next, the temperature was raised to 200 ° C. and reacted for about 4 hours to obtain a hybrid resin.

The molecular weight measurement result of THF-soluble matter by GPC of the obtained hybrid resin was Mw of 8.9 × 10 ⁴ and Mn of 3.8 × 10 ³ . The glass transition point was 62 ° C.

(Production Examples 2 to 16 of the hybrid resin M)
In the production example 1 of the hybrid resin M, the hybrid resins M-2 to M-16 are produced while adjusting the reaction conditions so that the molecular weight, glass transition point, and softening point shown in Table 3 are adjusted. did. Table 3 shows the physical properties of the obtained hybrid resin M.

<Production Example 1 of Color Toner>
Low molecular weight polyester resin L-1 75.00 parts by mass High molecular weight polyester resin H-1 25.00 parts by mass Fischer-Tropsch wax (peak temperature of maximum endothermic peak 90 ° C) 5.00 parts by mass I. Pigment Blue 15: 3 5.00 parts by mass, 3,5-di-t-butylsalicylic acid aluminum compound 0.50 parts by mass The raw materials shown in the above recipe are Henschel mixers (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) Were mixed at a rotation speed of 20 s ⁻¹ and a rotation time of 5 min, and then kneaded in a biaxial kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 125 ° C. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely crushed material was finely pulverized with a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were classified at a classifying rotor rotational speed of 50.0 s ⁻¹ . The obtained toner particles had a weight average particle diameter (D4) of 6.8 μm.

  To 100.0 parts by mass of the obtained toner particles, 0.5 parts by mass of titanium oxide fine particles having a primary average particle diameter of 50 nm surface-treated with 15.0% by mass of isobutyltrimethoxysilane and 20.0% by mass of hexamethyldisilazane. 1.0 parts by mass of hydrophobic silica fine particles having a primary average particle diameter of 15 nm and surface-treated with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), and ultrasonic vibration with an opening of 54 μm A color toner 1 was obtained by passing through a sieve.

<Color toner production examples 2 to 18>
Color toners 2 to 18 were obtained in the same manner as in Color toner production example 1 except that the low molecular weight polyester resin L-1 and the high molecular weight polyester resin H-1 were changed to the resins shown in Table 4, respectively. Table 4 shows the physical properties of the obtained color toner.

<Production Example 1 of Transparent Toner>
Hybrid resin M-1 100.00 parts by mass Fischer-Tropsch wax (peak temperature of maximum endothermic peak 75 ° C.) 5.00 parts by mass Aluminum compound 3,5-di-t-butylsalicylate 0.50 parts by mass The above formulation Were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 20 s ⁻¹ and a rotation time of 5 min, and then a twin-screw kneader (PCM) set at a temperature of 125 ° C. -30 type, manufactured by Ikegai Co., Ltd.). The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained coarsely crushed material was finely pulverized with a mechanical pulverizer (T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were classified at a classifying rotor rotational speed of 50.0 s ⁻¹ . The obtained toner particles had a weight average particle diameter (D4) of 5.8 μm.

  To 100.0 parts by mass of the obtained toner particles, 0.5 parts by mass of titanium oxide fine particles having a primary average particle diameter of 50 nm surface-treated with 15.0% by mass of isobutyltrimethoxysilane and 20.0% by mass of hexamethyldisilazane. 1.0 parts by mass of hydrophobic silica fine particles having a primary average particle diameter of 15 nm and surface-treated with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), and ultrasonic vibration with an opening of 54 μm A color toner 1 was obtained by passing through a sieve.

<Production Examples 2 to 16 of transparent toner>
Transparent toners 2 to 16 were obtained in the same manner as in Production Example 1 of the transparent toner, except that the hybrid resin M-1 was changed to the hybrid resins M-2 to M-16. Table 5 shows the physical properties of the obtained transparent toner.

<Example of production of magnetic core particle 1>
-Process 1 (weighing / mixing process):
Fe ₂ O ₃ 62.0 parts by mass MnCO ₃ 30.0 parts by mass Mg (OH) ₂ 7.0 parts by mass SrCO ₃ 1.0 parts by mass Ferrite raw materials were weighed so that the above composition ratio was as described above. Thereafter, the mixture was pulverized and mixed for 5 hours in a dry vibration mill using 1/8 inch diameter stainless steel beads.
-Process 2 (temporary baking process):
The obtained pulverized product was formed into pellets of about 1 mm square using a roller compactor. After removing the coarse powder from the pellets with a vibrating sieve having a mesh opening of 3 mm, and then removing the fine powders with a vibrating sieve having a mesh opening of 0.5 mm, using a burner-type firing furnace, under a nitrogen atmosphere (oxygen concentration of 0.1. And calcined at a temperature of 1000 ° C. for 4 hours to prepare calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393
-Step 3 (grinding step):
After pulverizing to about 0.3 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and pulverized with a wet ball mill for 1 hour. The slurry was pulverized for 4 hours by 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).
-Process 4 (granulation process):
To the ferrite slurry, 1.0 part by mass of ammonium polycarboxylate as a dispersant and 100 parts by mass of polyvinyl alcohol as a binder are added to 100 parts by mass of the calcined ferrite, and a spray dryer (manufacturer: Okawara Kako) is used. Granulated into spherical particles. After adjusting the particle size of the obtained particles, using a rotary kiln, it was heated at 650 ° C. for 2 hours to remove the organic components of the dispersant and the binder.
-Process 5 (firing process):
In order to control the firing atmosphere, the temperature was raised from room temperature to 1300 ° C. in a nitrogen atmosphere (oxygen concentration: 1.00 vol%) in an electric furnace in 2 hours, and then fired at a temperature of 1150 ° C. for 4 hours. Thereafter, the temperature was lowered to 60 ° C. over 4 hours, returned from the nitrogen atmosphere to the atmosphere, and taken out at a temperature of 40 ° C. or lower.
-Process 6 (screening process):
After crushing the agglomerated particles, the low-magnetic force product is cut by magnetic separation, and the coarse particles are removed by sieving with a sieve having an opening of 250 μm, and a 50% particle size (D50) of 37.0 μm based on volume distribution. Magnetic core particles 1 were obtained.

<Preparation of coating resin 1>
Cyclohexyl methacrylate monomer 26.5% by mass
Methyl methacrylate monomer 0.5% by mass
Methyl methacrylate macromonomer 8.0% by mass
(Macromonomer having a weight average molecular weight of 5000 having a methacryloyl group at one end)
Toluene 30.0% by mass
Methyl ethyl ketone 30.0% by mass
Azobisisobutyronitrile 2.0% by mass
Among the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, methyl ethyl ketone are put into a four-necked separable flask equipped with a reflux condenser, thermometer, nitrogen introduction tube and stirring device, and nitrogen gas is supplied. The system was replaced with nitrogen gas. Thereafter, 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 a copolymer, and the precipitate was filtered off and dried under vacuum to obtain coating resin 1. The obtained coating resin 1 was dissolved in 30 parts by mass, 40 parts by mass of toluene, and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content 30% by mass).

<Preparation of coating resin solution 1>
Polymer solution 1 (resin solid content concentration 30%) 33.5% by mass
Toluene 66.0% by mass
Carbon black (Regal 330; manufactured by Cabot) 0.5% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption 75 ml / 100 g)
Was dispersed with a paint shaker for 2 hours using zirconia beads having a diameter of 0.5 mm. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Example of production of magnetic carrier 1>
(Resin coating process):
The coating resin solution 1 was charged into a vacuum degassing kneader maintained at room temperature so that the resin component was 2.5 parts by mass with respect to 100 parts by mass of the filled core particles 1. After the addition, the mixture was stirred for 15 minutes at a rotation speed of 30 rpm, and after the solvent was volatilized above a certain level (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure, and toluene was distilled off over 2 hours, followed by cooling. The obtained magnetic carrier is separated by low-magnetization by magnetic separation, passed through a sieve having an opening of 70 μm, and then classified by an air classifier, and a magnetic carrier having a 50% particle size (D50) of 38.2 μm based on volume distribution. 1 was obtained.

<Example of production of two-component developer 1 for color toner>
The color toner 1 and the magnetic carrier 1 are mixed with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) at a toner concentration of 9% by mass for 0.5 s ⁻¹ and a rotation time of 5 min. A two-component developer 1 for toner was obtained.

<Production Examples of Two-Component Developers 2 to 18 for Color Toner>
Color toner two-component developers 2 to 18 were obtained in the same manner as in the production example of the color toner two-component developer 1 except that the color toner 1 was changed to the color toners 2 to 18.

<Production example of two-component developer 1 for transparent toner>
The transparent toner 1 and the magnetic carrier 1 are mixed with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.) with a toner concentration of 9% by mass for 0.5 s ⁻¹ and a rotation time of 5 min. A two-component developer 1 for toner was obtained.

<Production Examples of Two-Component Developers 2 to 16 for Transparent Toner>
Two-component developers 2 to 16 for transparent toner were obtained in the same manner as in the production example of the two-component developer 1 for transparent toner, except that the transparent toner 1 was changed to the transparent toners 2 to 16.

[Example 1]
The toner performance was evaluated according to the following methods (1) to (4).

The two-component developer 1 for color toner is placed in the cyan station of a Canon full-color copier imagePRESS C800 so that the amount of toner on the paper on the FFH image (hereinafter solid portion) is 1.2 mg / cm ^2. The development conditions were appropriately adjusted, and a fixed image in which a solid image of 4 cm × 15 cm was formed at a position 3 cm from the leading edge of the A4 evaluation paper and at the center of the evaluation paper was output. The fixing speed at this time was adjusted to 400 mm / sec.

Subsequently, the two-component developer 1 for clear toner is placed in the clear station of a Canon full-color copier imagePRESS C1 +, and the amount of toner on the paper for the FFH image (hereinafter, solid portion) is 0.45 mg / cm. ^The development conditions were adjusted appropriately so that the image becomes ² and the above cyan output image was used to form a solid toner image with clear toner of 5 cm from the tip of the A4 evaluation paper and 4 cm × 15 cm at the center of the evaluation paper. Was output. The fixing speed at this time was adjusted to 200 mm / sec.

  As shown in FIG. 1, the output image includes a cyan toner monochrome image portion 1 (2 cm × 15 cm), an image portion 2 (2 cm × 15 cm) formed by cyan toner and transparent toner, and a white background portion formed by transparent toner. (2 cm × 15 cm) was formed.

As an evaluation paper, coated paper: OK top coat + (A4 127.9 g / m ² ) (Oji Paper) was used.

(1) Image portion-white background gloss uniformity evaluation In the above image sample, glossiness (gross) of 10 points on each of the image portion 2 formed with cyan toner and transparent toner and the white background portion formed with transparent toner. The average value was defined as the glossiness (%) of the image portion and the white background portion, and the gloss uniformity was evaluated by the difference Δ (image portion glossiness (%) − white background portion glossiness (%)). Table 7 shows the evaluation results.

  The image glossiness (gloss) was measured using a handy type gloss meter PG-1M (manufactured by Nippon Denshoku Industries Co., Ltd.) with the posting angle and the light receiving angle adjusted to 60 °.

The evaluation criteria were as follows.
A: Less than 1.0% (very good)
B: 1.0% or more and less than 3.0% (excellent)
C: 3.0% or more and less than 5.0% (slightly better)
D: 5.0% or more and less than 7.0% (prior art level; acceptable level in the present invention)
E: 7.0% or more (inferior to conventional; unusable level in the present invention)

(2) “Watermark” image recognition evaluation In the above evaluation sample, the glossiness (gross) of 10 points on each of the image portion 1 formed only with cyan toner and the image portion 2 formed with cyan toner and transparent toner. The average value is defined as the glossiness (%) of the image portion 1 and the image portion 2, and the difference Δ (the glossiness (%) of the image portion 1−the glossiness (%) of the image portion 2) is used as “watermark” "The image was evaluated for cognition. Table 7 shows the evaluation results.

The evaluation criteria were as follows.
A: 8.0% or more (very good)
B: 6.0% or more and less than 8.0% (excellent)
C: 4.0% or more and less than 6.0% (slightly better)
D: 2.0% or more and less than 4.0% (prior art level; acceptable level in the present invention)
E: Less than 2.0% (inferior to conventional; unusable level in the present invention)

(3) Fixability evaluation A full-color copying machine imagePRESS C800 made by Canon is equipped with a developing unit containing a two-component developer 1 for color toner in the cyan station, and a two-component developer 1 for transparent toner is placed in the black station. A developer was installed and the image was modified so that an image could be formed with the fixing temperature removed, and an unfixed image was formed. For the evaluation, plain paper: OSE TOP COLOR PAPER (A4 100.0 g / m ² ) (sold from Canon Marketing Japan Inc.) was used.

The amount of toner on the paper of the color toner image FFH image (hereinafter, solid portion) is 1.2 mg / cm ² , and the amount of toner on the paper of the FFH image (hereinafter, solid portion) of the transparent toner image is 0 The development conditions were adjusted as appropriate so as to be .45 mg / cm ^2, and a solid unfixed image of 3 cm from the leading edge of the A4 evaluation paper and 2 cm × 10 cm was formed at the center of the evaluation paper. The unfixed image was conditioned for 24 hours at room temperature and low humidity (25 ° C./5% RH).

  Take out the fixing unit from Canon full color copier imagePRESS C800 and prepare it in a low temperature and low humidity environment (15 ° C / 10% RH) using a fixing test jig modified so that the process speed and upper and lower fixing member temperatures can be controlled independently. did. With the fixing speed adjusted to 400 mm / sec and the lower belt temperature fixed at 90 ° C., the upper belt temperature of the fixing test jig was adjusted every 5 ° C. within the range of 100 to 200 ° C. The moisture-adjusted unfixed image was passed through. The fixed image that has passed through the fixing device is rubbed 5 times with a lens cleaning wiper (Dasper Ozu Sangyo Co., Ltd.) applied with a load of 4.9 kPa, and the gloss reduction rate before and after rubbing becomes 5% or less. The point was taken as the fixing temperature. Based on the criterion that fixing is not possible when glossiness decreases by 5% or less, the lowest upper belt set temperature that does not exceed 5% of the glossiness reduction rate is set as the fixing start temperature, and evaluated according to the following evaluation criteria. . Table 7 shows the evaluation results.

(Evaluation criteria: low temperature fixability)
A: Less than 110 ° C. (very good)
B: 110 ° C. or higher and lower than 140 ° C. (excellent)
C: 140 degreeC or more and less than 155 degreeC (slightly excellent)
D: 155 ° C or higher and lower than 180 ° C (prior art level; acceptable level in the present invention)
E: 180 ° C. or higher (inferior to conventional; unusable level in the present invention)

(4) Hot offset resistance Plain paper: CS-680 (A4; 68.0 g / m ² ) (sold from Canon Marketing Japan Inc.) was used for evaluation.

The amount of the FFH image (hereinafter referred to as a solid portion) of the color image applied to the toner on the paper is 0.10 mg / cm ² , and the amount of the toner of the FFH image (hereinafter referred to as the solid portion) of the transparent toner image is 0.1. The development conditions were adjusted to be 04 mg / cm ² to obtain an unfixed FFH image.

Thereafter, as in the low-temperature fixing property evaluation, evaluation was performed in a normal temperature and low humidity environment (23 ° C./10% RH) using a fixing evaluation jig obtained by modifying a fixing device removed from the Canon full color copying machine imagePRESS C800. With the fixing speed adjusted to 200 mm / sec and the lower belt temperature fixed at 90 ° C., the fixing temperature is adjusted every 5 ° C. within the range of 100 to 200 ° C., and the white background portion of the fixed image at each fixing temperature is reflected. The rate was measured and the maximum value was taken as D _B (%).

D _A (%) is the average value of the reflectance at 5 locations on the evaluation paper before printing, and the difference between D _A (%) and D _B (%) does not exceed 0.5%, the highest The fixing temperature was set as the fixing upper limit temperature (hot offset start temperature), and the hot offset resistance was evaluated according to the following criteria. Table 7 shows the evaluation results.

The reflectance was measured by a reflectometer (“REFLECTOMETER MODEL TC-6DS”, manufactured by Tokyo Denshoku Co., Ltd.).

(Evaluation criteria: Hot offset resistance)
A: 220 ° C. or higher (very good)
B: 205 ° C or higher and lower than 220 ° C (excellent)
C: 190 ° C or higher and lower than 205 ° C (slightly better)
D: 175 ° C. or higher and lower than 190 ° C. (prior art level; acceptable level in the present invention)
E: Less than 175 ° C. (Inferior to conventional; unusable level in the present invention)

[Example 2]
In Example 1, the fixing speed of the Canon full color copier imagePRESS C800 for producing samples for evaluation of gloss uniformity and “watermark” image recognition is 350 mm / sec, and the Canon full color copier imagePRESS C1 + Evaluation was performed in the same manner except that the fixing speed was changed to 175 mm / sec. Table 7 shows the evaluation results.

[Example 3]
The two-component developer 1 for color toner is placed in the cyan station of the Canon full-color copying machine imagePRESS C800, the two-component developer 1 for transparent toner is placed in the black station, and an FFH image (hereinafter referred to as a solid part) is used. ), The development conditions are appropriately adjusted so that the amount of the toner loaded on the paper is 0.45 mg / cm ^2, and a solid image of 4 cm × 15 cm of transparent toner at the center of the evaluation paper, 5 cm from the front edge of the A4 evaluation paper. An image was formed so that the image could be transferred to a primary transfer member.

Thereafter, using cyan toner, the development conditions were adjusted as appropriate so that the amount of the FFH image (hereinafter, solid portion) toner applied to the paper was 1.2 mg / cm ^2, and the evaluation was 3 cm from the leading edge of the A4 evaluation paper. An image was formed so that a 4 cm × 15 cm solid image was formed at the center of the paper, and transferred to the primary transfer member. Thereafter, the formed composite image was secondarily transferred to an evaluation paper, fixed at once, and a fixed image was output. At this time, the fixing speed was 325 mm / sec.

  In the obtained fixed image, a transparent toner is disposed on the upper layer of the cyan toner, and as shown in FIG. 1, a cyan toner monochromatic image portion 1 (2 cm × 15 cm), an image portion 2 formed by cyan toner and transparent toner. (2 cm × 15 cm), a white background portion (2 cm × 15 cm) formed of a transparent toner was formed.

As the evaluation paper, coated paper: OK top coat + (A4; 127.9 g / m ² ) (Oji Paper) was used.

[Examples 4 to 27, Comparative Examples 1 to 5]
In Example 3, as shown in Table 6, the evaluation was made in the same manner except that the two-component developers 2 to 18 for color toner and the two-component developers 2 to 16 for transparent toner were changed. Table 7 shows the evaluation results.

Claims (4)

A charging step of charging the electrostatic latent image carrier by a charging means;
An exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image;
A developing step of developing the electrostatic latent image with a developer containing toner and a magnetic carrier to form a toner image using a developing device;
In an image forming method comprising a transfer step of transferring the toner image to a transfer material with or without an intermediate transfer member, and a fixing step of fixing the transferred toner image to the transfer material.
The image forming method forms a color toner image by combining one or more color toners selected from the group consisting of yellow toner, magenta toner, cyan toner, and black toner and a transparent toner, on the transfer material. An image forming method for forming a transparent toner image on the uppermost layer;
The colored toner and the transparent toner are toners containing a binder resin and a release agent,
The storage elastic modulus G ′ _Cl (90) of the colored toner at 90 ° C. and the storage elastic modulus G ′ _Tr (90) of the transparent toner at 90 ° C. satisfy the following formulas (1) to (3). An image forming method.
3.0 × 10 ⁵ ≦ G ′ _Tr (90) ≦ 1.0 × 10 ⁷ (1)
5.0 × 10 ⁴ ≦ G ′ _Cl (90) ≦ 1.0 × 10 ⁶ (2)
7.0 ≦ G ′ _Tr (90) / G ′ _Cl (90) ≦ 100.0 (3) The storage elastic modulus G ′ _Cl (130) of the colored toner at 130 ° C. and the storage elastic modulus G ′ _Tr (130) of the transparent toner at 130 ° C. satisfy the following expressions (4) and (5). The image forming method according to claim 1.
1.0 × 10 ³ ≦ G ′ _Cl (130) ≦ 1.0 × 10 ⁵ (4)
0.5 ≦ G ′ _Tr (130) / G ′ _Cl (130) ≦ 5.0 (5) Charging means for charging the electrostatic latent image carrier,
Exposure means for exposing the charged electrostatic latent image carrier to form an electrostatic latent image;
A developing unit having a developer containing toner and a magnetic carrier, and developing the electrostatic latent image with the developer to form a toner image;
In an image forming apparatus having a transfer unit for transferring the toner image to a transfer material with or without an intermediate transfer member, and a fixing unit for fixing the transferred toner image to the transfer material,
The image forming apparatus forms a color toner image by combining one or more color toners selected from the group consisting of yellow toner, magenta toner, cyan toner, and black toner and a transparent toner, on the transfer material. An image forming apparatus for forming a transparent toner image on the uppermost layer;
The colored toner and the transparent toner are toners containing a binder resin and a release agent,
The storage elastic modulus at 90 ° C. of the colored toner is G ′ _Cl (90) and the storage elastic modulus G ′ _Tr (90) of the transparent toner at 90 ° C. satisfies the following formulas (1) to (3). An image forming apparatus.
3.0 × 10 ⁵ ≦ G ′ _Tr (90) ≦ 1.0 × 10 ⁷ (1)
5.0 × 10 ⁴ ≦ G ′ _Cl (90) ≦ 1.0 × 10 ⁶ (2)
5.0 ≦ G ′ _Tr (90) / G ′ _Cl (90) ≦ 100.0 (3) A charging step of charging the electrostatic latent image carrier by a charging means;
An exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image;
A developing step of developing the electrostatic latent image with a developer containing toner and a magnetic carrier using a developing device to form a toner image;
In a toner kit used in an image forming method including a transfer step of transferring the toner image to a transfer material with or without an intermediate transfer member, and a fixing step of fixing the transferred toner image to the transfer material,
The image forming method forms a color toner image by combining one or more color toners selected from the group consisting of yellow toner, magenta toner, cyan toner, and black toner and a transparent toner, on the transfer material. An image forming method for forming a transparent toner image on the uppermost layer;
The colored toner and the transparent toner are toners containing a binder resin and a release agent,
The storage elastic modulus at 90 ° C. of the colored toner satisfies G ′ _Cl (90), and the storage elastic modulus G ′ _Tr (90) of the transparent toner at 90 ° C. satisfies the following formulas (1) to (3). A toner kit for use in an image forming method.
3.0 × 10 ⁵ ≦ G ′ _Tr (90) ≦ 1.0 × 10 ⁷ (1)
5.0 × 10 ⁴ ≦ G ′ _Cl (90) ≦ 1.0 × 10 ⁶ (2)
5.0 ≦ G ′ _Tr (90) / G ′ _Cl (90) ≦ 100.0 (3)

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