JP2019012158A - toner - Google Patents

Abstract

To provide a toner excellent in anti-adhesion property of a discharged sheet, in which adhesion of a discharged sheet does not occur even at the time of high-speed output.MEANS FOR SOLVING THE PROBLEM: The toner contains binder resin, wax and toner particles having silica microparticles. A number average diameter (D1) of primary particles of the silica microparticles is 60 nm or more and 300 nm or less. In a cross section of the toner particle, a relation between a toner cross section area St and an area S occupied by the silica microparticles is 0.05≤S/St≤0.50. In the cross section of the toner particle, in each section obtained by dividing a rectangle circumscribed to the cross section of the toner into 9 sections, a variation coefficient of an area ratio occupied by the silica microparticle to the cross sectional area of the toner particle is 0.45 or less.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system.

In an image forming apparatus using an electrophotographic method, a digital printing technique that directly prints without going through a plate making process called “print on demand (POD)” has attracted attention. POD printing has advantages over conventional offset printing because it can handle variable printing and distributed printing with different contents for each sheet. At the same time, there are increasing demands for power saving and shortened wait time. In order to cope with these, a toner having improved low-temperature fixability is required as the toner. In order to cope with catalog printing and the like, high-quality images are required not only for high-speed output but also for double-sided printing using various recording media (plain paper, cardboard, special paper).
In general, many color images used for catalogs and the like have a large print image area such as a picture or a photograph. For this reason, when output prints are stacked, a phenomenon in which images are bonded to each other (paper discharge bonding) may occur. Patent Document 1 proposes a toner that can store an image at a high temperature and can be fixed at a lower temperature by including light-colored or colorless internal fine particles in the toner particle.

JP 2001-305781 A

However, in the toner proposed in the above document, the fixing property is improved by lowering the softening temperature of the toner, but there is a case where the paper discharge adhesion occurs at the time of high-speed output.
The object of the present invention is to solve the above-mentioned problems. An object of the present invention is to provide a toner having excellent sheet discharge adhesion resistance that does not cause sheet discharge adhesion even during high-speed output.

The above problem can be solved by the toner having the following configuration.
That is, the present invention is a toner having toner particles having a binder resin, wax and silica fine particles,
The number average diameter (D1) of primary particles of the silica fine particles is 60 nm or more and 300 nm or less,
In the cross section of the toner particles, the relationship between the cross sectional area St of the toner particles and the area S occupied by the silica fine particles is 0.05 ≦ S / St ≦ 0.50,
In the cross section of the toner particle, the coefficient of variation of the area ratio occupied by the silica fine particle with respect to the cross sectional area of the toner particle in each section obtained by dividing the rectangle circumscribing the cross section of the toner into nine is 0.45 or less. This invention relates to a toner.

  According to the present invention, it is possible to provide a toner having excellent sheet discharge adhesion resistance that does not cause sheet discharge adhesion even during high-speed output.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

  The toner of the present invention is a toner having toner particles having a binder resin, wax and silica fine particles, wherein the number average diameter (D1) of primary particles of the silica fine particles is 60 nm or more and 300 nm or less, and the toner particles In the cross section, the relationship between the cross sectional area St of the toner particles and the area S occupied by the silica fine particles is 0.05 ≦ S / St ≦ 0.50, and the cross section of the toner circumscribes the cross section of the toner. The variation coefficient of the area ratio occupied by the silica fine particles with respect to the cross-sectional area of the toner particles in each section obtained by dividing the rectangle into nine is 0.45 or less.

  The toner as described above does not cause discharge adhesion even at high-speed output, and has excellent discharge resistance.

  In the present invention, the reason for solving the above problem is not necessarily clear, but is considered as follows.

  In order to increase the paper discharge resistance, it is effective to increase the heat resistance of the printed image by generally increasing the softening point temperature of the toner. Further, in order to suppress the occurrence of adhesion of discharged paper, it is effective to reduce the number of printed sheets per unit time so that the heat of the discharged printed matter is dissipated and no heat is accumulated even if they are stacked. However, in recent years, power saving, high-speed output, and adaptation to various recording media are required.

  Thus, it has been found that the image (toner layer) after fixing can be protected by dispersing silica fine particles in the toner particles. This is considered to be because pressure and heat are applied during fixing, and the toner particles in the toner layer are crushed, but the silica fine particles retain their shape and can exert a spacer effect. As a result, even if the discharged printed matter has heat, the silica fine particles, which are spacers, can be prevented from adhering to the entire fixed image (toner layer), and excellent anti-discharge adhesiveness can be obtained. Obtained.

  However, the above-mentioned effects cannot be obtained by simply dispersing silica fine particles in the toner. In order to obtain the spacer effect, it is important that the area occupied by the silica fine particles is a constant value in the cross section of the toner particles. Further, the silica fine particles present in the toner may be primary particles or aggregated particles, but it is also important that they are uniformly distributed in the toner. It turns out that the silica fine particles occupy a certain area in the toner particles and spread uniformly, so that the spacer effect is obtained over the entire image after fixing, and the paper discharge adhesion resistance is most improved. did. In addition, when the silica fine particles are unevenly distributed in the toner particles, the adhesion between the recording medium and the binder resin is lowered, so that the toner fixing property is deteriorated, which may cause a fixing inhibition such as peeling of the toner layer. there were.

In the present invention, the fine particles dispersed in the toner particles are most preferably silica fine particles having a high volume resistance value from the viewpoint of charging stability of the toner. Generally, in the case of silica fine particles, alumina or titania tends to have a low volume resistance value compared to 1.0 × 10 ¹⁴ Ω · cm or more.

  For the above-mentioned reasons, the silica fine particles are dispersed in the toner particles under a certain condition, thereby obtaining a toner having excellent sheet discharge adhesion resistance that does not cause sheet discharge adhesion even during medium and high speed output.

  In the toner according to the present invention, the number average diameter (D1) of primary particles of the silica fine particles is 60 nm or more and 300 nm or less, preferably 70 nm or more and 250 nm or less, more preferably 80 nm or more and 200 nm or less. When the number average particle diameter (D1) of the primary particles is within the above range, the image storage stability is excellent, and no paper discharge adhesion occurs even at high-speed output. When the number average diameter of the primary particles is less than 60 nm, the primary particles are likely to be completely embedded in the fixed image at the time of fixing, and the paper discharge resistance may deteriorate.

  In the toner according to the present invention, in the cross section of the toner particle, the relationship between the cross sectional area St of the toner particle and the area S occupied by the silica fine particles is 0.05 ≦ S / St ≦ 0.50. Preferably, 0.08 ≦ S / St ≦ 0.40, and more preferably 0.10 ≦ S / St ≦ 0.30. When the relationship of S / St is within the above range, the sheet discharge adhesion is further improved, and sheet discharge adhesion does not occur even at high-speed output on both sides.

  In the toner according to the present invention, in the cross section of the toner particle, the area ratio of the silica fine particles to the cross sectional area of the toner particle in each section obtained by dividing the rectangle circumscribing the cross section of the toner into nine is The coefficient of variation is 0.45 or less. Preferably it is 0.35 or less, More preferably, it is 0.30 or less. When the coefficient of variation is in the above range, the sheet discharge resistance is improved even in a high temperature and high humidity environment where sheet discharge adhesion is more likely to occur.

  A preferable toner structure in the present invention will be described in detail below.

[resin]
The toner according to the present invention has a binder resin. The binder resin used for the toner 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, from the viewpoints of low-temperature fixability and chargeability control, it is preferable to use a polyester resin, and it is more preferable to use a crystalline polyester resin and an amorphous polyester resin.

[Amorphous polyester resin]
The amorphous polyester resin used in the toner of the present invention is preferably a polycondensation resin of an alcohol component mainly composed of an aromatic diol and a carboxylic acid component. In addition, in this invention, a main component shows that the content is 50 mass% or more.

  The aromatic diol used in the amorphous polyester resin is not particularly limited, but bisphenol derivatives represented by the following formula (A) and diols represented by the following formula (B) are preferable.

（式中、Ｒはエチレン又はプロピレン基、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２以上７以下である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 or more and 7 or less.)

  Examples of the bisphenol derivative represented by the above formula (A) include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2- Bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2 , 2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, and the like. In some cases, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5 -Diols such as pentanediol, 1,6-hexanediol, and other diols such as bisphenol A and hydrogenated bisphenol A are bisphenol derivatives represented by the above formula (A) or diols represented by the above formula (B) It is also possible to use in combination with a kind.

  Other alcohol components that can be used in the amorphous polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 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, 2-methylpropane triol, 2-methyl-1,2,4-butane triol, trimethylol ethane, trimethylol propane, 1,3,5-trihydroxy methyl benzene.

  As described above, the main component of the alcohol component constituting the amorphous polyester resin is an aromatic diol. Here, in the alcohol component constituting the amorphous polyester resin, the aromatic diol is preferably contained in a proportion of 80 mol% or more and 100 mol% or less, and more preferably contained in a proportion of 90 mol% or more and 100 mol% or less. .

  As the polyvalent carboxylic acid monomer used in the polyester unit of the polyester resin, the following polyvalent carboxylic acid monomers can be used.

  Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids and These lower alkyl esters are mentioned. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenyl succinic acid are preferably used.

  Examples of the trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid. 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra ( Methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, acid anhydrides thereof, or lower alkyl esters thereof. Among these, in particular, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or its derivative, is inexpensive and easy to control, so that it is preferably used. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination.

  The amorphous polyester resin may be a hybrid resin containing other resin components as long as the polyester resin is a main component. 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 conducting a polymerization reaction of one or both resins is preferable.

  For example, among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, itaconic acid, and anhydrides thereof. Can be mentioned. Among the monomers constituting the vinyl copolymer component, those that can react with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  Further, in the present invention, as a non-crystalline polyester resin, if a polyester resin is a main component, various resin compounds conventionally known as binder resins can be used in addition to the above-mentioned vinyl resins. . Examples of such resin compounds include phenol resin, natural resin-modified phenol resin, natural resin-modified male resin, acrylic resin, methacrylic resin, polyvinyl acetate resin, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy Examples include resins, xylene resins, polyvinyl butyral, terpene resins, coumarone indene resins, petroleum resins, and the like.

  The amorphous polyester in the present invention can be produced according to a normal polyester synthesis method. For example, a desired polyester resin can be obtained by subjecting the above-mentioned carboxylic acid component and alcohol component to an esterification reaction or transesterification reaction and then performing a polycondensation reaction according to a conventional method under reduced pressure or by introducing nitrogen gas. it can.

  The esterification or transesterification reaction can be carried out using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, and magnesium acetate as necessary.

  The polycondensation reaction can be carried out using a conventional polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide. .

  The peak molecular weight of the amorphous polyester resin is preferably 8000 or more and 13000 or less from the viewpoint of low-temperature fixability and hot offset resistance. The number average molecular weight of the amorphous polyester resin is preferably 1500 or more and 3500 or less from the viewpoint of low-temperature fixability.

[Crystalline polyester resin]
In the present invention, the crystalline polyester resin can be obtained from an alcohol component and a carboxylic acid component. Polycondensation of an alcohol component containing 80 to 100 mol% of an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing 80 to 100 mol% of an aliphatic dicarboxylic acid having 6 to 12 carbon atoms Resins are preferred. More preferably, it is an alcohol component containing 85 mol% or more and 100 mol% or less of an aliphatic diol, and a carboxylic acid component containing 85 mol% or more and 100 mol% or less of an aliphatic dicarboxylic acid.

  The aliphatic diol is not particularly limited, but is preferably a linear (more preferably linear) aliphatic diol, such as butanediol, pentanediol, hexanediol, heptanediol, octanediol, and nonanediol. And decanediol are preferably exemplified.

  In the present invention, a polyhydric alcohol component other than the aliphatic diol can also be used as the alcohol component of the crystalline polyester resin. Among the polyhydric alcohol components, examples of the dihydric alcohol include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; 1,4-cyclohexanedimethanol and the like. Among the polyhydric alcohol monomers, trihydric or higher polyhydric alcohols include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1, Aliphatic alcohols such as 2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, etc. Is mentioned.

  Furthermore, in this invention, you may use monohydric alcohol collectively as an alcohol component of crystalline polyester resin. Examples of the monovalent alcohol include monofunctional groups such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, and dodecyl alcohol. And alcohol.

  On the other hand, the aliphatic dicarboxylic acid is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, glutaconic acid, azelaic acid, sebacic acid, etc., and hydrolyses these acid anhydrides or lower alkyl esters. Also included.

  As the carboxylic acid component of the crystalline polyester resin, a polyvalent carboxylic acid other than the aliphatic dicarboxylic acid can be used in combination. Among other polyvalent carboxylic acids, divalent carboxylic acids include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid; cyclohexanedicarboxylic acid and the like. Examples thereof include alicyclic carboxylic acids, and these acid anhydrides or lower alkyl esters are also included. Among other carboxylic acids, trivalent or higher polyvalent carboxylic acids include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4. -Aromatic carboxylic acids such as naphthalenetricarboxylic acid and pyromellitic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxy Examples thereof include aliphatic carboxylic acids such as propane, and derivatives of these acid anhydrides or lower alkyl esters are also included.

  Furthermore, you may contain monovalent carboxylic acid together as a carboxylic acid component of crystalline polyester resin. Examples of the monovalent carboxylic acid include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, Examples thereof include monocarboxylic acids such as dodecanoic acid and stearic acid.

  The crystalline polyester in the present invention can be produced according to an ordinary polyester synthesis method. For example, a desired polyester resin can be obtained by subjecting the above-mentioned carboxylic acid component and alcohol component to an esterification reaction or transesterification reaction and then performing a polycondensation reaction according to a conventional method under reduced pressure or by introducing nitrogen gas. it can.

  The esterification or transesterification reaction is carried out using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, tin 2-ethylhexanoate, manganese acetate, magnesium acetate, etc., if necessary. be able to.

  The polycondensation reaction is carried out using a conventional polymerization catalyst such as titanium butoxide, dibutyltin oxide, tin 2-ethylhexanoate, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. Can be done using. The polymerization temperature and the catalyst amount are not particularly limited, and may be determined appropriately.

  In the esterification or transesterification reaction or polycondensation reaction, all monomers may be charged all at once in order to increase the strength of the resulting crystalline polyester resin. In order to reduce the low molecular weight component, a method in which a divalent monomer is first reacted and then a trivalent or higher monomer is added and reacted may be used.

  The molar ratio (carboxylic acid component / alcohol component) between the alcohol component and the carboxylic acid component, which are raw material monomers of the crystalline polyester resin, is preferably 0.80 or more and 1.20 or less.

  In the present invention, the content of the crystalline polyester is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 1 part by mass or more and 22 parts by mass or less, with respect to 100 parts by mass of the amorphous polyester resin. Preferably they are 2 mass parts or more and 18 mass parts or less. When the content of the crystalline polyester resin is in the above range, the adhesion between the recording medium and the binder resin is further increased. Therefore, even when the image is folded, the toner layer can be further prevented from peeling off (image folding resistance).

[wax]
The toner of the present invention contains a wax. Examples of the wax include the following.

  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 Products: Waxes mainly composed of fatty acid esters such as carnauba wax; Deoxidized part or all of 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, carnauvir alcohol, ceryl alcohol , Saturated alcohols such as merisyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, and carnauvir alcohol , Esters with alcohols such as ceryl alcohol, melyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylenebisstearic acid amide, ethylene Saturated fatty acid bisamides such as scapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N 'Unsaturated fatty acid amides such as dioleyl sebacic acid amide; m-xylene bis stearic acid amide, N, N' aromatic bisamides such as distearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate , Aliphatic metal salts such as magnesium stearate (generally referred to as metal soap); waxes grafted to aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; behenine Acid monoglycerin And methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable fats and oils; fatty acids with polyhydric alcohols of the partial ester such as.

  Among these waxes, a hydrocarbon wax such as paraffin wax and Fischer-Tropsch wax, or a fatty acid ester wax such as carnauba wax is preferable from the viewpoint of improving low-temperature fixability and hot offset resistance. In the present invention, a hydrocarbon wax is more preferable in that the hot offset resistance is further improved.

  The content of the wax 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. When the content of the wax is within this range, it is easy to efficiently exhibit hot offset properties at a high temperature.

  Further, from the viewpoint of achieving both storage stability and high-temperature offset property, the maximum endotherm existing in the temperature range of 30 ° C. to 200 ° C. in the endothermic curve at the time of temperature rise measured by a differential scanning calorimeter (DSC). The peak temperature is preferably 50 ° C. or higher and 110 ° C. or lower.

[Colorant]
Examples of the colorant (coloring material) that can be contained in the toner of the present invention include the following.

  Examples of the black colorant include carbon black; a yellow colorant, a magenta colorant, and a cyan colorant that are toned in 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 content of the colorant is preferably 0.1 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

[Magnetic material]
The toner of the present invention may be a magnetic toner or a non-magnetic toner. When used as a magnetic toner, it is preferable to use magnetic iron oxide as the magnetic material. As the magnetic iron oxide, iron oxides such as magnetite, maghematite, and ferrite are used. The amount of magnetic iron oxide contained in the toner is preferably 25 parts by mass or more and 95 parts by mass or less, and more preferably 30 parts by mass or more and 45 parts by mass or less 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. For example, as a negative charge control agent, a salicylic acid metal compound, a naphthoic acid metal compound, a dicarboxylic acid metal compound, a sulfonic acid or a polymer compound having a carboxylic acid in the side chain, a sulfonate or a sulfonate esterified product And a polymer compound having a side chain with a carboxylate or a carboxylic acid ester, 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 10.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

[Silica fine particles]
The toner particles according to the present invention contain silica fine particles. The content of the silica fine particles is preferably 5 parts by mass or more and 30 parts by mass or less, more preferably 7 parts by mass or more and 20 parts by mass or less, and still more preferably 10 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the binder resin. It is below mass parts. When the content of the silica fine particles is 30 parts by mass or less, the fixability (image bending resistance) is improved.

  Examples of the method for producing silica include the following methods. Flame melting method in which silicon compound is gasified and decomposed and melted in a flame, and gas phase method in which silicon tetrachloride is combusted at a high temperature together with a mixed gas of oxygen, hydrogen, and a diluent gas (for example, nitrogen, argon, carbon dioxide, etc.) (Dry process silica or fumed silica) A wet process (sol-gel) that removes the solvent from the silica sol suspension obtained after hydrolyzing and condensing alkoxysilane with a catalyst in an organic solvent containing water. silica).

  Furthermore, a method of making the silica particles obtained by the above production method into a desired number average particle diameter by classification treatment and / or crushing treatment may be used.

  Furthermore, the silica fine particles are preferably silica fine particles that have been subjected to a hydrophobic treatment. The hydrophobizing treatment is not particularly limited, and a known method can be used.

  Examples of the silane coupling agent include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilamen, dimethyldiethoxysilane, Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisi Examples thereof include loxane, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and having one hydroxyl group on each terminal silicon atom.

  Examples of the silicone oil used for treating the silica fine particles include dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. The silicone oil is not limited to the above formula. A known technique can be used as a method for treating the silicone oil. For example, silicate fine powder and silicone oil are mixed using a mixer; silicone oil is sprayed into the silicate fine powder using a sprayer; or after the silicone oil is dissolved in a solvent, the silicate fine powder is mixed. The method of mixing is mentioned. The processing method is not limited to this.

  The silica fine particles are more preferably those using hexamethyldisilazane as a surface treating agent.

[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 magnetic carriers 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 those Generally known materials such as magnetic particles such as alloy 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 of the present invention can be produced by a conventionally known toner production method such as an emulsion aggregation method, a melt-kneading method, or a dissolution suspension method, and is not particularly limited.

  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, a predetermined amount of other components such as a binder resin, wax, inorganic fine particles, and, if necessary, an organic metal compound and a colorant are weighed and mixed 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 of continuous production, a single-screw or twin-screw extruder has become the mainstream. ing. 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 Kay Sea Kay Co., Ltd.) ), 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. The set temperature for melt kneading is preferably set within Tm + 15 ° C. with respect to the softening point (Tm) of the main binder resin, and more preferably set to a temperature equal to or lower than Tm. The main binder resin here refers to a binder component occupying 50% by mass as a material composition. In the case described above, a sufficient share is applied to the melt-kneaded product, so that the material dispersibility becomes better.

  Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization process, 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), turbo Finely pulverize with a mill (manufactured by Turbo Kogyo) or an air jet type pulverizer.

  After that, if necessary, such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification type 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 classifier or a sieving machine.

  In the present invention, additives such as inorganic fine powder and resin particles are added and mixed and dispersed on the obtained toner particle surfaces as necessary, and the additives are fixed to the toner particle surfaces by surface treatment with hot air in the dispersed state. A heat treatment step may be performed. Through the heat treatment step, the toner particle shape can be adjusted.

  To the toner particles produced by the above production method, an external additive selected as necessary may be added and mixed (externally added). Examples thereof include inorganic fine powders such as silica, alumina, titania and calcium carbonate, and resin particles such as vinyl resins, polyester resins and silicone resins. These inorganic fine powders and resin particles function as external additives such as charge control, fluidity aid, and cleaning aid. 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, a method for measuring each physical property will be described.

<Measuring method of softening point (Tm) of amorphous polyester 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 Amorphous Polyester 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 heating 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 and peak molecular weight of crystalline polyester and amorphous polyester 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 multiple commercially available polystyrene gel columns, for example, the following combinations are mentioned. A combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK and TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H (manufactured by Tosoh Corporation) HXL), G5000H (HXL), G6000H (HXL), G7000H (HXL), and a combination of TSKgourd column.

  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 crystalline polyester resin and wax>
The melting point of the crystalline polyester resin and 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 Volume Average Particle Size (D4) of Toner>
The volume average particle diameter (D4) of the toner is determined based on a precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a pore electric resistance method equipped with an aperture tube of 100 μm and measurement conditions. 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 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 of (1) installed in the sample stand, the electrolytic solution of (5) in which the toner is dispersed is dropped using a pipette, and the measured 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 volume 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 volume average particle diameter (D4).

<Measurement of toner cross section by TEM observation>
Cross-sectional observation of the toner with a transmission electron microscope (TEM) can be performed as follows. In the present invention, in the cross-sectional observation of the toner, the cross-sectional area St of the toner and the area S occupied by the silica fine particles were evaluated.

  By crystalline ruthenium tetroxide on the cross section of the toner, a crystalline polyester resin can be obtained as a clear contrast. The crystalline polyester resin is dyed weaker than the organic component constituting the inside of the toner. This is presumably because the infiltration of the dye material into the crystalline polyester resin is weaker than the organic component inside the toner due to a difference in density.

  Because the amount of ruthenium atoms varies depending on the intensity of staining, the strongly stained part has many of these atoms, the electron beam does not pass through, it becomes black on the observation image, and the part that is weakly stained is The electron beam is easily transmitted and becomes white on the observation image.

  Using an osmium plasma coater (filgen, OPC80T), an Os film (5 nm) and a naphthalene film (20 nm) were applied to the toner as a protective film, and embedded with a photo-curable resin D800 (JEOL). Using a sonic ultramicrotome (Leica, UC7), a toner cross section having a film thickness of 60 nm (or 70 nm) was prepared at a cutting speed of 1 mm / s.

The obtained cross section was dyed for 15 minutes in a RuO ₄ gas 500 Pa atmosphere using a vacuum electron dyeing apparatus (filgen, VSC4R1H), and STEM observation was performed using the STEM function of TEM (JEOL, JEM2800). The STEM probe size was 1 nm, and the image size was 1024 × 1024 pixels.

  For the obtained image, image processing software “Image-Pro Plus (manufactured by Media Cybernetics)” was used.

  In the obtained cross-sectional image, the total area S occupied by the silica fine particles and the cross-sectional area St of the toner are measured. In the present invention, cross sections of 20 toners were observed. It is assumed that the observed toner cross section exhibits a long diameter R (μm) satisfying a relationship of 0.9 ≦ R / D4 ≦ 1.1 with respect to the weight average particle diameter (D4).

  Further, in the cross section of the toner particle, the coefficient of variation of the area ratio occupied by the silica fine particle with respect to the cross sectional area of the toner particle in each section obtained by dividing the rectangle circumscribing the toner cross section into nine was calculated as follows.

  For each toner particle, a rectangular area obtained by dividing the circumscribed rectangle of the toner particle having the major axis of the toner particle as a long side into nine parts was analyzed.

  When a background other than the toner particle surface is reflected in the nine-divided rectangular area image, the following analysis is performed after setting only the toner surface portion as an AOI (Area of Interst). The AOI can be defined by selecting a free curve AOI button from the AOI tool and drawing a closed curve that traces the contour of the toner surface. Select “Measure” and “Count / Size” in the toolbar, and select “Automatically extract bright objects” in the “Select luminance range” field. Select 8 connections in the object extraction option and set smoothing to 0. In addition, sorting, filling holes, and inclusion lines are not selected, and “exclude boundary lines” is set to “none”. Select “Measurement Item” from “Measurement” on the toolbar, and set the area selection range to 2 to 107. Press “Count” to extract the silica fine particle component.

  On the image, double-click the object number of the fine particle that is not the analysis target. Select "Exclude" in the attribute window of the opened object. By repeating this operation, only silica fine particles to be analyzed are extracted.

The ratio of the area occupied by the silica fine particles to the cross-sectional area of the toner particles is calculated by calculating the total cross-sectional area (P) of the extracted target silica fine particle components and the above-described nine divided rectangular areas as the AOI. From the area (S), it is obtained using the following formula.
Ratio of area occupied by silica fine particles to cross-sectional area of toner particles = P / S

  The average value / standard deviation was determined from the area ratio of the silica fine particles to the cross-sectional area of the toner particles divided into nine rectangular areas, and the coefficient of variation was calculated. The same operation was repeated for 20 toner particles, and the average value was used.

<Measurement method of number average particle diameter (D1) of primary particles of silica fine particles>
Toner particles dispersed in a water-soluble resin were placed in a cryomicrotome (ULTRACUT UCT manufactured by Leica) apparatus. The apparatus was cooled to −80 ° C. with liquid nitrogen, and the water-soluble resin in which the toner particles were dispersed was frozen. The frozen water-soluble resin was trimmed with a glass knife so that the cutting surface shape was about 0.1 mm wide and about 0.2 mm long. Next, an ultra-thin section (thickness setting: 70 nm) of toner containing a water-soluble resin was prepared using a diamond knife, and moved onto a TEM observation grid mesh using an eyelash probe. After returning the ultra-thin slice of the toner particles containing the water-soluble resin to room temperature, the water-soluble resin was dissolved in pure water to obtain an observation sample of a transmission electron microscope (TEM). The sample was observed with a transmission electron microscope H-7500 manufactured by Hitachi, Ltd. at an acceleration voltage of 100 kV, and an enlarged photograph of the cross section of the toner particles was taken. The magnification of the enlarged photograph was 20000 times.

  The TEM image obtained by the above photography was converted into binary image data using image analysis software Image-ProPlus 5.1J (manufactured by Media Cybernetics). Of these, only silica fine particles were analyzed randomly.

  The number average particle diameter of the primary particles of the silica fine particles was defined as the average value of the major and minor axes of the particles. 100 primary particles were randomly selected, and the number average of the primary particle diameters was defined as the number average particle diameter (D1) of the primary particles of the silica fine particles.

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

<Production Example 1 of Amorphous Polyester Resin>
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane:
100.0 mol% based on the total number of moles of polyhydric alcohol
・ Terephthalic acid: 80.0 mol% based on the total number of moles of polycarboxylic acid
Trimellitic anhydride: 20.0 mol% with respect to the total number of polycarboxylic acids
The above materials were put into a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. And 1.5 mass parts of 2-ethylhexanoic acid tin (esterification catalyst) dioctylic acid tin was added as a catalyst with respect to 100 mass parts of monomer total amount. 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, reacted as it was, and after confirming that the softening point measured according to ASTM D36-86 reached 122 ° C. To stop the reaction. The resulting amorphous polyester resin had a softening point (Tm) of 112 ° C. and a glass transition temperature (Tg) of 63 ° C.

<Production Example 1 of Crystalline Polyester Resin>
-1,6-hexanediol 50.0 parts by mass-Dodecanedioic acid 50.0 parts by mass-Tin dioctylate 1.0 part by mass In a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple The above materials were weighed. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, the reaction was performed for 6 hours while stirring at a temperature of 140 ° C., and then the reaction was performed while increasing the temperature to 200 ° C. at 10 ° C./hour. Polyester resin 1 was obtained. The obtained crystalline polyester resin 1 had a weight-average molecular weight of 10,000 and a maximum endothermic peak at 70 ° C. in a DSC curve by differential scanning calorimetry.

[Example 1]
<Production Example of Toner 1>
Noncrystalline polyester resin 93.0 parts by mass Crystalline polyester resin 4.0 parts by mass Hydrophobic silica fine particles having a number average particle diameter of 110 nm of primary particles surface-treated with 10% by mass of hexamethyldisilazane (in Table 1) Silica fine particles 1) 12.0 parts by mass, aluminum 3,5-di-t-butylsalicylate compound
0.5 parts by mass Fischer-Tropsch wax (peak temperature of the maximum endothermic peak 90 ° C)
5.0 parts by mass I. Pigment Blue 15: 3 5.0 parts by mass After mixing the raw materials shown in the prescription with a Henschel mixer (FM75J type, manufactured by Mitsui Miike Chemical Co., Ltd.) at a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes, It knead | mixed with the biaxial kneader (PCM-30 type | mold, Ikegai Co., Ltd.) set to the temperature of 110 degreeC. 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 condition of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) was set to 50.0 s ^-1 for the speed of the classifying rotor. The obtained toner particles had a weight average particle diameter (D4) of 5.6 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 (FM75J type, manufactured by Mitsui Miike Chemical Co., Ltd.), and an ultrasonic vibration sieve having an opening of 54 μm Then, toner 1 was obtained.

  The obtained toner 1 had an endothermic peak derived from the crystalline polyester resin at 70 ° C. and an endothermic peak derived from the wax component at 90 ° C. in the DSC curve by differential scanning calorimetry. Further, a TEM cross section of the toner 1 was observed. The measurement results are shown in Table 2.

The toner 1 and magnetic ferrite carrier particles (number average particle size 35 μm) coated with a silicone resin are used to form a toner concentration of 9% by mass with a V-type mixer (V-10 type: Tokuju Seisakusho Co., Ltd.). The mixture was mixed at 0.5 s ⁻¹ for 5 minutes to obtain a two-component developer 1. Using the two-component developer 1, the evaluation described later is performed and the results are shown in Table 3.

[Examples 2 to 16, Comparative Examples 1 to 5]
As shown in Table 2, toners 2 to 21 were prepared in the same manner as in Example 1 except that the crystalline polyester resin, silica fine particles, and kneading temperature were changed, and further two-component developers 2 to 21 were prepared. did. The obtained developer was evaluated in the same manner as in Example 1. The toner measurement results are shown in Table 2, and the developer evaluation results are shown in Table 3.

[Image evaluation]
As an evaluation machine, an on-demand printer Canon full-color copier imagePRESS C10000VP (output speed: 100 sheets / min (A4)) was used. Evaluation is performed in a normal environment (23 ° C./50% RH, hereinafter also referred to as “N / N environment”) and in a high temperature and high humidity environment (30 ° C./80% RH, hereinafter also referred to as “H / H environment”). It was.

  The performance of the toner was evaluated according to the following method.

<Evaluation of paper discharge adhesion resistance>
For the evaluation, the thickest paper for CLC5000 (A4, basis weight 250 g / m ² , sold by Canon Marketing Japan Inc.) was used. 300 solid images were output by duplex printing so that the applied toner amount was 1.1 mg / cm ² . After the output of 300 sheets, the output image was left for 10 minutes while being overlaid. After leaving for 10 minutes, whether or not the printed image is adhered was evaluated for each sheet. The evaluation results are shown in Table 3. The results were ranked A to D according to the following criteria, but in the present invention, up to rank C is an acceptable level.
A: There is no bonded image and good image quality is maintained.
B: Although there are adhered images, they are easily separated and maintain good image quality.
C: There are 3 or less images that have adhered images and have image defects after separation.
D: There are 4 or less images that have adhered images and have image defects after separation.

<Evaluation of bending resistance>
The bending resistance of the image in the N / N environment was evaluated. The development voltage was adjusted so that the applied amount of toner was 0.55 mg / cm ^2, and a solid image having a size of 10 cm × 10 cm was output. Subsequently, the fixed image was folded in a cross shape and rubbed 5 times with a soft thin paper (for example, “Dasper”, manufactured by Ozu Sangyo Co., Ltd.) while applying a load of 4.9 kPa. When the toner is peeled off at the cross, a sample in which the paper background can be seen is obtained. Next, a cross section of 512 pixels was photographed with a CCD camera at a resolution of 800 pixels / inch. The threshold is set to 60%, the image is binarized, and the part where the toner is peeled is a white part, and the smaller the area ratio of the white part is, the better the bending resistance is. In the present invention, C or higher was determined to be good.

The following paper was used for evaluation of bending resistance.
Paper: Mirror Coat Platinum 209 (Glossy Cardboard) (209 g / m ² )
(Sold from Canon Marketing Japan Inc.)

(Evaluation criteria)
A: Area ratio of white part is less than 1.0% B: Area ratio of white part is 1.0% or more and less than 3.0% C: Area ratio of white part is 3.0% or more and less than 5.0% D : Area ratio of white part is 5.0% or more and less than 7.0% E: Area ratio of white part is 7.0% or more

Claims (3)

A toner having toner particles having a binder resin, wax and silica fine particles,
The number average diameter (D1) of primary particles of the silica fine particles is 60 nm or more and 300 nm or less,
In the cross section of the toner particles, the relationship between the cross sectional area St of the toner particles and the area S occupied by the silica fine particles is 0.05 ≦ S / St ≦ 0.50,
In the cross section of the toner particles, the coefficient of variation of the area ratio of the silica fine particles to the cross sectional area of the toner particles in each section obtained by dividing the rectangle circumscribing the cross section of the toner particles into nine is 0.45 or less. A toner characterized by being.   The toner according to claim 1, wherein the content of the silica fine particles is 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.   The toner according to claim 1, wherein the binder resin includes a crystalline polyester resin and an amorphous polyester resin.