JP2996629B2 - Toner composition and method for controlling gloss in toner image - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to toner compositions suitable for direct electrostatic printing and for developing electrostatic images or magnetic patterns. The invention also relates to an electrostatographic method for forming an image with dry toner particles wherein the toner image is fixed to a final support by a non-contact fusing method.

[0002]

BACKGROUND OF THE INVENTION Electrostatic printing methods are diverse, for example, in direct electrostatic printing, where the electrostatic printing is performed directly from a toner carrier onto a receiving support, the latter by means of an electrically addressable printhead structure. It does not carry any electrostatic latent image according to the image.

[0003] In another form of electrostatic printing, a toner image is formed on an imaging material in the form of a rotating drum provided with an electrostatic layer made up of a number of controllable electrodes under and in a guide layer. The voltage applied imagewise to the controllable electrodes attracts charged toner particles from a toner source.

It is also a technique of electrophotographic printing and copying that forms an electrostatic latent image corresponding to digitized data describing an electrically available image or an original to be copied. Is well known in

In electrophotography, an electrostatic latent image is formed by the process of uniformly charging a photoconductive member and discharging it imagewise by photographic exposure modulated imagewise.

In electronic recording, an electrostatic latent image is formed by image-wise depositing electrically charged particles on a dielectric support from, for example, an electron beam or ionized gas.

The resulting latent image is usually triboelectrically charged,
Developed, ie, converted to a visible image, by selectively depositing light absorbing particles, referred to as toner particles, thereon.

[0008] Two techniques apply to toner development of electrostatic latent images: "dry" powder and "liquid" dispersion development.
Of these, dry powder development is the most frequently used today.

[0009] The visible image of electrostatically or magnetically attracted toner particles is not permanent, but rather by adhering the toner particles to one another and to a support by softening or melting and then cooling the toner particles. It must be established. Typically, fusing is performed on more or less porous paper by allowing the softened or melted toner material to penetrate into the surface irregularities of the paper.

Dry development toners are thermoplastic resins or mixtures of resins containing coloring substances (for example carbon black or finely dispersed pigments) (for example US-P 4271).
249). The triboelectric charging property is determined by the substance, and may be changed by a charge control agent. Dry development toners can be of various types. It can be, for example, magnetic toner particles used in a single component dry developer, which can be used, for example, in a non-magnetic single component developer or mixed with magnetic carrier particles to form a two (multi) component dry developer. Non-magnetic particles.

In order to have a toner composition in which the composition flows freely without aggregation of the toner particles, addition of a fluidity improver to the toner composition is a widely known technique. For example, U
S370617 teaches the addition of 0.01 to 15% hydrophobized silica to the toner composition to increase the life of the developer and its fluidity. It is further disclosed that the addition of a mixture of powdered inorganic additives in the toner composition has a beneficial effect on the performance of the toner composition.

US Pat. No. 5,312,711 discloses the addition of hydrophobized silica hydrophobized with a fluorine-containing silane compound to a toner composition. By doing so, the fluidity and uniform chargeability of the toner particles are increased.

[0013] EP-A 479 815 discloses that silica blends hydrophobic silica with small (less than 7 μm diameter) toner particles characterized by the product of the methanol number (degree of hydrophobicity) and the BET surface area.
The mixing is performed in such a way as to reach a defined ratio between the apparent density and the bulk density of the toner composition. The purpose of that disclosure is to improve the flowability of small toner particles.

For example, US Pat. No. 4,623,605 discloses the use of two different types of hydrophobic additives, one being hydrophobized silica and the other being hydrophobized titania. The technique of said application is directed to an electrostatic imaging method in which toner particles are fixed on a final support by heat and pressure (by hot-press rollers). JP-A 62/129866
Describes the use of silica additives together with non-silica inorganic additives in a very general manner over a wide range of concentrations so as to keep the positive chargeability of the multi-component developer stable. It is taught that the concentration of silica should be less than that of other inorganic additives and that the relative proportion of silica in other additives ranges from 0.01 to 0.50. US Pat. No. 4,626,487 discloses two different types of inorganic particles (one having a BET surface area of 0.2 to 30 m ² / g, preferably 1.0 to 6.0 m ² / g and another having a BET surface area of 40 to 400 m ² / g). A single component developer (i.e., a developer without magnetic carrier particles) in which a BET surface area of ² / g is present is disclosed. Low BE
The particles having T are hard and are preferably strontium titanate or cerium oxide.

In GB-A 2222269, the maximum is 0.1
An electrophotographic toner is disclosed that includes a binder resin and a colorant containing fine SiO ₂ powder having an average particle size of μm and TiO ₂ particles having an average particle size of up to 0.1 μm. The use of these toner particles minimizes blurring (eg, poor toning and collateral formation) due to the formation of oppositely charged toner. It can be used with or without a carrier.
The fusing of the cited patents is performed by a hot roller fusing machine, a contact fusing machine.

US Pat. No. 5,120,631 describes fine toners for full color systems. Mixtures of both inorganic hydrophobic and hydrophilic additives are described. From the theory of wetting, the use of a hydrophilic additive in a toner composition will result in the proper melting of the hydrophobic binder of the toner, and thus during the fusing step when no additional force is used, such as in a non-contact fusing process. Can be expected to slow the good penetration of. In the cited patent,
The toners described are used in fusing systems using heat and pressure, and the electrophotographic apparatus includes a hot roller fusing system.

From the above references, the addition of a mixture of hydrophobic and hydrophilic inorganic additives to toner particles is useful in electronic recording systems that include a fixing step using heat and pressure, but systems that use non-contact fixing. Would not be profitable.

Among the parameters such as resolution, fog, graininess, etc., one of the quality parameters of the image formed by the dry toner particles is the gloss of the final image. Methods of producing toner images using a non-contact fusing method are often preferred because the disadvantages of hot roller fusing (addition of silicone oil which has a detrimental effect on gloss, hot-offset) are avoided. However, they pose a problem that the toner resin exhibits a low-viscosity behavior above the softening point of the toner. This includes the fact that the toner mixes very well and provides a fairly smooth surface and therefore tends to impart a fairly high gloss. A single layer is the same as paper and gives less smooth images. However, the double, triple and quadruple layers are more shiny.
Thus, apart from the rather glossy appearance, there is the problem of differences in gloss with thickness.

A means for controlling the gloss of a non-contact fixed toner image is disclosed in EP-A 656129, in which two slightly incompatible polymers are blended or the toner resin is blended. It is disclosed to add compounds that are slightly incompatible with the toner particles and to use the blends as toner resins.

Another solution for improving the gloss of a toner image discloses the application of a layer of colorless toner particles on top of four color toner images. Representative examples of such layers and other methods for applying such layers are described, for example, in EP-A-629921, EP-A-486235, U.S. Pat.
S 5234783, US Pat. No. 4,828,950, EP-A
554981, WO 93/07541 and Xerox
Research DisclosureJournal, Vol.16, No.1,6
9 (Jan / Feb 1991).

However, these disclosures have common properties, each of which requires an additional toner station in the electronic recording device to provide and deposit colorless toner particles. This complicates the equipment, slows down the process and increases the cost of the equipment.

Therefore, a method and means for achieving uniform gloss in a multicolor toner image without the need for an additional toner station is highly desirable. The teachings of EP-A 656129 cited above provide a solution to the gloss problem due to the composition of the toner resin used in the color toner. However, there is still a need for toner compositions that allow for additional gloss control.

[0023]

It is an object of the present invention to provide a method for fixing a toner image on a final support that easily controls the gloss of the final image.

Another object of the present invention is to provide a toner composition which can be used in electronic recording, magnetography, and ionographic image forming methods including a non-contact melting method and gives an image having a uniform gloss.

It is a further object of the present invention to provide a toner composition wherein the toner particles are fixed to the final support by radiant heat to provide a final image having uniform gloss when used in an imaging method using solid toner particles. Is to do.

[0026]

The object of the present invention is achieved by providing a toner composition comprising: i) toner particles, wherein said toner particles comprise a toner resin and have a When measured with a plate / plate rheometer at 100 revolutions / second, 250 Pa · s ≦ η ≦ 1500 P
a. s melt viscosity η and 0.4 m ² / g ≦ BET _ton
≦ 1.5 m ² / g average BET surface area (BE
T _ton )) and ii) two different types of hydrophobic inorganic particles (IP
The first inorganic hydrophobic particles, designated as 1, (BEP _ip1 )
≧ 150 meters has a BET surface area of ² / g, the second inorganic particles called IP2 is _{(BEP ip2)} ≦ 150m ² /
g BET surface area, and each hydrophobic inorganic particle is present in the toner composition at A ₁ , A ₂ % by weight (% wt) with respect to the toner particles, and in the following formula, 150 ≦ BR ≦ 375
Is).

(Equation 2)

[0027]

DETAILED DESCRIPTION OF THE INVENTION The gloss of a toner image fixed on a final support by non-contact fusing is improved by adjusting the melt viscosity of the toner particles and by increasing the total BET surface area of the inorganic particles relative to the BET surface area of the toner particles. It has been found that control can be achieved by adding hydrophobic inorganic particles in such a way as to establish the relationship defined in the above.

When a toner image is fixed by non-contact fusing, two different types of hydrophobic inorganic particles (I
The first inorganic hydrophobic particles, designated P1, are (BE
_Pip1 ) ≧ 150 m ² / g with a BET surface area and I
The second inorganic particles, referred to as P2, have (BEP _ip2 ) ≦ 1
The toner particles (having a BET surface area of 50 m ² / g) are measured as 250 Pa · s ≦ η ≦ 150 when measured with a plate / plate rheometer at 120 ° C. and 100 rpm / s.
0 Pa. s having a melt viscosity η of 0.4 m ² / g to 1.
(Having an average BET _ton surface area of 5 m ² / g) and in an amount such that 150 ≦ BR ≦ 375 (weight% based on toner particles) (A ₁ , A ₂ )
It has been found that adding each of the two different types of hydrophobic inorganic particles is beneficial for gloss control.

(Equation 3)

BE of both toner particles and hydrophobic inorganic particles
T surface area was determined by Nelsen and Eggertsen in “Determi
nation of Surface Area Adsorption measurement
s by continuous Flow Method ”, Analytical Ch
emistry, Vol.30, No.9 (1958) 1387-1
It can be measured by the method described on page 390. Toner particles having a BET surface area of 0.4m ² /g~1.5m ² / g are toner particles having an average volume diameter of 10～3Myuemu. BET _ton thus represents the BET surface area of the toner particles.

Gloss control was found to be even better when 200 ≦ BR ≦ 300.

In the present invention, the toner particles have a particle size of 250 to
1500 Pa. s.

In the present invention, two different types of inorganic hydrophobic particles are included in the toner composition, and the first type of inorganic hydrophobic particles (IP1) are the BET surface area (BET _ip2 ) of the second type of inorganic particles. ) _{Has a} larger BET surface area (BET _ip1 ), and each of the two types of inorganic hydrophobic particles has an A relative to all toner particles such that 150 ≦ BR ≦ 375, more preferably 200 ≦ BR ≦ 330. _1, present in the toner composition in an amount by weight% of _{a 2} (% wt).

In a preferred embodiment of the present invention, when two types of inorganic hydrophobic particles are used, each of the two types of inorganic hydrophobic particles is 0.25% wt <A ₁ + A
₂ <2.5% wt and 0.4 <A ₁ / A ₂ <2, so that the weight percentage of A ₁ and A ₂ (% w
It is present in the toner composition in an amount of t). Further BET
_ip1 > 150 m ² / g and BET _ip2 <150 m ²
/ G, most preferably BET
_ip1 ≧ 200 m ² / g and 30 m ² / g <BET
_ip2 ≦ 100 m ² / g.

In a more preferred embodiment of the present invention, said two different types of inorganic hydrophobic particles comprise 0.5% wt <A ₁ + A
₂ <1.5% wt and 0.5 <% by weight of A ₁ / A ₂ <A ₁ with respect to the total toner particles as is 1.5, A ₂ (%
wt) in each of the toner compositions. Preferably, the inorganic hydrophobic particles having a larger BET surface area are hydrophobic silica particles, and the inorganic hydrophobic particles having a smaller BET surface area are hydrophobic titania (TiO ₂ ). Preferably, the hydrophobic titania is a rutile or anatase crystal.

[0035] Suitable hydrophobic silicas can be fumed silicas as well as precipitated silicas. Silicas useful in the present invention are German DEGU under the trade name AEROSIL.
It can be found from various types of hydrophobic silica sold by SSA. Especially suitable is 260m
AEROSIL R81 with a BET surface area of ² / g
AEROS having a BET surface area of 2,170 m ² / g
BET of AEROSIL R805,100m ² / g with a BET surface area of IL R974,150m ² / g
AEROSIL R202 and 110m with surface area
AEROSIL R97 with a BET surface area of ² / g
2. Other useful silica-type inorganic hydrophobic particles are precipitated silica particles that have been rendered hydrophobic. Such silica particles have a SILICA having a BET surface area of 87 m ² / g.
SS10, SI having a BET surface area of 113 m ² / g
LICA SS20,59m BET of SILICA SS40 and 42m ² / g with a BET surface area of ² / g
It is available through NIPPON SILICA of Japan under the trademark SILICA SS70 with surface area.

A suitable hydrophobic TiO ₂ is, for example, 45 m ² /
TITANDIOXID T with BET surface area of g
805 (trademark of DEGUSSA, Germany).

The use of a mixture of two different types of hydrophobic inorganic particles has been found to be advantageous over the use of only one type. The amount of the one type of hydrophobic inorganic particles is 150 to 375 or 200 to 3 when the BET ratio is n = 1.
When it is 30, good gloss control is possible, but at first glance the hydrophobic inorganic particles had a strong effect on the charge of the toner particles. This is because one type of the inorganic particles cannot achieve an appropriate optical density with a moderate developing ability at all.
It has been found that in the toner composition according to the present invention, when two different types of inorganic hydrophobic particles are present, both good gloss control and optical density control are possible. Hydrophobic SiO ₂ particles and inorganic particles as inorganic particles IP1 IP2
Better results were obtained in gloss control and optical density when using hydrophobic TiO ₂ particles as The best results were obtained when the hydrophobic TiO ₂ particles are crystalline particles of rutile or anatase type.

In the toner composition used in the method according to the invention, the inorganic hydrophobic particles are simply mixed with the toner particles. Mixing is performed by mechanical melting (mechanofusin
g), the effect of gloss control is substantially the same as when the inorganic particles are simply mixed with the toner particles, when performed in such a way that it also appears (for example by a long mixing time in a HENSCHEL mixer above room temperature). Met.

The toner particles to be mixed in the toner composition according to the present invention are such that the toner particles are 150 Pa. s (1500
Poise) ≦ η ≦ 2000 Pa. s (20,000 poise)
Any known toner resin and any pigment or dye may be included as long as the resin has a melt viscosity η of. Preferably the toner particles are 250 Pa. s (2500 poise) ≦ η
≦ 1500 Pa. Melt viscosity η of s (15000 poise)
Having.

It has been found that the limit on the melt viscosity of the toner particles is very critical. 150 Pa. Very low melt viscosities below s result in good fixing, but very high gloss that cannot be reduced by the addition of different types of hydrophobic inorganic particles to the toner particles.
2000 Pa. The toner particles having a very high melt viscosity exceeding s cannot be properly fixed by the non-contact melting method.

Therefore, the toner resin for the toner particles useful in the present invention is first selected with an emphasis on its melting behavior, but other characteristics such as chargeability and hardness must also be considered.

The toner resin can be a polycondensation polymer or a mixture of polycondensation polymers together with an addition polymer or a mixture of addition polymers. Also, mixtures of polycondensation polymers and addition polymers are suitable as toner resins for the toner particles according to the present invention. When a polycondensation polymer is used, the use of a polyester is preferred.

Polyester resins suitable for use in the toner particles according to the present invention include (i) difunctional organic acids such as maleic acid, fumaric acid, terephthalic acid and isophthalic acid and (ii) difunctional alcohols (diols) such as Bisphenols such as ethylene glycol, linear polycondensates of triethylene glycol, aromatic dihydroxy compounds, preferably 2,2-bis (4-hydroxyphenyl) -propane referred to as "bisphenol A" or alkoxylated bisphenols (e.g., Examples of such propoxylated bisphenols are given for example from the group given in U.S. Pat. No. 4,331,755). See GB-P 1373220 for the preparation of suitable polyester resins.

When an addition polymer is used, styrene /
It is preferable to use an acrylic resin. Preferred styrene-acrylic resins are relatively high (> 70 mol%)
Copolymers of styrene-acrylic resin or styrene-methacrylic resin having a styrene content, such as copoly (styrene / n-butyl methacrylate) or copoly (styrene / 2-ethyl-hexyl acrylate), are particularly preferred.

Representative useful resins for the toner resin in the toner particles according to the present invention are listed in Table 1.

Other suitable resins for use in the toner resin are disclosed in US Pat. No. 5,395,726, which is incorporated herein by reference.

In another preferred embodiment, the toner particles comprise a resin mixture of at least two resins selected to be slightly incompatible with each other. H for polymer
The solubility of the ILDEBRAND parameter is described in the literature "Prope
rties of Polymers "DW Van Krevelen, 2nd
Ed., Elseviers Scientific Publishing Company, Ne
w York, 1976, Chapter 7. The combination of the inorganic particles according to the present invention with toner particles comprising a resin mixture of at least two resins selected to be slightly incompatible with each other provides a useful method for gloss control. Generally, the desired slight incompatibility can be obtained by combining a polyester resin P1 (eg, polyester) with another polyester P2 having a greater polarity than said polyester resin P1. Mixtures of such resins and of resins and incompatible compounds are described in EP-A
656129, which is incorporated herein by reference.

[0048]

[Table 1]

Polyester P1 is ATLAC T500
(Trademark). Polyester P2 is terephthalic acid (100 mol%) as aromatic diacid and DI as diol
An aromatic polyester resin derived from a mixture of ANOL 33 (50 mol%) and ethylene glycol (50 mol%). Polyester P3 has terephthalic acid (40 mol%) and isophthalic acid (60 mol
1%) and an aromatic polyester resin derived from a mixture of DIANOL 22 (40 mol%) and ethylene glycol (60 mol%). DIANOL 22
Is diethoxylated bisphenol A. DIANO
L 33 is dipropoxylated bisphenol A.
Bisphenol A = 4,4 'isopropylidene diphenol. Polyester P4 is an aromatic polyester resin derived from terephthalic acid (64 mol%), isophthalic acid (36 mol%) and ethylene glycol (100 mol%) as aromatic diacids. Styr / acryl S1 is a 65/35 molar ratio copolymer of styrene and methyl acrylate. Styr / acryl S2 is a terpolymer of styrene, methyl acrylate and dimethylaminoethyl methacrylate in a 87/3/10 molar ratio. Styr /
Acrylics S3, S4, S5 and S6 are copolymers of styrene and methyl acrylate in a molar ratio of 80/20 and differ only in the molecular weight.

Particularly when the tackiness and water repellency of the fixing layer of the toner particles have to be increased, the toner resin of the toner particles according to the present invention can comprise 3% by weight or more based on the total resin content, or Polysiloxane component (P
S) and a polysiloxane-modified resin containing another polymer component (POL). Such resin is JP-
A 08/297380, which is incorporated herein by reference.

It is often desirable to reduce the energy required to melt a toner for use in a non-contact fusing system, and have good flowability at fairly low fusing temperatures. Therefore, the toner particles used in the toner composition according to the present invention preferably contain an amorphous complex polymer compound containing the following (i) and (ii) in the polymer structure as a toner resin. (I) the amorphous polycondensation backbone (the corresponding backbone polymer has a Tg of at least 45 ° C.); (ii) at least one of the terminal and / or side chains attached to said backbone. One of the polymer chain (number average molecular weight of the polymer chain is 400 ≦ M _avg ≦ 4000 (M
_{av g),} and the melting point and the melting point range of up to 15 ℃ of 50 ° C. to 150 DEG ° C. is derived from a polymer having about itself). Such resin and toner particles containing them are 199
JP-A 08/2256 filed on November 9, 5
52, which is incorporated herein by reference.

The toner particles to be mixed in the toner composition according to the present invention may be magnetic particles containing a magnetic pigment,
Alternatively, it can preferably be non-magnetic. The non-magnetic toner particles in the toner composition according to the present invention can advantageously use a two (or multiple) component developer comprising the toner composition according to the present invention together with the magnetic carrier particles.

The toner particles used in the toner composition according to the present invention can have an average volume diameter of 1 to 50 μm, preferably 3 to 20 μm. When the toner particles are intended for use in color imaging, it is desirable that the average volume diameter be from 3 to 10 μm, most preferably from 3 to 8 μm. The particle size distribution of the toner particles may be of any type. However, with a coefficient of variation (dividing the standard deviation by the mean) (v) of less than 0.5, more preferably 0.3, the Gaussian or normal particle size distribution (either by number or volume) substantially (undistorted) Positive distortions that give less particles smaller than the distribution are preferred, but some negative or positive distortions are acceptable).

The toner particles used in the toner composition according to the present invention can contain conventional toner components such as charge control agents, colored and black pigments, inorganic fillers and the like. A description of charge control agents, pigments and other additives useful for the toner particles to be used in the toner composition according to the invention can be found, for example, in EP-A 601 235.

The image formed by the adhesion of the toner composition according to the present invention is preferably fixed by a non-contact fusing method. In such a method, there is no direct contact between the solid heating element and the toner image. Such non-contact fusing methods include various examples such as: (1) oven heating, in which heat is applied to the toner image by hot air over a large area of the support sheet, (2) red absorbed by the toner. A radiant heating method in which heat is supplied by external and / or visible light (the light source is, for example, an infrared lamp or a flash lamp); (3) heat is generated by heating the side of the support opposite to the side carrying the image; How to transfer to toner image. This last method is heating means (eg heating roller)
And can be implemented in a non-contact system as by contacting the side opposite the image bearing side. In the present invention, the non-contact melting system described in the above (1) and (2) is preferable.

In order to control the gloss in the image formed by the toner composition according to the present invention, which is fixed by a non-contact fusing method, the image (ie, the fused toner) is fixed with a pressure roller to further homogenize the image. (Particles) is beneficial. Pressure roller is 100N / m-500N /
It is preferable to apply pressure to the fixed image of m (m represents a linear nip length), and the post-processing is preferably 30 to 1
This is performed in a time of 50 ms. According to the invention, there are two ways to operate the post-processing. The two systems differ in the temperature of the post-treatment. In the first mode, after leaving the non-contact fusing station, the cooled, almost cold fused image passes through a pressure roller. The pressure roller controls the softening temperature of the toner resin (which in most cases is 12
(Meaning a temperature near 0 ° C.) between 10 ° C. below and 10 ° C. above. In a second mode of operation, the fused image is passed from a fusing station through a pressure roller without cooling. There, no additional heat is applied to the fused image, but the temperature of the post-treatment roller is maintained between 5 ° C. and 15 ° C. above the Tg of the toner resin. Optionally, providing a tack-free compound (eg, silicone oil, liquid wax, etc.) on the surface of the post-treatment roller, if necessary for good tackiness between the fused image and the post-treatment roller Can be.

In a preferred embodiment of the present invention, for a color image,
For a single color, the dispersion and / or amount of pigment in the toner particles is adjusted so that sufficient saturation in the color is achieved by the deposition of a thin, almost single layer of toner particles. In doing so, differences in gloss due to (large) differences in the height of the various layers of deposited toner particles are minimized. Further, when using the toner composition according to the present invention, the amount of toner particles (toner mass, TM) deposited to achieve the maximum optical density for each single color follows the formula: TM ≦ 0.8 × d _v50 × ρ where TM is expressed in mg / cm ² and d _v50 is c
the average volume diameter of the toner particles expressed in m;
ρ is the bulk density of the toner particles in mg / cm ³ . The maximum optical density of each of the single colors means an optical density on the reflective support of 1.4 to 1.6 for yellow, magenta and cyan, and an optical density of 1.6 to 2.0 for black. The image is, for example, EP-A 656129, EP-A
629921, EP-A 486235, US 523
4783, US Pat. No. 4,828,950, EP-A 5549
81, WO 93/07541 and Xerox Research
Disclosure Journal, Vol. 16, No. 1, p. 69 (1
When finished by the application of a colorless toner as exemplified in (January / February 991) it is advantageous to use a colorless toner composition according to the present invention. The colorless toner is applied in an amount TM satisfying the above equation.

Accordingly, the present invention encompasses a toner composition comprising: i) toner particles, wherein the toner particles comprise a toner resin and are measured at 120 ° C. at 100 revolutions / sec with a plate / plate rheometer. Then 250Pa.s ≦ η ≦ 1500P
a. s melt viscosity η and 0.4 m ² / g ≦ BET _ton
Average BET surface area (BET _ton ) ≦ 1.5 m ² / g
And ii) two different types of hydrophobic inorganic particles (IP
The first inorganic hydrophobic particles, designated as 1, (BEP _ip1 )
≧ 150 meters has a BET surface area of ² / g, the second inorganic particles called IP2 is _{(BEP ip2)} ≦ 150m ² /
g BET surface area, and each hydrophobic inorganic particle is present in the toner composition at A ₁ , A ₂ % by weight (% wt) with respect to the toner particles, and in the following formula, 150 ≦ BR ≦ 375
Is)

(Equation 4) iii) Colorant (where the colorant is included in the toner particles by attaching the amount TM of the toner particles according to the following formula: TM ≦ 0.8 × _dv50 × ρ, where TM is mg / cm ² unit) in represented, d _v50 is the average volume diameter of the toner particles represented in cm, [rho is the bulk density of toner particles in mg / cm ³ units, resulting in maximum optical density).

[0059]

【Example】

1. Production of Toner Particles Toner 1 (T1) 49 parts of polyester P1 in Table 1 and polyester in Table 1
49 parts of P3 were mixed with 2 parts of a Cu-phthalocyanine pigment (color index PB 15: 3) and 1 part with an experimental kneader.
Melt blended at 10 ° C for 30 minutes.

After cooling, the solidified substance was removed from ALPINE Fliessbettgeg.
It was pulverized using enstrahlmuehle type 100AFG (trademark) and further classified using ALPINE multiplex zigzag classifier type 100MZR (trademark). The average particle size of the separated toner is calculated using the Coulter Counter model.
8.0 μm as measured by Multisizer ™
(Volume average). This was a toner having a BET surface area BET _ton = 0.65 m ² / g. The melt viscosity (η) of the toner particles is 100 revolutions / second at 120 ° C. and a plate / plate rheometer
heometer) (C by TA instruments Ltd, Dorking UK
400 Pa. When measured with an ARIMED RHEOMETER CSL500 (trademark). s.

Toner 2 (T2) 98 parts of polyester P1 in Table 1 was melt-blended with 110 parts of a Cu-phthalocyanine pigment (color index PB 15: 3) at 110 ° C. for 30 minutes using a laboratory kneader.

After cooling, the solidified substance was removed from ALPINE Fliessbettgeg.
It was pulverized using enstrahlmuehle type 100AFG (trademark) and further classified using ALPINE multiplex zigzag classifier type 100MZR (trademark). The average particle size of the separated toner is calculated using the Coulter Counter model.
8.3 μm as measured by Multisizer ™
(Volume average). This was a toner having a BET surface area BET _ton = 0.63 m ² / g. The melt viscosity (η) of the toner particles is 150 Pa. s.

Toner 3 (T3) No. 10 styrene / acrylate resin in Table 1 (S6)
Was mixed with 2 parts of a Cu-phthalocyanine pigment (color index PB 15: 3) at 110 ° C. using a laboratory kneader.
For 30 minutes.

After cooling, the solidified substance was removed from ALPINE Fliessbettgeg.
It was pulverized using enstrahlmuehle type 100AFG (trademark) and further classified using ALPINE multiplex zigzag classifier type 100MZR (trademark). The average particle size of the separated toner is calculated using the Coulter Counter model.
8.0 μm as measured by Multisizer ™
(Volume average). This was a toner having a BET surface area BET _ton = 0.65 m ² / g. The melt viscosity (η) of the toner particles is 2300 Pa. s.

2. Toner Composition Table 2 lists the type of toner, the type of inorganic particles, the BET surface area of the inorganic particles, and the amount of inorganic hydrophobic particles added to the toner particles to form the toner composition described immediately below.

Toner Composition 1 (TC1) Toner 1 (T1) and one type of inorganic hydrophobic particles were mixed with a HENSCHEL mixer at a filling factor of 30% by volume, a rotation speed of 35 m / sec and 30 seconds. Used and mixed. 110 m ² / g for inorganic hydrophobic particles
Fumed SiO ₂ particles having a specific surface area of
EROSIL R972). The inorganic hydrophobic particles were added to the toner composition at a concentration of 1 part per 100 parts of the toner particles.

Toner Composition 2 (TC2) Fumed hydrophobic S having a specific surface area of 170 m ² / g
iO ₂ (AEROSIL R974) is used as one of the toner particles.
The procedure for producing toner composition TC1 was repeated, except that the toner particles were mixed with the toner particles at a concentration of 1 part to 00 parts.

Toner Composition 3 (TC3) Fumed hydrophobic S having a specific surface area of 260 m ² / g
iO ₂ (AEROSIL R812) is used as one of the toner particles.
The procedure for producing toner composition TC1 was repeated, except that the addition was at a concentration of 1 part to 00 parts.

Toner Composition 4 (TC4) The procedure for producing toner composition TC1 was repeated, except that the concentration of hydrophobic silica was 0.5 parts per 100 parts of toner particles.

Toner Composition 5 (TC5) The procedure for producing toner composition TC1 was repeated, except that no hydrophobic inorganic particles were present.

Toner Composition 6 (TC6) Hydrophobic precipitated SiO ₂ having a specific surface area of 113 m ² / g
The process for producing toner composition TC1 was repeated, except that (SILICA SS20) was added at a concentration of 1 part per 100 parts of toner particles.

Toner Composition 7 (TC7) Hydrophobic precipitated SiO ₂ having a specific surface area of 42 m ² / g
The process for producing toner composition TC1 was repeated, except that (SILICA SS70) was added at a concentration of 1 part per 100 parts of toner particles.

Toner Composition 8 (TC8) The procedure for producing toner composition TC1 was repeated, except that two types of inorganic hydrophobic particles were present. 260m ² / g
Fumed SiO ₂ particles having a specific surface area of
EROSIL R812) and hydrophobic precipitated SiO ₂ particles having a specific surface area of 42 m ² / g (SILICA SS)
70) for each 100 parts of toner particles.
5 parts by weight were added to the toner composition.

Toner Composition 9 (TC9) The procedure for producing toner composition TC1 was repeated, except that two types of inorganic hydrophobic particles were present. 260m ² / g
Fumed SiO ₂ particles having a specific surface area of
EROSIL R812) and hydrophobic precipitated SiO ₂ particles having a specific surface area of 113 m ² / g (SILICA S
S20) was added to the toner composition at a concentration of 0.5 part per 100 parts of toner particles.

Toner Composition 10 (TC10) The procedure for producing toner composition TC1 was repeated, except that two types of inorganic hydrophobic particles were present. 260m ² / g
Fumed SiO ₂ particles having a specific surface area of
EROSIL R812) and hydrophobic TiO ₂ particles having a specific surface area of 50 m ² / g (TITANDIOXID
T805) was added to the toner composition at a concentration of 0.5 part per 100 parts of toner particles.

Toner Composition 11 (TC11) The procedure for producing toner composition TC10 was repeated, except that each of the two types of hydrophobic inorganic particles was present in 0.3 parts per 100 parts of toner particles.

Toner Composition 12 (TC12) Fumed hydrophobic silica (AEROSIL R812)
Was present in 0.5 parts per 100 parts of toner particles, and 0.7 parts of hydrophobic TiO ₂ (TITANDIOXID T805) was present in 100 parts of toner particles. Repeated.

Toner Composition 13 (TC13) Fumed hydrophobic silica (AEROSIL R812)
Is present in 0.45 parts per 100 parts of toner particles,
Hydrophobic TiO ₂ (TITANDIOXID T805)
Was made in the same manner as above, except that 0.65 part was contained with respect to 100 parts of the toner particles.

Toner Composition 14 (TC14) Fumed hydrophobic silica (AEROSIL R812)
Was repeated, except that fumed hydrophobic silica (AEROSIL R974) having a BET surface area of 170 m ² / g was used.

Hydrophobic titania (TITANDIOXID)
T805) was replaced by a precipitated hydrophobic silica having a BET surface area of 42 m ² / g (SILICA SS70), except that the process for producing toner composition TC14 was repeated.

Toner Composition 16 (TC16) The procedure for producing toner composition TC10 was repeated, except that toner T2 was used.

Toner Composition 17 (TC17) The procedure for producing toner composition TC10 was repeated, except that toner T3 was used.

3. Developer Compositions Each of the toner compositions TC1 to TC17 is used at a concentration of 5% by weight of toner with respect to the carrier, and each component is mixed with a coated ferrite carrier having a volume average particle size of 50 μm to form a multi-component. A developer was prepared and activated for 30 minutes to obtain a stable charge level.

4. Printing and Gloss Evaluation Images containing uniform density patches were made on smooth copy paper with deposition rates corresponding to single, double, triple and quadruple layers corresponding to a full color system. 0.6 mg / cm ² of toner particles was adhered to each layer. They are passed through a non-contact fusing station at 12.5 cm / sec over a length of 40 cm and the resulting image is applied by applying heat to the support such that the surface of the fused image has a temperature of 125 ° C. Was fused. The gloss was evaluated visually and given a quality symbol. These symbols are given in Table 3.
The symbols have the following meanings: ++ Excellent uniformity of gloss + Good uniformity 0 Acceptable uniformity-Uneven gloss--Extremely uneven gloss

In the same way, the optical density (magnitude of the amount of transferred toner substance) was evaluated and ranked according to the following ranking symbols: ++ excellent + good 0 acceptable-unacceptable--not at all acceptable

The result of the measurement was expressed as BET-ratio (BR), A ₁
It is listed in Table 3 together with + A ₂ and A ₁ / A ₂ .

[0087]

[Table 2]

[0088]

[Table 3]

As shown in Table 3, no inorganic particles are present or only one type of inorganic particles is present (TC1 to TC
7) It can be seen that the gloss can be controlled when the BET-ratio is in the range of Formula I (n = 1), but the optical density is only acceptable in the best case. There are two types of inorganic particles and the melt viscosity of the toner particles is 400 Pa.s. s (TC8 to TC15), gloss control and optical density are both good, and hydrophobic silica and hydrophobic titania are present (for example, TC10, TC12 and TC1).
3) Excellent in both gloss control and optical density. Gloss control is no longer possible when the melt viscosity of the toner resin is 150 or 2300 (TC10 compared to TC10).
16 and TC17).

──────────────────────────────────────────────────の Continuing on the front page (72) Inventor Jean-Pierre Jequiel Morseer, Belgium Sepceptrat 27 Inside Agfa Geverth na Mroseze Bennoutchap (72) Inventor Wernel op de Béke Belgium Motzeel, Septetrat 27 Agfa Geverth na Mulose Bennoutchap (72) Inventor Theofiel Stuell Motzeel, Septegrat 27 Belgium Agfa Gewert na Mlose Bennoutchap (56) References JP-A-2-293862 (JP, A) JP-A-5-346682 (JP, A) JP-A-5-53369 (JP, A) JP-A-60-136755 (JP, A) JP-A-62-129866 (Japanese) J JP-A-4-51156 (JP, A) JP-A-1-1303065 (JP, A) JP-A-3-200157 (JP, A) JP-A-60-135957 (JP, A) (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (7)

(57) [Claims] 1. A toner composition comprising: i) toner particles, wherein said toner particles comprise a toner resin and are measured at 250 rpm at 120 ° C. at 100 revolutions / sec with a plate / plate rheometer. ≤1500P
a. s melt viscosity η and 0.4 m ² / g ≦ BET _ton
≦ 1.5 m ² / g average BET surface area (BE
T _ton )) and ii) two different types of hydrophobic inorganic particles (IP
The first inorganic hydrophobic particles, designated as 1, (BEP _ip1 )
≧ 150 meters has a BET surface area of ² / g, the second inorganic particles called IP2 is _{(BEP ip2)} ≦ 150m ² /
g BET surface area, and each hydrophobic inorganic particle is present in the toner composition at A ₁ , A ₂ % by weight (% wt) with respect to the toner particles, where 150 ≦ BR ≦ 375
Is). (Equation 1) 2. The toner composition according to claim 1, wherein 200 ≦ BR ≦ 375. 3. Inorganic hydrophobic particles (IP1) of the first type having a BET specific surface area (BET _ip1 ) of more _than 200 m ² / g and 30 m ² / g ≦ BET _ip2 ≦ 100 m
^Second having a BET specific surface area (BET _ip2 ) of ² / g
3. The toner composition according to claim 1, comprising inorganic particles (IP2) of the type. Wherein said first type of inorganic particles is present in an amount of A ₁ wt% (% wt) with respect to the toner particles, A ₂ weight relative to said second type of inorganic particles wherein the toner particles % (% Wt), where 0.25% wt <A ₁ +
The toner composition according to claim 1, wherein A ₂ <2.5% wt and 0.4 <A ₁ / A ₂ <2. 5. The toner composition according to claim 4, wherein the inorganic particles IP1 are hydrophobic SiO ₂ particles, and the inorganic particles IP2 are hydrophobic TiO ₂ particles. 6. The toner composition of claim 1, wherein said toner particles further comprise a significant amount of a colorant by depositing an amount TM of toner particles according to the following formula: TM ≦ 0.8 × _dv50 × ρ. _Where TM is expressed in mg / cm ² , _dv50 is the average volume diameter of the toner particles in cm, ρ is the bulk density of the toner particles in mg / cm ³ , Produces maximum optical density. 7. The toner composition according to claim 1, which is used in electro (stato) graphic printing wherein the image is fused by non-contact fusing means.