JPH11249341A - Color toner for non-magnetic one-component development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color toner used in a non-magnetic one-component developing device, which has good and stable developability even during long-term stirring, and without applying a fixing oil to a fixing device. To provide a color toner having good fixability, gloss, transparency, and release property. SOLUTION: In a non-magnetic one-component developing color toner containing at least a binder resin, a colorant, a wax and a charge controlling agent as main components, the glass transition temperature (T
g) is 62 ° C. or more, the 流出 outflow starting temperature (T1 / 2) of the toner is 110 to 130 ° C., and the relationship with the melting point (Wmp) of the wax is as follows. A nonmagnetic one-component color toner for development. (T1 / 2) − (Wmp) = 5 to 20 ° C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a color toner for non-magnetic one-component development.

[0002]

2. Description of the Related Art In recent years, the development of hard copy technology using an electrophotographic system has been rapidly expanding from black and white to full color, and the full color market is particularly expanding. Color image formation by full-color electrophotography generally reproduces all colors using three color toners of three primary colors, yellow, magenta, and cyan, or four colors including black.

In the general method, first, an electrostatic latent image is formed on a photoconductive layer by passing light from a document through a color separation light transmitting filter having a complementary color relationship with the color of the toner. Then development,
After the transfer step, the toner is held on the support. Next, the above-described steps are sequentially performed a plurality of times, and while the registration is being performed, the toner is superimposed on the same support, and the final full-color image is obtained by performing the fixing only once. In such a color electrophotographic method in which development is performed a plurality of times and a plurality of toner images of different colors are superimposed on the same support as a fixing step, the fixing characteristics that the color toner should have are extremely important. Element. That is, the fixed color toner is required to suppress irregular reflection due to toner particles as much as possible and to have appropriate glossiness and gloss. Further, the color toner must be transparent and have a wide color reproduction range so as not to obstruct the toner layers of different color tones under the toner layer.

On the other hand, a fixing device used for fixing a color toner uses a roller or the like using a material having excellent surface releasability, but in most cases, an oil is applied to the surface of the roller or the like. However, application of a large amount of oil to enhance the releasability requires problems such as oil contamination of the transfer paper, cost increase, and a space for storing oil, and an increase in the size of the fixing device.

[0005] The reason why oil is generally used for fixing a color toner is as follows. That is, it is necessary for the color toner to have higher heat melting property and lower viscosity at the time of fixing and heating than black toner for black and white printing to obtain gloss and transparency. However, in a toner using such a resin, the intermolecular cohesion at the time of heat melting is apt to decrease, so that the toner adheres to the heat roller when passing through the fixing roller, and a high-temperature offset phenomenon occurs. Therefore, in order to prevent the high-temperature offset, it is common to apply oil to the fixing roller to reduce the adhesion of the toner to the fixing roller.

[0006] So-called oil-less toners that do not apply oil to the fixing roller have been tried, and it has been generally proposed to disperse wax in the toner. However, in the case of a color toner, as described above, the wax needs to sufficiently exude from the toner whose viscosity has been reduced, and it is difficult to prevent offset. Also,
In the case of a highly viscous toner, such as a black toner for black-and-white printing, since the intermolecular cohesion at the time of thermal melting of the toner is high, offset can be prevented by exuding a small amount of wax, but sufficient toner No melting has taken place and the gloss and transparency are insufficient.

On the other hand, with respect to development, there has been proposed a non-magnetic one-component phenomenon which is excellent in miniaturization and weight reduction and does not require a carrier. In this developing method, since the replenishing property of the toner to the developing roller and the toner retaining property of the developing roller are poor, the toner is forcibly rubbed against the developing roller or the amount of toner on the developing roller is regulated by a blade. As a result, the toner tends to be filmed on the developing roller, and the life of the developing roller is shortened, and the charge amount of the toner becomes unstable. This also prevents good development.
Therefore, in a color toner for non-magnetic one-component development, in addition to the characteristics required for a general color toner, it is necessary to prevent the toner from being filmed on the developing roller.

Japanese Patent Publication No. Hei 8-12475 discloses an etherified diphenol component, a hydrocarbon group-substituted divalent carboxylic acid or a derivative thereof, a trivalent or higher polycarboxylic acid and / or a polyol, or a polyol thereof. JP-A-51-144625 describes a color toner comprising a derivative component and using a polyester resin having a limited apparent viscosity and DSC endothermic peak.
Polyester resin having a molecular weight of 500 to 20
Magenta toner obtained by adding a certain pigment to a resin mixture of solid silicone varnish of No. 00
JP-A-158281 discloses a haze value of 7 to 10 for a dispersion of a binder resin.
A 30% toner is described, and the binder resin uses a weakly cross-linked resin. However, there is a problem that oil-less fixing is insufficient in offset resistance.

JP-A-5-158282 discloses a phthalic acid-based divalent aromatic acid component, trimellitic acid-based acid component, succinic acid-based acid component, and etherified diphenols. OH number: 10-20, Mw:
13000-20,000, Mn: 5000-8000,
A color toner containing a polyester resin having Mw / Mn = 2 to 3.5 and a method for forming a color image are described. Japanese Patent Application Laid-Open No. 7-219274 discloses that a polyolefin wax and a water-containing paste of a pigment are mixed into a resin solution for dispersing a pigment, and then a heat-treated pigment-dispersed resin is contained. A color toner having a molecular weight of 1.5 to 0.5 is described, which aims at high dispersion of a polyolefin wax in a binder resin. There is a problem that it is not enough to expect only the effect of the wax.

Japanese Patent Application Laid-Open No. 7-31479 discloses that an elastic layer coated with a fluororesin is used as a surface layer for a fixing roller using a toner described in Japanese Patent Application Laid-Open No. 7-219274. This aims at increasing the dispersion of the polyolefin wax in the binder resin, but it is not sufficient to expect only the effect of the polyolefin wax in order to impart oillessness. Is mentioned. Also, Japanese Patent Application Laid-Open No. 7-333
No. 903, Mn: 2500-3500, Mw:
Although 50,000 to 300,000 toners containing a polyester resin not containing a THF (tetrahydrofuran) -insoluble component are described, there is a problem that a trace amount of fixing oil is required, and the oil-less operation is insufficient.

Japanese Patent Application Laid-Open No. 7-333904 discloses that a polyester resin having a wax and a THF insoluble content of 15 to 40% and a polyhydric alcohol component being limited is used to limit the difference in refractive index between the binder resin and the wax. However, there is a problem that it has a large amount of THF-insoluble components and it is difficult to obtain high gloss. Further, Japanese Patent Application Laid-Open No.
No. 0367 discloses that in a wax-containing toner, the molecular weight of the wax has a maximum value in each of 350 to 850 and 900 to 4000, and Mn: 350 to 4000;
Although an ester wax-containing toner having an Mw of 200 to 4000 is described, there is a problem that a sufficient oil-less property cannot be obtained only by limiting the properties of the wax.

Further, Japanese Patent Application Laid-Open No. 8-50368 discloses that
50 to 95 ester compounds having the same total carbon number
Although a toner containing a wax contained in a weight percent ester wax is described, there is a problem that sufficient oillessness cannot be obtained only by limiting the properties of the wax. Also, JP-A-3-39971 discloses that toluene-insoluble components are not contained and the molecular weight is 500-2000.
And a peak in the range of 10,000 to 100,000, and Mw: 10,000 to 8
Although a resin-containing color toner having Mn: 1500 to 8000 and Mw / Mn> 3 is described, there is a problem that sufficient oillessness cannot be obtained. Japanese Patent Application Laid-Open No. 4-57062 discloses that the softening temperature of a flow tester having a melt viscosity of 10 ⁵ poise is 90 to 120 ° C.
15,000 to 50,000, Mn: 2000 to 10,000, Mw /
Although a resin-containing color toner having Mn of 5 to 15 is described, there is a problem that sufficient oillessness cannot be obtained.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color toner used in a one-component developing apparatus, which has good and stable developability even under long-term stirring, and
An object of the present invention is to provide a color toner having good fixing properties, glossiness, transparency, and releasability without applying a fixing oil to a fixing device.

[0014]

According to the present invention, first,
In a color toner for non-magnetic one-component development containing at least a binder resin, a colorant, a wax, and a charge control agent as main components, the glass transition temperature (Tg) of the toner is 62 ° C. or more, and is １ ／ of that of the toner. Outflow start temperature (T1 / 2)
Is 110 to 130 ° C., and the relationship with the melting point (Wmp) of the wax is as follows. (T1 / 2) − (Wmp) = 5 to 20 ° C. Secondly, the first binder resin contains a polyester or / and polyol resin having a THF (tetrahydrofuran) insoluble content of 5 wt% or less. A non-magnetic one-component color toner for development is provided. Third, there is provided a color toner for non-magnetic one-component development, wherein a metal salt of a salicylic acid derivative is used as the first charge control agent. Fourth, the non-magnetic color toner is characterized in that the color toner shown in the first is coated on the surface of the base colored particles with an external additive, and contains hydrophobic silica and titanium oxide in combination as the external additive. A color toner for one-component development is provided.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The contents of the present invention will be specifically described below. In the pressure fixing method using a heat fixing roller or belt to obtain a color image in the electrophotographic method,
As a result of studies by the present inventors, it is possible to obtain sufficient offset resistance, transparency, and gloss without using oil on a fixing roller or the like by using the color toner having the configuration of the present invention. And good and stable developability was obtained even with long-term stirring in a one-component developing apparatus.

The glass transition temperature (Tg) of the toner is 62 ° C.
And the half flow start temperature (T1 / T1) of the toner
2) is 110 to 130 ° C., and the relationship with the melting point (Wmp) of the wax is (T1 / 2) − (Wmp) =
When the temperature is 5 to 20 ° C., the above-mentioned characteristics relating to fixing and stable developability in a one-component developing device can be compatible. Since the glass transition temperature (Tg) of the toner is 62 ° C. or higher, there is no generation of toner deformation and pulverization even during long-term stirring in a one-component developing apparatus, and toner filming on the developing roller and toner Can be prevented from being fused to a member such as a blade for reducing the thickness of the layer.

Further, the temperature at which the toner starts to flow out at a half (T
１ ／) is 110 to 130 ° C., and the relationship with the melting point (Wmp) of the wax is (T1 / 2) − (Wm).
p) = 5 to 20 ° C., and by making the relationship between the two thermal properties close to each other, the dispersion of the wax in the toner becomes good,
Wax is prevented from oozing out of the surface of the toner even during long-term stirring in a one-component developing device, and wax is prevented from being detached. Filming of the toner on the developing roller, a blade for thinning the toner, etc. It became clear that the fusion of the toner to the member can be prevented. This is because, when kneading the toner, in the process of dispersing the wax in the toner, if the melting point of the wax is too low, the wax is melted too much, so that the shearing force is less likely to be applied and sufficient wax is applied. It is considered that the dispersion of the above is not performed. On the other hand, if the melting point of the wax is too high, the wax does not sufficiently exude to the toner surface at the time of fixing, and the offset resistance cannot be obtained. Further, the temperature at which 1/2 of the toner starts flowing (T1 / 2) is 110.
When the temperature is from 130 ° C. to 130 ° C., it is possible to obtain transparency and gloss required as a color toner.

Incidentally, the temperature at which 1/2 of the toner starts flowing (T1)
/ 2) was measured as follows. That is, using an elevated flow tester (CFT-500: manufactured by Shimadzu Corporation)
When the sample of 1 cm ³ is melted and flowed out under the conditions of a die pore diameter of 1 mm, a pressure of 20 kg / cm ² , and a temperature rise rate of 6 ° C./min, the height from the flow start point to half the height of the flow end point. Indicates the corresponding temperature. Further, the glass transition temperature (T
g) and the melting point (Wmp) of the wax were measured as follows. That is, Rigaku THER manufactured by Rigaku Denki.
MO FLEX TG8110 type heats up 10 ° C
/ Min, and the main peak of the exothermic endothermic curve is defined as the melting point.

As the wax used in the toner of the present invention, any wax can be used as long as it satisfies the above relationship. Specific examples include the following. Micro wax, candelilla wax, carnauba wax, rice wax, montan wax, paraffin wax, polyethylene wax, polypropylene wax and the like can be used, but are not limited thereto.

Further, as a binder resin, THF-insoluble content is 5%.
By containing the polyester resin and / or the polyol resin in an amount of not more than wt%, the dispersion of the wax in the toner becomes more uniform, and it is possible to obtain offset resistance, transparency and gloss required for a color toner, and Both fixing-related characteristics and stable developability in a one-component developing device, such as preventing filming of toner on the developing roller and fusion of toner to members such as a blade for thinning the toner, can be achieved. It became clear what we could do.

The THF insoluble content of the binder resin was measured as follows. That is, about 1 g of binder resin (W1 g) was placed in a 100 ml conical flask (W0 g).
g), about 5 g (W2 g) of a filter aid, and after mixing, TH
Add F60ml, dissolve at room temperature for 3 hours (extraction)
Let it. Dehumidified and constant weight filter paper (qualitative filter paper NO2, 9 cm,
After drying at 135 ° C. for 2 hours, wrapped in aluminum foil and cooled in a desiccator) (W3 g) was brought into close contact with a Buchner-type funnel equipped with a suction filter using a small amount of THF, and the sample thus adjusted was filtered off. The sample container is washed off and provided for filtration. The sample on the filter paper was washed with about 100 ml of THF, and the sample was transferred together with the filter paper onto the aluminum foil so that the sample did not stick out. The sample was placed in a circulating constant temperature air dryer adjusted to 135 ° C.
After drying for an hour, the mixture is cooled to room temperature in a desiccator, and weighed (W4 g). From the following formula, THF of the binder resin
Calculate the insoluble content.

[0022]

(Equation 1)

As the binder resin, it is particularly preferable to use a polyester resin and / or a polyol resin from the viewpoints of fixability and wax dispersion. The following are particularly preferred for use in the present invention. [Polyester resin]

[0024]

Embedded image (Wherein R ¹ is an alkylene group having 2 to 4 carbon atoms, x,
y is a positive integer, and the average value of the sum is 2 to 16. A) a diol component represented by the following general formula (II) or (II) selected from the group consisting of divalent or higher polycarboxylic acids, anhydrides thereof and lower alkyl esters thereof.
I)

[0025]

Embedded image

[0026]

Embedded image (Wherein R ² and R ³ are a saturated or unsaturated hydrocarbon group having 4 to 20 carbon atoms), or an acid component containing an anhydride thereof or trimellitic acid. And a polyester resin obtained by condensation polymerization of an acid component also containing its anhydride.

Further, phthalic acid, isophthalic acid, terephthalic acid,
Compounds such as maleic acid, fumaric acid, and their anhydrides and lower alkyl esters can be used.
Examples of the compounds represented by the general formulas (II) and (III) include n-dodecenyl succinic acid, n-dodecyl succinic acid, n-butyl succinic acid, iso-dodecenyl succinic acid,
Examples thereof include succinic acid derivatives such as iso-octylsuccinic acid. In particular, when these are used, the fixability of the toner at a low temperature is sufficient and the gloss is further improved.

Examples of the diol represented by the general formula (I) include polyoxypropylene (2,2)-
2,2-bis (4-hydroxyphenyl) propane, polyoxyester (2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6)-
Examples thereof include 2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (16) -2,2-bis (4-hydroxyphenyl) propane. It should be noted that a bifunctional or higher polyhydroxy compound as described below may be used as the diol component in an amount of about 5 mol% or less. Ethylene glycol, propylene glycol, glycerin,
Pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, or etherified polyhydroxyl compounds thereof. The polyester resin can be usually produced by polycondensing a polyol component and a polycarboxylic acid component at a temperature of 180 to 250 ° C. in an inert gas atmosphere.

As the polyol resin, various types can be used, but the following are particularly preferable as those used in the present invention. That is, particularly, as a polyol resin, an epoxy resin, an alkylene oxide adduct of a dihydric phenol or a glycidyl ether thereof, a compound having one active hydrogen that reacts with an epoxy group in a molecule, and an active hydrogen that reacts with an epoxy group It is preferable to use a polyol obtained by reacting a compound having two or more of the above in the molecule. Furthermore, the epoxy resin is particularly preferably at least two or more bisphenol A type epoxy resins having different number average molecular weights. This polyol resin gives good gloss and transparency, and is effective in offset resistance.

The epoxy resin used in the present invention is preferably obtained by combining bisphenol such as bisphenol A or bisphenol F with epichlorohydrin. Epoxy resin is a bisphenol A type epoxy resin of at least two or more different in number average molecular weight, in order to obtain stable fixing properties and gloss, the number average molecular weight of the low molecular weight component is 360-2000, the high molecular weight component It is preferable that the number average molecular weight is 3,000 to 10,000. Further, it is preferable that the low molecular weight component is 20 to 50 wt% and the high molecular weight component is 5 to 40 wt%. If the low molecular weight component is too large, or if the molecular weight is lower than 360, gloss may be too high and storage stability may be deteriorated. Also, there are too many high molecular weight components or a molecular weight of 100
If the polymer is more than 00, gloss may be insufficient,
Further, there is a possibility that the fixing property is deteriorated.

As the compound used in the present invention, the following are exemplified as the alkylene oxide adduct of dihydric phenol. That is, a reaction product of ethylene oxide, propylene oxide, butylene oxide, and a mixture thereof with a bisphenol such as bisphenol A or bisphenol F can be used. The obtained adduct may be glycidylated with epichlorohydrin or β-methylepichlorohydrin before use. In particular, the following general formula (I
Diglycidyl ether of an alkylene oxide adduct of bisphenol A represented by V) is preferred.

[0032]

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The alkylene oxide adduct of dihydric phenol or its glycidyl ether is preferably contained in an amount of 10 to 40% by weight based on the polyol resin. If the amount is small, problems such as increased curl may occur, and if n + m is 7 or more, or if the amount is too large, gloss may be excessively obtained, and furthermore, storage stability may be deteriorated. Examples of the compound having one active hydrogen that reacts with the epoxy group in the molecule used in the present invention include monohydric phenols, secondary amines, and carboxylic acids. The following are illustrated as monohydric phenols. Phenol,
Cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol and the like can be mentioned. Secondary amines include diethylamine, dipropylamine, dibutylamine, N-methyl (ethyl) piperazine, piperidine and the like. Examples of the carboxylic acids include propionic acid and caproic acid.

In order to obtain a polyol resin having an epoxy resin part and an alkylene oxide part in the main chain of the present invention, various combinations of raw materials are possible. For example, it can be obtained by reacting an epoxy resin having glycidyl groups at both terminals and an alkylene oxide adduct of dihydric phenol having glycidyl groups at both terminals with dihalide, diisocyanate, diamine, dithiol, polyhydric phenol, or dicarboxylic acid. Of these, the reaction with dihydric phenol is most preferable in terms of reaction stability. In addition, two or more polyhydric phenols or polycarboxylic acids are used as long as they do not gel.
It is also preferable to use together with a phenol. Here, the amount of polyhydric phenols and polycarboxylic acids is 15% of the total amount.
Or less, preferably 10% or less.

The compound having two or more active hydrogens which react with the epoxy group in the molecule used in the present invention is 2
And polyhydric phenols, polyhydric phenols, and polyhydric carboxylic acids. Examples of the dihydric phenol include bisphenols such as bisphenol A and bisphenol F. As polyhydric phenols, ortho-cresol novolaks, phenol novolaks, and tris (4-
(Hydroxyphenyl) methane, 1- [α-methyl-α-
(4-Hydroxyphenyl) ethyl] benzene is exemplified. Examples of polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid,
Examples include phthalic acid, terephthalic acid, trimellitic acid, and trimellitic anhydride.

When these polyester resins and polyol resins have a high crosslinking density, it is difficult to obtain transparency and glossiness. Therefore, it is preferable that these polyester resins and polyol resins are not crosslinked or weakly crosslinked (THF insoluble content is 5 wt% or less). ) Is preferable.

As the binder resin used in the present invention, the following may be added in addition to the above-mentioned ones. For example, polystyrene, poly-p-chlorostyrene, homopolymers of styrene such as polyvinyltoluene and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, Styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene
Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer,
Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl Ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid Styrene copolymers such as copolymers and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacryl Le acid resin, rosin, modified rosin,
Terpene resins, phenolic resins and the like can be mentioned.

In particular, as a charge controlling agent, a metal salt of a salicylic acid derivative shown below is used in order to obtain a uniform thin layer of toner on a developing roller in a one-component developing device and to obtain stable charging characteristics. Is preferred.

[0039]

Embedded image (Wherein, R ³ , R ⁴ and R ⁵ are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an allyl group,
Particularly, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an allyl group is desirable. Here, R ³ , R ⁴ and R ⁵ may be the same or different at the same time. Me is any metal selected from zinc, nickel, cobalt, copper and chromium. )

This compound was obtained from Clark, J .;
L, Kao, H (1948) J. Amer. Chem.
Soc. 70, 2151. For example, 2 mol of salicylic acid sodium salt (including the sodium salt of salicylic acid derivative) and 1 mol of zinc chloride are added to a solvent, mixed, heated and stirred to obtain a zinc salt. This metal salt is a white crystal and does not show coloring even when dispersed in a toner binder. Even when the metal salt is other than a zinc salt, it can be produced according to the above method. The compounding amount of this compound is 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight, based on 100 parts by weight of the binder resin.

Specific examples of this compound include the following.

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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Further, for unknown reasons, it is possible to impart sufficient fluidity and stable chargeability to the toner by coating the surface of the toner base colored particles with hydrophobic silica and titanium oxide. , Sufficient phenomenon characteristics can be imparted. First, the silica used in the present invention generally includes those produced by a wet method or a dry method. In particular, so-called fumed silica produced by a dry method (vapor phase oxidation of a silicified halogen compound) is used. What is called is preferred from the viewpoint of fluidity.
This is manufactured by a conventionally known technique. For example, the reaction formula utilizing the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame is shown below.

[0051]

Embedded image

In this production step, for example, by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide, it is possible to obtain a composite fine powder of silica and another metal oxide. They are also included. It is desirable that the average primary particle diameter is in the range of 0.001 to 2 μm, and it is particularly preferable to use silica fine powder in the range of 0.002 to 0.2 μm.

Commercially available fine silica powder produced by vapor phase oxidation of a silicon halide compound preferably used in the present invention includes, for example, those commercially available under the following trade names. AEROSIL (Nippon Aerosil) 130 AEROSIL (Nippon Aerosil) 200 AEROSIL (Nippon Aerosil) 300 AEROSIL (Nippon Aerosil) 380 AEROSIL (Nippon Aerosil) TT600 AEROSIL (Nippon Aerosil) MOX 80 AEROSIL (Japan) MOX 80 AEROSIL (Japan) AEROSIL (Aerosil Japan) COK 84 Ca-O-SiL (CABOT Co.) M-5 Ca-O-SiL (CABOT Co.) MS-7 Ca-O-SiL (CABOT Co.) MS-75 Ca-O -SiL (CABOT Co.) HS-5 Ca-O-SiL (CABOT Co.) EH-5 Wacker HDK N20 (WACKER-CHFMIEGMBH) V1S Wacker HDK N20 (WACKER-CHFMIEG) MBH) N20E Wacker HDK N20 (WACKER-CHFMIEGMBH) T30 Wacker HDK N20 (WACKER-CHFMIEGMBH) T40

The hydrophobic treatment of the fine silica powder can be performed by treating the surface of the fine silica powder with a silane compound or the like. That is, the silane compound is reacted with the hydroxyl group bonded to the silica fine powder, and the hydroxyl group is replaced with a siloxyl group or the like.Therefore, the degree of hydrophobicity means that the hydroxyl group existing before the hydrophobicization is lost by the above reaction. In other words, it can be translated into the ratio of the hydroxyl group. The hydrophobic treatment is carried out by reacting a silica fine powder with a dialkyldihalogenated silane, a trialkylhalogenated silane, a hexaalkyldisilazane, an alkyltrihalogenated silane or the like at a high temperature.

The "hydrophobization degree" of the silica fine powder
Can be measured by the following method. 200ml
50 ml of water is placed in a beaker, and 0.2 g of silica fine powder is further added. Then, while gently stirring with a magnetic stirrer, add methanol from the burette whose tip was immersed in water at the time of dropping, the floating silica fine powder began to sink, and read the number of ml of methanol dropped when completely sinking, Hydrophobicity = ｛ml of suboptimal methanol
Number / (50 + ml of dropped methanol)｝ × 100
(%). In this case, methanol acts as a surfactant, and the fine silica powder floating with the dropwise addition of methanol is dispersed in water via methanol.
The greater the value of the degree of hydrophobicity, the higher the degree of hydrophobicity of the silica fine powder. The amount of the silica fine powder added to the toner is 0.1.
The amount is preferably 1 to 2.0 parts by weight, particularly preferably 0.2 to 1.0 part by weight.

As the titanium oxide fine particles used in the present invention, there are those produced by a sulfuric acid method and a chlorine method, and any of rutile type, anatase type, amorphous type and a mixed type thereof can be used. Specific examples of the titanium oxide fine particles include P-25 (manufactured by Degussa); IT-S, IT-P
B, IT-PC (all manufactured by Idemitsu Kosan); R-82
0, R-830, R-680, CR-50, CR-6
0, A-100, A-220 (all manufactured by Ishihara Sangyo Co., Ltd.); JA-1, JA-2, JR, JRNC, JR60
0E, MT-150W, MT-500B, MT-600
B (manufactured by Teica); STT-30A (manufactured by Titanium Industries) and the like. The titanium oxide fine particles to be used are suitably those having a particle size in the range of 0.01 to 1 μm, and particularly preferably those having a particle size of 0.01 to 0.5 μm. About hydrophobic treatment, it is the same as that of silica. Further, the addition amount of the titanium oxide fine particles to the toner is preferably 0.1 to 2.0 parts by weight, particularly preferably 0.2 to 1.0 part by weight.

Next, dyes and pigments capable of obtaining yellow, magenta, cyan and black toners can be used as the colorant. For example, carbon black, lamp black, ultramarine blue, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G, lake, chaco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, etc. Any conventionally known dyes and pigments such as the dyes and pigments described above can be used alone or in combination. The amount of these coloring agents to be used is generally 1 to 30% by weight, preferably 3 to 20% by weight, based on the binder resin.

Further, the particle diameter of the toner of the present invention is preferably about 3 to 10 μm in terms of volume average particle diameter. If the particle diameter is smaller than this, it may cause background contamination during development and deteriorate flowability. This may hinder toner replenishment and cleaning performance. Further, when the particle diameter is larger than this, dust in an image, deterioration of resolution, and the like may cause a problem.

As the charge controlling agent used in the toner of the present invention, it is particularly preferable to use the above-mentioned metal salt of a salicylic acid derivative, but if necessary, a transparent or white substance which does not impair the color tone of the color toner is used. And add
The chargeability of the toner can be stably provided. Specifically, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene-based compounds, and the like are used, but are not limited thereto. Further, as an external additive, in addition to the hydrophobic silica and titanium oxide used in the present invention, alumina, and further, if necessary, fatty acid metal salts and polyvinylidene fluoride are added for the purpose of improving the fluidity of the toner. You may.

[0060]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Also,
The characteristics were measured as follows. Offset non-occurrence temperature range Using a Ricoh color copying machine Pretail 550, transfer paper (Ricoh type 6000-70W) to yellow,
The solid image composed of red, blue, and green is adjusted as a single color of magenta, cyan, and black so that a toner of 1.0 ± 0.1 mg / cm ² is developed in a single color. It was remodeled and adjusted so that the temperature of the fixing roller was variable, and the density at which no offset occurred was measured. The evaluation was performed under the condition that oil was not applied to the fixing roller.

Gloss The gloss of the above monochrome image sample when the surface temperature of the fixing roller was 160 ° C. was measured by a gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. at an incident angle of 60 °. The glossiness increases as the value increases. As a full-color copy image, moderate gloss is preferred, and about 10 to 30% is preferred.

Haze degree The above monochromatic image sample was used as transfer paper by Ricoh OH
Using a P sheet (type PPC-DX), the degree of haze of the sample when the surface temperature of the fixing roller was 160 ° C. was measured using a direct read haze degree computer HG manufactured by Suga Test Instruments Co.
It was measured by M-2DP type. The haze is also referred to as haze, and is measured as a measure of the transparency of the toner. The lower the value, the higher the transparency, and the better the color developability when an OHP sheet is used. Further, the value of the haze indicating good color development is preferably 30% or less, and especially 2%.
The case where it is 0% or less is preferable.

Characteristics of Toner on Developing Roller (Evaluation Apparatus) Developing apparatus (developing roller (2)) shown in FIG.
As shown in FIG. 1, a toner supply roller (3) made of a polyurethane material and having a silicone resin as a main component as a surface layer and in contact with the main developing roller, and a blade (4) made of a urethane material and in contact with the main developing roller, as shown in FIG. (Set). In FIG. 1, 1 is a latent image carrier (belt photoconductor), 2 is a developing roller, 2-1 is a metal core, 2-2 is a resin coat layer, 3 is a toner supply member, 4 is a developer application blade, Is an agitator and 6 is a development zone.

-1 Charge amount -2 Amount of toner attached A toner sucking toner on the developing roller through a Faraday cage having a filter layer on the outlet side, and measuring the specific charge of the toner trapped in the Faraday cage. The charge amount is measured by a normal specific charge measuring device. At the same time, the toner adhesion amount is calculated from the relationship between the weight of the trapped toner and the area of the sucked developing roller. The appropriate values of these characteristics vary depending on the linear velocity (ratio) of the developing roller and the photoconductor, but are generally as follows, and are particularly stable even when the developing roller is stirred for a long time by a large number of prints. Is preferable from the viewpoint of stabilizing the amount of toner to be developed. Charge amount 10 to 25 (μc / g) in absolute value Adhesion amount 0.5 to 1.5 (mg / cm ² )

-3 Thin layer property of toner The thin layer property of the toner on the developing roller was visually observed. Further, after the developing roller was stirred for a long period of time, the developing unit was disassembled, and after removing the toner, the filming state of the toner on the developing roller and the fixing state of the toner to the developer application blade were visually observed.

(Example 1)-Binder resin 1 (polyester resin: THF-insoluble content 6 wt%) 80 parts by weight-Binder resin 2 (styrene-acrylic copolymer: THF-insoluble content 5 wt%) 20 parts by weight-Wax (Microwax: melting point (Wmp) = 100 ° C.) 4 parts by weight ・ Charge controlling agent (fluorinated quaternary ammonium salt compound) 3 parts by weight ・ Colorant <for yellow toner> Disazo yellow pigment (CIPigment Yellow17) 5 parts by weight Part <for magenta toner> 4 parts by weight of quinacridone-based magenta pigment (CIPigment Red 122) <for cyan toner> 2 parts by weight of copper phthalocyanine blue pigment (CIPigment Blue 15) <for black toner> 5 parts by weight of carbon black

After the above-mentioned materials were sufficiently mixed for each color by a blender, they were melt-kneaded by two rolls heated to 100 to 110 ° C. After the kneaded product was allowed to cool naturally, it was coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then used to obtain base colored particles of each color using an air classifier. In addition, the volume average particle diameter of each color base coloring particle was as follows. (Volume average particle size is Coulter Electronics Coulter Counter Model TA-I
I measured. ) Yellow: 7.8 (μm), Magenta: 7.9 (μm) Cyan: 7.5 (μm), Black: 8.1 (μm) Further, an external additive is added to 100 parts by weight of the base colored particles. Was mixed with a Henschel mixer to obtain toners of yellow, magenta, cyan, and black, respectively. The glass transition temperature (Tg) of the present toner is 64 ° C., and the 流出 outflow start temperature (T1 /
2) was 118 ° C.

The obtained toner was set in a modified model of Myricop M-5 manufactured by Ricoh, and the characteristics of the toner layer on the developing roller were evaluated. The thin toner layer on the developing roller was uniform and did not change even after printing 30,000 sheets, and there was little change in the charge amount and the toner adhesion amount.

Further, when the temperature range in which offset did not occur, the glossiness, and the haze were evaluated by the method described above, good results were obtained in all cases. Table 1 shows a summary of the evaluation results.

(Example 2) 100 parts by weight of binder resin (polyester resin: 3% by weight of THF insoluble matter) 5 parts by weight of wax (polyethylene wax: melting point (Wmp) = 101 ° C.) 5 parts by weight Charge control agent (fluorine-containing 4 Ammonium salt compound) 3 parts by weight ・ Coloring agent is the same as in Example 1.

The above materials were treated in the same manner as in Example 1 to obtain base colored particles having the following volume average particle diameter. Yellow: 7.7 (μm), Magenta: 8.2 (μm) Cyan: 7.8 (μm), Black: 7.9 (μm) Further, as an external additive to 100 parts by weight of the base colored particles And 0.8 parts by weight of hydrophobic silica were mixed with a Henschel mixer to obtain toners of yellow, magenta, cyan and black. The glass transition temperature (Tg) of this toner is 65 ° C., and the 流出 outflow starting temperature (T1 /
2) was 114 ° C.

Further, the same evaluation as in Example 1 was performed, and good results were obtained as in Example 1. Table 1 shows a summary of the evaluation results.

(Example 3) 100 parts by weight of binder resin (polyester resin: THF insoluble content 1 wt%) 5 parts by weight of wax (polypropylene wax: melting point (Wmp) = 120 ° C.) 5 parts by weight Charge control agent (salicylic acid derivative metal) Salt: Compound Example 4) 3 parts by weight ・ Coloring agent is the same as in Example 1.

The above-mentioned materials were treated in the same manner as in Example 1 to obtain base colored particles having the following volume average particle diameters. Yellow: 8.9 (μm), Magenta: 8.6 (μm) Cyan: 8.8 (μm), Black: 8.5 (μm) Further, as an external additive to 100 parts by weight of the base colored particles , 1.0 part by weight of hydrophobic titanium oxide was mixed with a Henschel mixer, and yellow, magenta, cyan,
Black toner of each color was obtained. The glass transition temperature (Tg) of the present toner is 63 ° C., and the 1/2 outflow start temperature (Tg)
）) Was 128 ° C. Further, the same evaluation as in Example 1 was performed, and good results were obtained as in Example 1. Table 1 shows a summary of the evaluation results.

Example 4 100 parts by weight of binder resin (polyol resin: 2% by weight of THF-insoluble matter) 3 parts by weight of wax (polyethylene wax: melting point (Wmp) = 110 ° C.) 3 parts by weight Charge control agent (salicylic acid derivative metal) Salt: Compound Example 1) 4 parts by weight-Colorant is the same as in Example 1.

The above materials were treated in the same manner as in Example 1 to obtain base colored particles having the following volume average particle diameters. Yellow: 7.9 (μm), Magenta: 8.1 (μm) Cyan: 7.8 (μm), Black: 8.3 (μm) Further, as an external additive to 100 parts by weight of the base colored particles 0.6 parts by weight of hydrophobic silica and 0.6 parts by weight of hydrophobic titanium oxide were mixed in a Henschel mixer,
Yellow, magenta, cyan, and black toners were obtained. The glass transition temperature (Tg) of this toner was 64 ° C., and the 1/2 outflow starting temperature (T1 / 2) was 119 ° C. Further, the same evaluation as in Example 1 was performed, and good results were obtained as in Example 1. Table 1 shows a summary of the evaluation results.

(Example 5) Binder resin (Polyester resin: THF insoluble content: 0 wt%) 100 parts by weight Wax (polyethylene wax: melting point (Wmp) = 113 ° C.) 5 parts by weight Charge control agent (salicylic acid derivative metal) Salt: Compound example 5) 3.5 parts by weight-Colorant is the same as in Example 1.

The above materials were treated in the same manner as in Example 1 to obtain base colored particles having the following volume average particle diameter. Yellow: 8.3 (μm), Magenta: 8.1 (μm) Cyan: 8.2 (μm), Black: 8.0 (μm) Further, as an external additive to 100 parts by weight of the base colored particles 0.7 parts by weight of hydrophobic silica and 0.6 parts by weight of hydrophobic titanium oxide were mixed with a Henschel mixer,
Yellow, magenta, cyan, and black toners were obtained. The glass transition temperature (Tg) of this toner was 63 ° C., and the 1/2 outflow starting temperature (T1 / 2) was 120 ° C. Further, the same evaluation as in Example 1 was performed, and good results were obtained as in Example 1. Table 1 shows a summary of the evaluation results.

(Comparative Example 1) Binder resin (polyester resin: THF insoluble content: 10 wt%) 100 parts by weight Wax (paraffin wax: melting point (Wmp) = 85 ° C.) 5 parts by weight Charging control agent (fluorine-containing 4 Ammonium salt compound) 3 parts by weight ・ Coloring agent is the same as in Example 1.

The above materials were treated in the same manner as in Example 1 to obtain base colored particles having the following volume average particle size. Yellow: 7.3 (μm), Magenta: 7.5 (μm) Cyan: 7.8 (μm), Black: 7.9 (μm) Further, as an external additive to 100 parts by weight of the base colored particles , 0.9 parts by weight of hydrophobic titanium oxide was mixed with a Henschel mixer, and yellow, magenta, cyan,
Black toner of each color was obtained. The glass transition temperature (Tg) of the present toner is 59 ° C., and the half flow start temperature (Tg)
）) Was 108 ° C. Further, the same evaluation as in Example 1 was performed.
The toner filmed on the developing roller, and the toner adhered to the developer application blade. The amount of charge and the amount of toner adhered were reduced, and the thin layer of toner became uneven. Table 1 shows a summary of the evaluation results.

(Comparative Example 2) Binder resin (polyol resin: THF insoluble content: 0 wt%) 100 parts by weight Wax (ester wax: melting point (Wmp) = 83 ° C.) 4 parts by weight Charge control agent (salicylic acid derivative) Metal salt: Compound example 2) 3.5 parts by weight-Colorant is the same as in Example 1.

The above materials were treated in the same manner as in Example 1 to obtain base colored particles having the following volume average particle diameters. Yellow: 7.9 (μm), Magenta: 7.7 (μm) Cyan: 7.8 (μm), Black: 7.9 (μm) Further, as an external additive to 100 parts by weight of the base colored particles And 0.7 parts by weight of hydrophobic silica were mixed with a Henschel mixer to obtain yellow, magenta, cyan and black toners. The glass transition temperature (Tg) of this toner is 65 ° C., and the 流出 outflow starting temperature (T1 /
2) was 136 ° C. Further, when the same evaluation as in Example 1 was performed, after printing 30,000 sheets, the toner filmed on the developing roller, the toner was fixed on the developer application blade, and the charge amount and the toner adhesion amount were reduced.
The thin layer of toner became non-uniform. Table 1 shows a summary of the evaluation results.

(Comparative Example 3) Binder resin (polyester resin: THF-insoluble content: 3 wt%) 100 parts by weight Wax (polypropylene wax: melting point (Wmp) = 135 ° C.) 5 parts by weight Charge control agent (fluorine-containing 4 Ammonium salt compound) 3 parts by weight ・ Coloring agent is the same as in Example 1.

The above materials were treated in the same manner as in Example 1 to obtain base colored particles having the following volume average particle diameters. Yellow: 7.9 (μm), Magenta: 7.7 (μm) Cyan: 8.3 (μm), Black: 7.9 (μm) Further, as an external additive to 100 parts by weight of the base colored particles 0.6 parts by weight of hydrophobic silica and 0.6 parts by weight of hydrophobic titanium oxide were mixed in a Henschel mixer,
Yellow, magenta, cyan, and black toners were obtained. The glass transition temperature (Tg) of this toner was 64 ° C., and the 1/2 outflow starting temperature (T1 / 2) was 125 ° C. Further, when the same evaluation as in Example 1 was performed, the toner was offset to the fixing roller. Table 1 shows a summary of the evaluation results.

[0085]

[Table 1-1]

[0086]

[Table 1-2]

[0087]

[Table 1-3]

[0088]

[Table 1-4]

[0089]

As is apparent from the detailed and concrete description, the color toner of the present invention is used for non-magnetic one-component development containing at least a binder resin, a colorant, a wax and a charge control agent as main components. In the color toner, the glass transition temperature (Tg) of the toner is 62 ° C. or more, and the half-flow start temperature (T1 / 2) of the toner is 110 to 130 ° C.
And the relationship with the melting point (Wmp) of the wax is (T1 / 2) − (Wmp) = 5 to 20 ° C., so that the chargeability of the toner on the developing roller, the toner adhesion amount, and the toner thinness The uniformity of the layer is stable even with long-term stirring, and without applying oil to the fixing roller,
High gloss and transparency, and can prevent the occurrence of offset. Further, by containing a polyester or / and polyol resin having a THF-insoluble content of 5 wt% or less as the binder resin, the gloss and transparency can be further improved while the toner characteristics on the developing roller are kept stable. By using a metal salt of a salicylic acid derivative as the charge control agent, the toner characteristics on the developing roller can be further stabilized and maintained. Further, the color toner is coated on the surface of the base colored particles with an external additive, and contains hydrophobic silica and titanium oxide in combination as the external additive,
Further, the present invention has an extremely excellent effect that the toner characteristics on the developing roller can be stably maintained.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of an example of a developing device useful for using the toner of the present invention, focusing on a developing roller unit.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 latent image carrier (belt photoreceptor) 2 developing roller 2-1 cored bar 2-2 resin coating layer 3 toner supply member 4 developer coating blade 5 agitator 6 development area

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI G03G 9/08 374 375 (72) Inventor Keiko Shiraishi 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company, Ltd.

Claims (4)

[Claims] In a non-magnetic one-component developing color toner containing at least a binder resin, a colorant, a wax, and a charge control agent as main components, the glass transition temperature (T
g) is 62 ° C. or more, the 流出 outflow starting temperature (T1 / 2) of the toner is 110 to 130 ° C., and the relationship with the melting point (Wmp) of the wax is as follows. A nonmagnetic one-component color toner for development. (T1 / 2) − (Wmp) = 5 to 20 ° C. 2. The binder resin has a THF-insoluble content of 5%.
The color toner for non-magnetic one-component development according to claim 1, wherein the color toner contains a polyester or / and polyol resin in an amount of not more than wt%. 3. The color toner for non-magnetic one-component development according to claim 1, wherein a metal salt of a salicylic acid derivative is used as the charge control agent. 4. The color toner according to claim 1, wherein the surface of the base colored particles is coated with an external additive, and the external additive further comprises hydrophobic silica and titanium oxide. The color toner for non-magnetic one-component development according to any one of the above.