JP2001166540A - Yellow toner and full-color developing toner using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a yellow toner which gives stable image density and hue of the print without causing toner fog on a photoreceptor even when the toner is used for a nonmagnetic single-component developing method and which is suitable for a full-color development, and to provide a full-color developing toner by using that yellow toner. SOLUTION: The yellow toner consists of a mixture of the following components (YA) and (YB). The component (YA) consists of toner particles containing a polyester resin, a yellow pigment such as C.I.pigment yellow 74, yellow 155 or the like, and a negative charge controlling agent. The polyester resin has <=30 KOHmg/g acid value, 2,000 to 20,000 number average mol.wt. (Mn), 5,000 to 300,000 weight average mol.wt. (Mw), 2 to 150 of Mw/Mn, 70 to 100 wt.% tetrahydrofuran-soluble content, 80 to 160 deg.C softening point, and 50 to 75 deg.C glass transition temperature. The component (YB) consists of inorganic fine powder such as silica, titania and alumina subjected to the surface treatment with silicone oil and having 5 to 500 m2/g specific surface area.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a yellow toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, and a full-color developing toner using the same. The present invention relates to a yellow toner suitable for full-color development as a three primary color toner of a toner and a cyan toner, and a full-color development toner using the same.

[0002]

2. Description of the Related Art Conventionally, as a method of forming an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc., for example,
A charging step of uniformly charging the photoconductive insulating layer,
An exposure step of exposing the layer, dissipating the charge in the exposed areas to form an electrostatic latent image, and visualizing the electrostatic latent image by applying charged toner to the unexposed areas After a development step, a transfer step of transferring the obtained visible image to a transfer material such as transfer paper, a method comprising a fixing step of fixing the visible image to the transfer material by heating, pressurizing, etc. is often used, The developing step includes a magnetic two-component developing method including a toner containing a colorant and a magnetic powder as a carrier for transporting the toner to an electrostatic latent image portion by magnetic force, and The magnetic one-component developing system contained therein has been mainly used.

On the other hand, in the magnetic two-component developing method and the magnetic one-component developing method, it is necessary to use a magnet for the developing roll. A non-magnetic one-component developing method that does not use powder and does not use a magnet for a developing roll has attracted attention. In this method, for example, in a developing process, a gap between a developing roller having a small diameter and a pressing regulation member is pressed. To form a thin toner layer, so that a sufficient amount of toner charge and toner adhesion cannot be obtained at the time of development. Problems such as increased fogging and white background fogging, and poor transparency of the color image of the sheet for an overhead projector occur. In response to this, various improvers are added to the toner. Although improved process has also been proposed,
In full color development using three primary color toners of magenta toner, cyan toner, and yellow toner, and in some cases, further using a black toner, none of the methods can solve the above problem in a well-balanced manner.

Incidentally, as a yellow toner in the non-magnetic one-component developing system, for example, C.I. I. Pigment Yellow 1, 3, 74, 97, 98, etc., acetoacetic arylamide monoazo yellow pigments, C.I. I. Azoacetate arylamide-based disazo yellow pigments such as CI Pigment Yellow 12, 13, 13, and 17; I. Pigment Yellow 93, 155 and the like, condensed monoazo yellow pigments, C.I. I. Pigment Yellow 109, 11
Isoindolinone pigments such as C.0, 137, 173;
I. Pigment Yellow 150, 180, 185
Other yellow pigments such as C.I. I. Solvent Yellow 19, 77, 79, C.I. I. A yellow toner containing a yellow colorant such as a yellow dye such as Disperse Yellow 164, a binder resin of a polyester resin, and a negative charge control agent is known (for example, Japanese Patent Application Laid-Open No. 8-234491). No., JP-A-10-171155,
JP-A-10-312089, JP-A-11-72959
No. publications).

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and has been made to solve the above problem from the viewpoint of yellow toner. Accordingly, the present invention has been applied to a non-magnetic one-component developing system. Even in this case, there is no excess or deficiency in the toner charge amount and toner adhesion amount, so that the image density and print hue are stable, the toner fog and white background fog on the photoreceptor are small, and the transparency is also low. A yellow toner that can form a good image and is suitable for full-color development as a three primary color toner of a magenta toner and a cyan toner,
And a full-color developing toner using the same.

[0006]

The gist of the present invention is a yellow toner comprising a mixture of the following components (Y _A ) and (Y _B ). (Y _A ); toner particles containing the following components (Y _A1 ), (Y _A2 ), and (Y _A3 ): (Y _A1 ); polyester satisfying the following characteristics (1) to (7): (1) Acid value ≦ 30 KOH mg / g (2) Number average molecular weight (M _n ) 2,000 to 20,000 (3) Weight average molecular weight (M _W ) 5,000 to 300,0
00 (4) number-average molecular weight The weight average molecular weight to the (M _n) (M _W) ratio _{(M W / M n) 2~150} (5) tetrahydrofuran-soluble matter of 70 to 100 wt% (6) Softening temperature 80 160 ° C. (7) Glass transition temperature 50-75 ° C. (Y _A2 ); I. Pigment Yellow 74, 15
5, a yellow pigment (Y _A3 ) selected from the group consisting of 180, and 185; a negatively chargeable charge control agent (Y _B ); surface-treated with silicone oil, and having a specific surface area of 5 to 500 m ² / G of any one of inorganic fine powders selected from the group consisting of silica, titania, and alumina

The present invention also provides a magenta toner comprising a mixture of the above yellow toner, the following (M _A ) component and the following (M _B ) component, and the following (C _A ) and (C _B ) components: And a full-color developing toner composed of at least three primary color toners and a cyan toner composed of a mixture of the above. (M _A ); toner particles containing the following components (M _A1 ), (M _A2 ), and (M _A3 ): (M _A1 ); polyester satisfying the following characteristics (1) to (7): (1) Acid value ≦ 30 KOH mg / g (2) Number average molecular weight (M _n ) 2,000 to 20,000 (3) Weight average molecular weight (M _W ) 5,000 to 300,0
00 (4) number-average molecular weight The weight average molecular weight to the (M _n) (M _W) ratio _{(M W / M n) 2~150} (5) tetrahydrofuran-soluble matter of 70 to 100 wt% (6) Softening temperature 80 160 ° C. (7) Glass transition temperature 50-75 ° C. (M _A2 ); I. Pigment Red 57: 1, 1
22, 146, 184, 238, and C.I. I. Any of a magenta pigment selected from the group consisting of Pigment Violet 19 (M _A3); negatively charged charge control agent (M _B); surface-treated with silicone oil, the specific surface area is 5 to 500 m ² / g Any inorganic fine powder selected from the group consisting of silica, titania, and alumina

(C _A ): The following (C _A1 ) component, (C _A2 )
Component, and (C _A3) toner particles containing a component (C _A1); following (1) to the polyester resin satisfying the characteristics of (7) (1) acid value ≦ 30 KOHmg / g (2) Number average molecular weight (M _n) 2,000~20,000 (3) a weight average molecular weight (M _W) 5,000~300,0
00 (4) number-average molecular weight The weight average molecular weight to the (M _n) (M _W) ratio _{(M W / M n) 2~150} (5) tetrahydrofuran-soluble matter of 70 to 100 wt% (6) Softening temperature 80 160 ° C. (7) Glass transition temperature 50-75 ° C. (C _A2 ); I. Pigment Blue 15: 3, and any of cyan pigments selected from the group consisting of 15: 4 (C _A3 ); negatively chargeable charge control agent (C _B ); Any one of inorganic fine powders selected from the group consisting of silica, titania, and alumina having a weight of ^{5 to} 500 m ² / g

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The yellow toner of the present invention is constituted.
(Y_AThe toner particles of the component _A1)component,
(Y_A2) Component, and (Y_A3) Indispensable to contain ingredients
And (Y_A1); A poly satisfying the following characteristics (1) to (7):
Ester resin (1) Acid value ≦ 30 KOHmg / g (2) Number average molecular weight (M_n) 2,000 to 20,000 (3) Weight average molecular weight (M_W) 5,000-300,0
00 (4) Number average molecular weight (M_nWeight average molecular weight for
(M_W) Ratio (M_W/ M_n) 2-150 (5) Tetrahydrofuran soluble matter 70-100% by weight (6) Softening temperature 80-160 ° C (7) Glass transition temperature 50-75 ° C (Y_A2); I. Pigment Yellow 74, 15
5, selected from the group consisting of 180, and 185
Any yellow pigment (Y_A3); Negative charge control agent

Here, as the characteristic (1) to be satisfied by the polyester resin (Y _A1 ), the acid value is 30 KOHm.
g / g or less, 25 KOHmg / g
It is preferred that: If the acid value exceeds the above range, it becomes difficult to obtain a stable charge amount against environmental changes such as temperature and humidity as a yellow toner, and the white background fog is deteriorated at high temperature and high humidity, and the image is deteriorated at low temperature and low humidity. This will cause the concentration to drop. In the present invention, the acid value is measured according to JIS K0070.

The polyester resin of the (Y _A1 ) component has a satisfactory property (2) in that the number average molecular weight (M _n ) measured by gel permeation chromatography is from 2,000 to 20,000. Is essential, and preferably 3,000 to 12,000,
Further, as the characteristic (3), the weight average molecular weight (M) similarly measured by gel permeation chromatography was used.
_W ) is required to be 5,000 to 300,000, preferably 6,000 to 250,000.
When the number-average molecular weight ( _Mn ) and the weight-average molecular weight ( _Mw ) are both below and above the above ranges, a sufficient temperature range cannot be obtained at the time of fixing an image, and the balance between transparency and glossiness as a color image is not obtained. It will collapse.

In the present invention, the measurement of the molecular weight by gel permeation chromatography is carried out by gel permeation chromatography (“H” manufactured by Tosoh Corporation).
LC-8020 ") and a polystyrene gel column (" PLgel 10μ Mix "manufactured by PL Co., Ltd.) as a column.
d type ", inner diameter 7.5 mm x length 30 cm, two connected) using a RI (refractive index) detector as a detector at a temperature of 40 ° C, a solvent of tetrahydrofuran, and a flow rate of 0.5.
ml / min, sample concentration 0.1% by weight, sample injection amount 100μ
This was carried out under the conditions of 1.

As a characteristic (4) that the polyester resin (Y _A1 ) should satisfy, the ratio (M _W ) of the weight average molecular weight (M _W ) to the number average molecular weight (M _n ) is sufficient.
_W / M _n ) must be 2 to 150, and 2 to 1
It is preferably 00, more preferably 2 to 50. Wherein said number of weight average molecular weight to the average molecular weight (M _n) ratio (M _W / M _n) is the range exceeding the (M _W), together with pulverizing property during toner production is lowered, the image fixing property and transparency On the other hand, below the above range,
The hot offset property is deteriorated, and the toner is pulverized during continuous printing, which causes problems such as deterioration of white background fog.

The polyester resin of the (Y _A1 ) component has a peak molecular weight in the molecular weight distribution of 3,000 to 3,000.
It is preferably in the range of 30,000, 4,000 to
More preferably, it is in the range of 25,000.

[0015] The polyester resin of the (Y _A1 ) component must satisfy the following requirement (5): a tetrahydrofuran-soluble content of 70 to 100% by weight;
Preferably it is 100% by weight. If the content of the tetrahydrofuran-soluble component is less than the above range, fixing of the image becomes poor, and it becomes difficult to obtain an image having good transparency. still,
In the present invention, the tetrahydrofuran-soluble component is measured by Soxhlet extraction for 6 hours using a tetrahydrofuran solvent.

The polyester resin of the (Y _A1 ) component has a satisfactory property (6) as having a softening temperature of 80 to 160.
° C is essential, and preferably 90 to 150 ° C. When the softening temperature is lower than the above range, the fixing of the image becomes poor, and it becomes difficult to obtain an image with good transparency. On the other hand, when the softening temperature is higher than the above range, the glossiness of the image becomes poor.

In the present invention, the softening temperature is determined according to JIS.
Using a flow tester (“CFT500” manufactured by Shimadzu Corporation) by the flow tester method based on K7210,
After preheating for 5 minutes by gently pressing a plunger with 1 g of resin in a cylinder at 80 ° C., the temperature is increased at a rate of 3 ° C./min while applying a pressure of 30 kg / cm ² , and a nozzle having a diameter of 1 mm and a length of 10 mm The temperature at which the plunger reached the middle point from the start to the end of the lowering of the plunger when the resin was extruded was defined as the softening temperature.

The polyester resin (Y _A1 ) should have a glass transition temperature of 50 to 50 as a characteristic (7) to be satisfied.
It is essential that the temperature be 75 ° C, and it is preferably 55 to 70 ° C. If the glass transition temperature is lower than the above range, aggregation or the like is likely to occur during the production of toner particles. On the other hand, if the glass transition temperature is higher than the above range, fixing of the image becomes poor and it becomes difficult to obtain an image with good transparency.

In the present invention, the glass transition temperature is
Using a differential thermal analyzer (“DT-30” manufactured by Shimadzu Corporation), about 20 mg of the resin was heated to 100 ° C. at a rate of 10 ° C./min, cooled to room temperature, and then again at a rate of 10 ° C./min. The glass transition temperature was defined as the intersection of the two tangents of the smooth curve before and after the inflection temperature portion of the DTA curve when the temperature was raised.

The above characteristics (1) to (7) are satisfied (Y
_A1 ) The polyester resin of the component is basically a polycondensate of one or more dicarboxylic acids and one or more diols. Specific examples of the dicarboxylic acids include, for example, terephthalic acid, Phthalic acid, isophthalic acid,
Phenylenedioxydicarboxylic acid, 2,2′-diphenyldicarboxylic acid, 4,4′-diphenyldicarboxylic acid,
4,4′-diphenyl ether dicarboxylic acid, 4,4 ′
Aromatic dicarboxylic acids such as diphenyl ketone dicarboxylic acid, 4,4′-diphenoxyethane dicarboxylic acid, 4,4′-diphenyl sulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and anhydrides thereof;
Alkyl esters and the like, among which terephthalic acid,
Isophthalic acid and the like are preferable, and specific examples of the diols include ethylene glycol, 1,2
-Propylene glycol, 1,3-propylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, neopentyl glycol, diethylene glycol, polyethylene glycol, polytetramethylene ether glycol, etc. Aliphatic diol, 1,2-cyclohexanediol, 1,4-cyclohexanediol,
Alicyclic diols such as 1,1-cyclohexane dimethylol and 1,4-cyclohexane dimethylol, xylylene glycol, 4,4′-dihydroxybiphenyl, 2,
2-bis (4'-hydroxyphenyl) propane, 2,
2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid, 2,2-bis (4′-hydroxyphenyl) propane And aromatic diols such as ethylene oxide adducts and propylene oxide adducts.
Preferred are alkylene oxide adducts such as ethylene oxide or propylene oxide adduct of -bis (4'-hydroxyphenyl) propane, and particularly preferably those having an average alkylene oxide addition number of 2 to 7.

In the polyester resin according to the present invention, in addition to a linear polycondensate obtained by polycondensation of the dicarboxylic acids and the diols, part or all of the dicarboxylic acids may be replaced with trivalent or higher carboxylic acids. And / or a non-linear polycondensate obtained by replacing a part or all of the diols with alcohols having a valency of 3 or more may be a polycondensed non-linear polycondensate. Include, for example, 1,2,4-benzenetricarboxylic acid,
1,2,5-benzenetricarboxylic acid, 1,2,4,5
-Benzenetetracarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid,
2,5-hexanetricarboxylic acid, tetra (methylenecarboxy) methane, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,7,8-
Octanetetracarboxylic acid, or their anhydrides, alkyl esters, and the like. Examples of the trivalent or higher alcohols include, for example, glycerol,
2-methylpropanetriol, 1,2,4-butanetriol, 2-methyl-1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,3,6
-Hexane tetrol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, sorbitol, 1,4-sorbitan, 1,3,5-trihydroxymethylpentene, sucrose and the like.

The yellow pigment of the component (Y _A2 ) includes C.I. I. Pigment Yellow 74, 155, 180, and 185 is essential, and any other yellow colorant can achieve the object of the present invention. Can not.

The negatively chargeable charge controlling agent of the (Y _A3 ) component is not particularly limited, but in the present invention, it is preferably represented by the following general formula (I). .

[0024]

Embedded image

[In the formula (I), R ¹ , R ² , R ³ and R
⁴ each independently have an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent, Represents an optionally substituted aryl group or a hydrogen atom, and X ⁺ represents a counter cation. ]

In the formula (I), examples of the alkyl group of R ¹ , R ² , R ³ and R ⁴ include, for example, methyl, ethyl, propyl and butyl, and examples of the alkenyl group include A vinyl group, an allyl group, an isopropenyl group, and the like, as the cycloalkyl group, for example, a cyclopentyl group, a cyclohexyl group, and the like, and as the aryl group, for example, a phenyl group, a naphthyl group, and the like, Examples of such a substituent include an alkyl group, an alkenyl group, an alkoxy group, an aryl group, a hydroxyl group, and a halogen atom.

The counter cation X ⁺ includes, for example, alkali metal ions such as lithium, sodium and potassium.

In the present invention, as the negatively chargeable charge control agent represented by the general formula (I), R ¹ , R ² ,
Preferably, at least two of R ³ and R ⁴ are aryl groups, and the counter cation X ⁺ is an alkali metal ion, and R ¹ , R ² , R ³ , and R ⁴ are all phenyl groups. In particular, those in which the counter cation X ⁺ is a potassium ion are particularly preferred.

The inorganic fine powder of the component (Y _B ) constituting the yellow toner of the present invention is surface-treated with silicone oil and comprises silica, titania and alumina having a specific surface area of 5 to 500 m ² / g. It is essential to be one selected from the group, and silica is preferred. The inorganic fine powder of the component (Y _B ) is silica, titania,
Or, other than alumina, the charging characteristics will be inferior, and even if any of these three types, if the specific surface area is less than the above range, the fluidity as toner particles will deteriorate, while if more than the above range, In addition, the aggregation of the inorganic fine powders easily occurs, and in any case, the object of the present invention cannot be achieved.

In the present invention, the specific surface area is AST
Based on MD3037, it was measured by a BET method using a flow-type specific surface area automatic measuring device ("Flow Soap 2300" manufactured by Shimadzu Corporation).

The silicone oil as a surface treating agent for the inorganic fine powder has a siloxane bond as a skeleton.
So-called organopolysiloxanes, specifically, for example, straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methyl hydrogen silicone oil, and acrylic-modified silicone oil, epoxy-modified silicone oil, and fluorine-modified silicone Examples thereof include modified silicone oils such as oil, polyether-modified silicone oil, and amino-modified silicone oil. Among them, straight silicone oil is preferred, and dimethyl silicone oil is particularly preferred.

The yellow toner of the present invention is preferably prepared by using the above (Y _A1 )
Component of the polyester resin, the (Y _A2) component yellow pigment, and the (Y _A3) containing component of the negative charge charge control agent and (Y _A) component of the toner particles, the (Y _B) components Although consisting of a mixture of inorganic fine powder, wherein (Y _B)
The proportion of inorganic fine powder component is preferably from 0.1 to 8 parts by weight based on the (Y _A) 100 parts by weight of component according to the particle size of the toner particles (Y _A) component, The range is appropriately selected so as not to cause an excessive coverage in this range.
If the proportion of the inorganic fine powder is less than the above range, the fluidity and long-term storage stability of the yellow toner tend to be inferior, whereas if the proportion exceeds the above range, the toner fog and white background fog on the photoreceptor tend to increase. In addition, the filming of the toner on the photoreceptor tends to occur.

The proportion of the yellow pigment in the component (Y _A2 ) is preferably 1.5 to 10% by weight based on the total amount of the component (Y _A ) and the component (Y _B ). It is particularly preferably 2 to 8% by weight. If the proportion of the yellow pigment is less than the above range, it tends to be difficult to obtain a sufficient image density, while if it exceeds the above range, the transparency of the image tends to deteriorate.

The proportion of the charge controlling agent in the component (Y _A3 ) is 0.1 to 6% by weight based on the total amount of the component (Y _A ) and the component (Y _B ). Is preferred,
It is particularly preferred that it is between 0.2 and 5% by weight. If the proportion of the charge control agent is less than the above range, it tends to be difficult to obtain a sufficient charge amount as a yellow toner, while if it exceeds the above range, the fixability and transparency of the image tend to deteriorate.

Incidentally, the yellow toner of the present invention has the above (Y)
_{As the} component ( _A ), in addition to the polyester resin of the component (Y _A1 ), for example, other polyester resins, styrene-acrylic resins, styrene resins, polyamide resins, polycarbonate resins, and polyvinyl chloride resins , Polyolefin-based resins, polyphenylene ether-based resins, polyvinyl butyral-based resins, ketone-based resins, acrylic resins, fluorine-based resins, urethane-based resins, epoxy-based resins, and other resins commonly used as binder resins. The toner may further contain various known internal additives for the purpose of improving the adhesiveness, cohesiveness, fluidity, chargeability, surface resistance, and releasability of the toner. In particular, it is preferable to contain a polyolefin-based wax such as a polyethylene wax and a polypropylene wax in order to improve fogging and white background fogging on the photoreceptor.

The toner particles of the (Y _A ) component constituting the yellow toner of the present invention are preferably 0.1 to 4 mm, particularly preferably 0.1 to 2 mm, of the polyester resin of the (Y _A1 ) component. A powder having a particle diameter of (Y _A2 )
After uniformly mixing the yellow pigment of the component, the negatively chargeable charge controlling agent of the (Y _A3 ) component, and other components used as necessary with a mixer such as a Henschel mixer or a super mixer, After melt kneading with a kneading machine such as a single-screw or twin-screw extruder to form a resin composition, and extruded to cool and solidify, the resin composition is, for example, a jaw crusher, a gyratory crusher, a feather mill, With a hammer mill, impeller breaker, or the like, after coarse pulverization or further medium pulverization to obtain coarse particles having a particle size of about several mm or less, the coarse particles are, for example,
Jet mill, finely pulverized into powder of about several tens μm or less by a collision type pulverizer or the like, and the obtained powder is classified by an air classifier, a Coander classifier or the like, preferably an average particle diameter of 4 to 20 μm, particularly Preferably, the particles are formed to have a prescribed particle size in the range of 4 to 12 μm, and then, if necessary, are subjected to sphering means or the like.

At this time, in the present invention, the (Y _A1 )
A polyester resin as the component, a yellow pigment as the component (Y _A2 ), and a _negatively chargeable charge control agent as the component (Y _A3 );
In addition, in melting and kneading other components used as necessary to form a resin composition, a polyester resin equivalent to or different from the (Y _A1 ) component and the (Y _A2 )
A master batch-treated product or a flashing-treated product in which the component (Y _A2 ) is contained in a high concentration by dispersing the component (Yellow pigment) with the yellow pigment is produced, and the treated product is treated with the polyester resin (Y _A1 ). It is preferable to adopt a method of adding the negatively chargeable charge control agent of the component (Y _A3 ) together with dilution.

The above (Y _A2 ) in the master batch
The content of the yellow pigment as a component is preferably from 10 to 55% by weight, particularly preferably from 15 to 50% by weight. The form of the master batch is preferably 0.1
It is preferable to use a powder having a particle size of from 4 to 4 mm, particularly preferably from 0.1 to 2 mm.

In order to produce the yellow toner of the present invention by mixing the toner particles of the component (Y _A ) and the inorganic fine powder of the component (Y _B ), the toner of the component (Y _A ) is used. The particles and the inorganic fine powder of the component (Y _B ) are uniformly mixed by, for example, a mixer such as a Henschel mixer or a super mixer, and the surface of the particles of the component (Y _A ) is coated with the component (Y _B ). Then, foreign matter, coarse particles, and the like are removed by a sieving machine.

In this case, for example, powders of fluorine resin such as polyvinylidene fluoride and polytetrafluoroethylene, resin beads such as polymethyl methacrylate and silicone resin, powders of fatty acid metal salts such as zinc stearate and calcium stearate, talc Various known external additives such as mineral powder such as hydrotalcite, ferroelectric fine powder such as strontium titanate, and conductive fine powder such as conductive titania may be used.

The yellow toner of the present invention can be used in a magnetic two-component developing system as a mixture with a magnetic powder as a carrier and a magnetic one-component developing system in which a magnetic powder is contained in a toner. It is suitable for use in a non-magnetic one-component developing system that does not use powder.

Further, the yellow toner of the present invention has the above (Y)
_A1 ) The same polyester resin (M _A1 ) component as the component,
I. Pigment Red 57: 1, 122, 14
6, 184, 238, and C.I. I. Pigment Violet 19 and a toner particle (M _A ) containing any magenta pigment (M _A2 ) component and the same negatively chargeable charge control agent (M _A3 ) component as the (Y _A3 ) component. ) component and the (Y _B) and magenta toner comprising a mixture of the same inorganic fine powder (M _B) component as a component, the (Y _A1) the same polyester resin as component (C _A1) component, C. I. Pigment Blue 15: 3 and 1
Toner particles (C _A ) containing any cyan pigment (C _A2 ) component selected from the group consisting of 5: 4 and the same negatively chargeable charge control agent (C _A3 ) component as the (Y _A3 ) component It is suitable for use as a full-color developing toner composed of three primary color toners, a cyan toner composed of a mixture of the component and the same inorganic fine powder (C _B ) component as the component (Y _B ).

The three primary color toners contain, for example, the same polyester resin component as the (Y _A1 ) component, a black pigment component such as carbon black, and a negative charge control agent component such as an azo dye. A toner particle component,
It is also suitable for use as a full-color developing toner composed of a four-color toner to which a black toner comprising a mixture of the same inorganic fine powder component as the component (Y _B ) is added.

[0044]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention.

Example 1 Ethylene oxide adduct of terephthalic acid, 2,2-bis (4'-hydroxyphenyl) propane, and 2,2-bis (4'-hydroxyphenyl) as the (Y _A1 ) component a polycondensate of propylene oxide adduct of propane, acid value 7KOHmg / g, number average molecular weight (M _n) 4,400, a weight average molecular weight (M _W) 45,0
00, the ratio of the number-average molecular weight The weight average molecular weight to the _{(M n) (M W)} (M W / M n) 10.2, a peak molecular weight of 8,000, tetrahydrofuran-soluble matter 100 wt%,
Softening temperature 110 ° C., a glass transition temperature of 65 ° C. Linear polyester resin 60 wt.%, (Y _A2) C. as component
I. Using 40% by weight of CI Pigment Yellow 74, a pre-dispersion treatment was performed to obtain a master batch-treated product, which was pulverized by a pulverizer to obtain a granular material having an average particle size of about 1 mm.

Next, ethylene oxide adduct of terephthalic acid with 2,2-bis (4'-hydroxyphenyl) propane and 2,2-bis (4'-hydroxyphenyl) propane as the (Y _A1 ) component Polycondensate with propylene oxide adduct and trimellitic acid, having an acid value of 5 KOH mg / g and a number average molecular weight (M _n )
7,200, weight average molecular weight (M _W) 81,000, a ratio of the number-average molecular weight The weight average molecular weight to the _{(M n) (M W)} (M W / M n) 11.3, a peak molecular weight 10,00
0, tetrahydrofuran soluble matter 90% by weight, softening temperature 1
35 ° C, glass transition temperature 63 ° C, average particle size about 0.7mm
94 parts by weight of the granular non-linear polyester resin, 10 parts by weight of the master batch-treated product, and R ¹ , R ² , R ³ , and R ⁴ in the general formula (I) as the (Y _A3 ) component 1 part by weight of a negatively chargeable charge control agent (“LR-147” manufactured by Nippon Carlit Co.), which is a phenyl group and the counter cation X ⁺ is a potassium ion, and ethylene-
Propylene copolymer (number average molecular weight 3,000, melting point 1
32 ° C., density 0.89 g / cm ³ ) 2 parts by weight were mixed with a Henschel mixer, melt-kneaded and extruded with a twin-screw extruder, cooled and solidified, and coarsely pulverized with a feather mill until a 2 mm aperture was passed. Then, the mixture was finely pulverized and classified by a jet pulverizer and an airflow classifier to produce toner particles as a (Y _A ) component having a volume average particle diameter of about 6.5 μm. Here, the average particle size was measured with a Multisizer manufactured by Beckman Coulter.

Subsequently, 100 parts by weight of the toner particles as the (Y _A ) component and dimethyl silicone oil as the (Y _B ) component were surface-treated to have a specific surface area of 30 m ^2.
/ G of silica (“RY50” manufactured by Nippon Aerosil Co., Ltd.) 3.
After mixing 2 parts by weight with a Henschel mixer,
Surface treatment with hexamethyldisilazane and specific surface area of 26
0 m ² / g silica (“R81” manufactured by Nippon Aerosil Co., Ltd.)
2)) A yellow toner was produced by adding 0.3 parts by weight and mixing with a Henschel mixer.

Separately, (Y_A2) Component instead of (M_A2)
C. as a component. I. Pigment Red 57: 1
Create a masterbatch treated product in the same way as above
And then (Y_A1) The same non-linear polyester as the component
Resin (M_A194.6 parts by weight of
9 parts by weight of the star batch processed product, (Y_A3) Same as component
(M)_A3) 1 part by weight as an ingredient,
And the same ethylene-propylene copolymer as above
In the same manner as described above, except for the parts used, _A)
To produce toner particles, and subsequently (Y
_BThe same silica as the component (M)_B) Used as an ingredient
A magenta toner was produced in the same manner as described above.

Separately, instead of the component (Y _A2 ), (C
_A2 ) C.I. I. Pigment Blue 15: 3 is used to prepare a masterbatch-treated product in the same manner as described above, and then 94.6 parts by weight of the same non-linear polyester resin as the (Y _A1 ) component as the (C _A1 ) component, 9 parts by weight of the master batch-treated product, 1 part by weight of the same negative charge control agent as the (Y _A3 ) component as the (C _A3 ) component, and 2 parts by weight of the same ethylene-propylene copolymer as described above. _A toner particle as the (C _A ) component is produced in the same manner as above except for the use of each, and subsequently, the same silica as the (Y _B ) component is used as the (C _B ) component in the same manner as above. To produce a cyan toner.

Separately, ethylene oxide adduct of terephthalic acid and 2,2-bis (4′-hydroxyphenyl) propane, propylene oxide adduct of 2,2-bis (4′-hydroxyphenyl) propane, and A polycondensate with trimellitic acid, having an acid value of 8 KOHmg /
g, number average molecular weight (M _n ) 2,400, weight average molecular weight (M _w ) 87,000, ratio of weight average molecular weight (M _w ) to number average molecular weight (M _n ) (M _w / M _n ) 3,
7,000 peak molecular weight, soluble in tetrahydrofuran 8
9% by weight of a granular non-linear polyester resin having an average particle size of about 1.2 mm having a softening temperature of 150 ° C. and a glass transition temperature of 65 ° C., and 4.5% by weight of carbon black (“MA77” manufactured by Mitsubishi Chemical Corporation). Parts, 1 part by weight of a negative charge control agent (“T-77” manufactured by Hodogaya Chemical Industry Co., Ltd.), and polyethylene wax (“PE” manufactured by Clariant Japan)
-190 ") and 3 parts by weight of a polypropylene wax (" 100TS "manufactured by Sanyo Chemical Industries, Ltd.) are mixed with a Henschel mixer, melt-kneaded with a twin-screw extruder, extruded into a sheet, and cooled and solidified. , 2mm with feather mill
Coarse pulverization is performed until the openings pass, and then finely pulverized and classified by a jet pulverizer and an airflow type classifier to produce toner particles having a volume average particle diameter of about 6.5 μm. 100 parts by weight of the particles and 0.3 part by weight of silica ("TG-308F" manufactured by Cabot Corporation) surface-treated with dimethyl silicone oil and having a specific surface area of 220 m ² / g were mixed with a Henschel mixer, and further mixed with dimethyl silicone. Surface treated with oil, specific surface area is 30m
² / g silica ("RY50" manufactured by Nippon Aerosil Co., Ltd.)
By adding 3.2 parts by weight and mixing with a Henschel mixer, a black toner was manufactured.

Using the yellow toner, magenta toner, cyan toner, and black toner obtained above,
Non-magnetic one-component contact development system, organic photoconductor photoreceptor, hot roll fixing system, development unit in order of magenta, cyan, yellow, black, color printing speed of A4 plain paper 12 sheets / min Actually photographed with a commercially available tandem color printer, and measured the yellow image characteristics such as toner charge amount and toner adhesion amount, image density, print hue, toner fog on the photoreceptor, white background fog, and transparency by the following methods The results are shown in Tables 1 and 2.

Toner charge amount and toner adhesion amount The toner is put into the developing tank unit of the printer, stirred for a predetermined time, and then connected to a powder charge amount measuring device ("210HS" manufactured by Trek Japan Co., Ltd.) with a suction pump. The toner on the roll was suction-separated to measure the one-component toner charge amount and the toner adhesion amount.

Image Density The image density when printed on plain paper was measured using a spectral color densitometer (“X-Rite 938” manufactured by Nippon Lithographic Equipment Co., Ltd.) to determine the reflection density using a light source D65, a viewing angle of 2 degrees, and a response T. It measured and it was set as the image density.

[0054] Using the image portion spectral side color densitometer when printed on the printing color plain paper (Nippondaira Version equipment manufactured by "X-Rite 938"), a light source D65, viewing angle 2 degrees, the response T, JI
The lightness L ^* and the color coordinates a ^* and b ^* in the L ^* a ^* b ^* color system defined in SZ8730 were measured and used as the print hue.

[0055]Toner fog on photoconductor Print on plain paper and stop forcibly during printing
On the photoreceptor, after the development part and before the transfer part
Mending the toner as toner fog on the photoconductor
Sampled by a 3M company (3M) and pasted on plain paper.
For the fogging part, use the spectral color densitometer (Nihon Planographic Equipment Co., Ltd.)
(X-Rite 938), light source D65,
A field angle of 2 degrees and a response T conform to JIS Z8730.
L defined ^*a^*b^*Lightness L in color system^*, Color coordinates
a^*And b^*On the other hand, on plain paper before fogging
Lightness L of pasted tape^*’, Color coordinates a^*'as well as
b^*′, And the color difference ΔE is calculated by the following equation.^* _abCalculate and expose
Toner fog on the body. Note that over paper is used instead of plain paper.
-Print on head projector (OHP) sheet
The measurement was performed in the same manner. ΔE^* _ab= [(L^*-L^*')^Two + (A^*-A^*')^Two +
(b^*-B^*')^Two]^1/2

A white background portion, which is a non-image portion when printed on plain paper with a white background fog , is measured using a color difference meter (“SZ- $ 80” manufactured by Nippon Denshoku Industries Co., Ltd.).
The Z of the tristimulus value XYZ in the XYZ color system specified in JIS Z8701 was measured, and the difference (Z-Z ') from the separately measured Z' value before printing was determined to be a white background fog.

[0057] to print a solid image to transparency overhead projector (OHP) sheet, a 2.5cm angle from the solid image was taken, the color difference meter (Nippon Denshoku Industries Co., Ltd., "SZ-Σ80")
Is used to measure the transmission pattern, and the wavelength is 680 ± 20 nm
Transmittance Q _max (%) at a wavelength of 400 ± 20
The difference from the minimum transmittance Q _min (%) in nm (Q _max −
Q _min ) was determined and defined as transparency.

Examples 2 to 4 and Comparative Examples 1 to 2 A yellow toner was produced in the same manner as in Example 1 except that the yellow pigment in the yellow toner was changed to the one shown in Table 1, and was actually photographed by a color printer. Yellow image characteristics such as toner charge amount and toner adhesion amount, image density, print hue, toner fog on the photoreceptor, white background fog, and transparency were measured. The results are shown in Tables 1 and 2.

From the comparison between the above Examples and Comparative Examples, in Comparative Example 1, toner fogging and white background fogging on the photoreceptor of the OHP sheet were large, and in Comparative Example 2, the image density was low. It is clear that there are problems such as poor transparency.

[0060]

[Table 1]

[0061]

[Table 2]

[0062]

According to the present invention, even when used in the non-magnetic one-component developing system, there is no excess or deficiency in the toner charge amount and the toner adhesion amount, and therefore, the image density and print hue are stable. And yellow toner suitable for full-color development as a three primary color toner of magenta toner and cyan toner, which has less toner fogging and white background fogging on the photoreceptor, and is capable of forming images with good transparency, and A full-color developing toner using the same can be provided.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 9/08 375 (72) Inventor Teruki Senoguchi 1 Fukudacho, Joetsu-shi, Niigata Mitsubishi Chemical Corporation Naoetsu Office (72) Inventor Masakazu Sugihara 1 Fukudacho, Joetsu City, Niigata Prefecture Mitsubishi Chemical Corporation Naoetsu Office F Term (Reference) 2H005 AA01 AA06 AA08 AA21 CA08 CA12 CA21 CA25 CB07 CB13 DA02 EA03 EA06 EA07 EA07 EA10 FA07

Claims (8)

[Claims] 1. _A yellow toner comprising a mixture of the following components (Y _A ) and (Y _B ). (Y _A ); toner particles containing the following components (Y _A1 ), (Y _A2 ), and (Y _A3 ): (Y _A1 ); polyester satisfying the following characteristics (1) to (7): (1) Acid value ≦ 30 KOH mg / g (2) Number average molecular weight (M _n ) 2,000 to 20,000 (3) Weight average molecular weight (M _W ) 5,000 to 300,0
00 (4) number-average molecular weight The weight average molecular weight to the (M _n) (M _W) ratio _{(M W / M n) 2~150} (5) tetrahydrofuran-soluble matter of 70 to 100 wt% (6) Softening temperature 80 160 ° C. (7) Glass transition temperature 50-75 ° C. (Y _A2 ); I. Pigment Yellow 74, 15
5, a yellow pigment (Y _A3 ) selected from the group consisting of 180, and 185; a negatively chargeable charge control agent (Y _B ); surface-treated with silicone oil, and having a specific surface area of 5 to 500 m ² / G of any one of inorganic fine powders selected from the group consisting of silica, titania, and alumina 2. The yellow toner according to claim 1, wherein the proportion of the inorganic fine powder of the component (Y _B ) is 0.1 to 8 parts by weight based on 100 parts by weight of the component (Y _A ). 3. The composition according to claim 1, wherein the proportion of the yellow pigment in the (Y _A2 ) component is 1.5 to 10% by weight based on the total amount of the (Y _A ) component and the (Y _B ) component. 3. The yellow toner according to item 1. 4. The composition according to claim 1, wherein the proportion of the charge controlling agent in the (Y _A3 ) component is 0.1 to 6% by weight based on the total amount of the (Y _A ) component and the (Y _B ) component. 3. The yellow toner according to any one of 3. 5. The yellow toner according to claim 1, wherein the charge control agent of the (Y _A3 ) component is represented by the following general formula (I). Embedded image [In the formula (I), R ¹ , R ² , R ³ , and R ⁴ are each independently an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, A cycloalkyl group which may have a substituent, an aryl group which may have a substituent, or a hydrogen atom, and X ⁺ represents a counter cation. ] 6. The compound represented by the formula (I) wherein R ¹ , R ² ,
The yellow toner according to claim 5, wherein R ³ and R ⁴ are both phenyl groups, and X ⁺ is a potassium cation. 7. The yellow toner according to claim 1, which is for non-magnetic one-component development. 8. _A magenta toner comprising a mixture of the yellow toner according to claim 1 and the following components (M _A ) and (M _B ), and the following (C _A ) components: (C _B ) A toner for full-color development, comprising at least three primary color toners and a cyan toner comprising a mixture with the component (C _B ). (M _A ); toner particles containing the following components (M _A1 ), (M _A2 ), and (M _A3 ): (M _A1 ); polyester satisfying the following characteristics (1) to (7): (1) Acid value ≦ 30 KOH mg / g (2) Number average molecular weight (M _n ) 2,000 to 20,000 (3) Weight average molecular weight (M _W ) 5,000 to 300,0
00 (4) number-average molecular weight The weight average molecular weight to the (M _n) (M _W) ratio _{(M W / M n) 2~150} (5) tetrahydrofuran-soluble matter of 70 to 100 wt% (6) Softening temperature 80 160 ° C. (7) Glass transition temperature 50-75 ° C. (M _A2 ); I. Pigment Red 57: 1, 1
22, 146, 184, 238, and C.I. I. Any of a magenta pigment selected from the group consisting of Pigment Violet 19 (M _A3); negatively charged charge control agent (M _B); surface-treated with silicone oil, the specific surface area is 5 to 500 m ² / g Any inorganic fine powder (C _A ) selected from the group consisting of silica, titania, and alumina; toner particles containing the following components (C _A1 ), (C _A2 ), and (C _A3 ): C _A1 ); Polyester resin satisfying the following characteristics (1) to (7) (1) Acid value ≦ 30 KOHmg / g (2) Number average molecular weight (M _n ) 2,000 to 20,000 (3) The weight average molecular weight (M _W) 5,000~300,0
00 (4) number-average molecular weight The weight average molecular weight to the (M _n) (M _W) ratio _{(M W / M n) 2~150} (5) tetrahydrofuran-soluble matter of 70 to 100 wt% (6) Softening temperature 80 160 ° C. (7) Glass transition temperature 50-75 ° C. (C _A2 ); I. Pigment Blue 15: 3, and any of cyan pigments selected from the group consisting of 15: 4 (C _A3 ); negatively chargeable charge control agent (C _B ); Any one of inorganic fine powders selected from the group consisting of silica, titania, and alumina having a weight of ^{5 to} 500 m ² / g