JP2001343781A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which has improved low temperature fixing property and offset resistance, showing good fixing performance, causing no deposition of the toner on a fixing member even used over long term and having superior image characteristics same which are similar to those of the initial period of use. SOLUTION: The toner contains at least a binder resin, coloring agent and hydrocarbon wax, and the wax has 5 to 150 mg KOH/g hydroxyl value (HV) and 1 to 50 mg KOH ester value (EV), satisfying the relation HV>EV.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic method, an image forming method for visualizing an electrostatic image, and a toner used for a toner jet.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Application Laid-Open Publication No. Sho. 43-24748, and the like. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. After forming the latent image with toner, the latent image is developed into a visible image, and if necessary, the toner is transferred to a transfer material such as paper. The toner is fixed to obtain a copy, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

In recent years, such copying apparatuses have begun to be used not only as office work copying machines for simply copying original documents, but also as printers as personal computer outputs or personal copying machines for individuals. .

For this reason, smaller, lighter, faster, and more reliable devices have been sought.
Machines are becoming simpler in various respects. As a result, the performance required of the toner becomes higher, and if the performance of the toner cannot be improved, a better machine cannot be realized.

For example, various methods and apparatuses have been developed for a process of fixing a toner image to a sheet such as paper.
There are a compression heating method using a heat roller and a heat fixing method in which a heating member is brought into close contact with a heating member via a film.

A heating method using a heating roller or a film is performed by passing a toner image surface of a sheet to be fixed onto a surface of a heat roller or a film formed of a material having a releasable property with respect to the toner while contacting the surface. The fixing is performed. In this method, since the surface of the heat roller or the film comes into contact with the toner image of the sheet to be fixed, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. Yes, very good in electrophotographic copiers. However, in the above method, a part of the toner image adheres and transfers to the fixing roller or the film surface because the heat roller or the film surface and the toner image come into contact in a molten state, and the toner image re-transfers to the next sheet to be fixed. A so-called offset phenomenon occurs, and the sheet to be fixed may be stained. Preventing toner from adhering to the heat fixing roller or the film surface is one of the essential conditions of the heat fixing method.

Conventionally, for the purpose of preventing toner from adhering to the surface of a fixing roller, for example, the surface of the roller is formed of a material having excellent releasability with respect to the toner, such as silicone rubber or a fluorine-based resin, and the surface of the roller is further prevented from offsetting. In order to prevent the roller surface from being fatigued, the roller surface is coated with a thin film of a liquid having good releasability such as silicone oil. Although this method is extremely effective in preventing toner offset, it has a problem that a fixing device is required because a device for supplying an anti-offset liquid is required. This is in the opposite direction to miniaturization and weight reduction, and moreover, silicone oil and the like may evaporate due to heat and contaminate the inside of the machine.

[0008] Accordingly, a release agent such as low molecular weight polyethylene or low molecular weight polypropylene is added to the toner from the idea of supplying the anti-offset liquid during heating from the toner instead of using a silicone oil supply device. A method has been proposed. However, if a large amount of such an additive is added in order to obtain a sufficient effect, filming on the photoreceptor or contamination of the surface of the toner carrier such as a carrier or a sleeve deteriorates the image, resulting in a practical problem. This is a problem.

For this reason, a small amount of release agent is added to the toner to such an extent that the image is not deteriorated, and a small amount of release oil is supplied, or the offset toner is taken up using a member such as a web. It has been practiced to use a cleaning device together with a cleaning device. However, in view of recent demands for miniaturization, weight reduction and high reliability, it is necessary and necessary to remove even these auxiliary devices, which is preferable. Therefore, it cannot be coped with without further improvement in performance such as toner fixing property and anti-offset property, and it is difficult to realize such improvement without further improvement of the binder resin and the release agent of the toner.

It is known that a wax is contained in a toner as a release agent. For example, JP-A-52-330
No. 4, JP-A-52-3305, JP-A-57-3305.
A technique such as 52574 is disclosed.

[0011] These waxes are used to improve the offset resistance of the toner at low and high temperatures. However, while these properties are improved, blocking resistance is deteriorated and developability is deteriorated.

Further, Japanese Patent Application Laid-Open No. 63-113558,
JP-A-63-188158, JP-A-2-1346
No. 48, JP-A-4-97162, JP-A-4-97162
No. 97163 discloses a technique of including an alcohol component in a toner. These alcohol components have the effect of improving the fixability of the toner at low temperatures and the anti-offset property at high temperatures, but sometimes deteriorate the developability of the toner.

JP-A-1-109359 discloses a technique in which a low molecular weight polyolefin-based polyol is contained in a toner. Although such a wax component has an effect on the fixing property and the developing property of the toner, the anti-blocking property and the anti-offset property at high temperature may be insufficient.

Further, Japanese Patent Application Laid-Open Nos. 4-184350, 4-194947, 4-194946.
Japanese Patent Application Laid-Open No. HEI 4-194948 discloses a technique in which a polyglycerin partially esterified product is contained in a toner. Even with the addition of such a polyglycerin compound, sufficient fixability and offset resistance have not yet been satisfied.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which has solved the above-mentioned problems.

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner having improved low-temperature fixability and offset resistance, and exhibiting good fixability.

An object of the present invention is to provide a toner which does not cause toner to adhere to a fixing member even when used for a long period of time and has excellent image characteristics as in the initial stage.

It is a further object of the present invention to provide a toner that achieves both low-temperature fixability and high durability of the toner even at a high process speed.

An object of the present invention is to provide a toner having excellent long-term storage properties.

[0020]

The present inventors have SUMMARY OF THE INVENTION As a result of extensive studies on the composition of the toner in order to solve the above problems, a hydroxyl value (H _V) is 5~150mgKOH / g
And an ester value (E _V ) of 1 to 50 mgKOH / g
It has been found that by using a hydrocarbon wax having a relationship of H _V > E _V in the toner, a toner exhibiting good fixability in a wide temperature range from a low temperature region to a high temperature region can be obtained. .

[0021] Namely, the present invention is a toner containing a binder resin, a colorant and a hydrocarbon wax, wherein the wax has a hydroxyl value (H _V) is 5～150MgKOH /
g and an ester value (E _V ) of 1 to 50 mgKOH /
g, and the relationship is H _V > E _V.

[0022]

DETAILED DESCRIPTION OF THE INVENTION The present inventors have conducted extensive studies results, the hydroxyl value (H _V) is 5~150mgKOH / g (preferably 10 to 100 mg / g, more preferably 20
90 mg KOH / g) and an ester value (E _V ) of 1
５０50 mgKOH / g (preferably 1-30 mgKOH
/ G, more preferably from 1 to 20 mgKOH / g, and particularly preferably from 1 to 15 mgKOH / g), good fixing performance in a wide temperature range from a low temperature range to a high temperature range by using a hydrocarbon-based wax for the toner. Was found to be obtained.

The wax used in the present invention has an appropriate hydroxyl group in the molecule, so that the wax can be dispersed in the binder resin in a fine particle form, so that an appropriate plasticizing effect can be obtained and the fixing property can be improved. improves. Further, since the toner is dispersed in the form of fine particles, the wax easily oozes out onto the toner surface when the toner is heated, and the offset resistance of the toner is improved. When the hydroxyl value of the wax is less than 5 mgKOH / g, the wax is not sufficiently finely dispersed, and the fixability and the offset resistance of the toner become insufficient. When the hydroxyl value of the wax is more than 150 mgKOH / g, the plasticizing effect of the wax becomes too large, and the blocking resistance of the toner decreases.

Further, since the ester group in the wax in the present invention has a high affinity with the binder resin component of the toner, the wax can be uniformly present in the toner, and the action of the wax can be effectively exhibited. Become like When the ester value of the wax is less than 1 mgKOH / g, the effect of the wax on the fixability and offset resistance of the toner cannot be sufficiently exerted. In addition, the ester value of the wax is 50 mg.
If it is larger than KOH / g, the affinity of the wax for the binder resin becomes too high, and the releasing effect of the wax is reduced, so that sufficient offset resistance cannot be obtained.

Further, the wax of the present invention is characterized in that it has a suitable hydroxyl value (H _V ) and ester value (E _V ) and satisfies the following relationship.

H _V > E _V

Further, it is preferable that the relationship of H _V > 2E _V is satisfied.

The present invention is characterized in that the hydroxyl value of the wax is larger than the ester value, whereby:
Adhesion of the toner to the fixing member can be reduced.
Hydroxyl groups in the wax enhance the slipperiness of the toner, and thus enhance the releasability of the toner from the fixing member. Further, since the ester group in the wax has a high affinity for the binder resin and the wax has a hydroxyl group at the same time, the wax is uniformly present in the fixing member and the toner, and the toner is fixed. It is possible to improve the slipperiness with the member and reduce the adhesion of the toner to the fixing member. If the ester value of the wax is higher than the hydroxyl value, the affinity between the wax and the binder resin increases, making it difficult for the wax to seep out of the toner surface, making it difficult for the wax to work, and causing the toner to adhere to the fixing member. Image stains occur. Further, since the ester group in the wax has a high affinity for the binder resin component and the hydroxyl group has a high affinity for the sheet to be fixed such as paper, it has an effect of discharging the toner from the fixing member. As a result, the releasability of the toner from the fixing member and the discharging property to the sheet to be fixed are improved, and the image stain due to the accumulation of the toner on the fixing member can be reduced.

Further, the wax of the present invention has an acid value (A _V ) of 1 to 30 mgKOH / g (preferably 1 to 1 mgKOH / g).
5 mg KOH / g, more preferably 1 to 10 mg KOH
/ G). When the wax has an acid group, the interfacial adhesion to other components constituting the toner increases, the effect of plasticizing the toner by the wax increases, and the fixability of the toner improves. If the acid value of the wax is less than 1 mgKOH / g, the interfacial adhesive strength with other components constituting the toner becomes small, the wax may be released, and the effect of the wax may not be sufficiently obtained.
On the other hand, if the acid value of the wax is larger than 30 mgKOH / g, on the contrary, the interfacial adhesive strength becomes too large, the plasticization of the toner proceeds greatly, and it may not be possible to maintain sufficient releasability.

The wax in the present invention preferably has an acid value (A _V ) and a hydroxyl value (H _V ) satisfying the following relationship.

H _V > A _V

Further, it is preferable to satisfy the relationship of H _V > 2A _V.

Since the acid group of the wax has a high adhesive force to other components of the toner, the wax component is held on the toner surface on the fixing member. As a result, the action of the wax works effectively at the interface between the toner and the fixing member. If the acid value of the wax is equal to or greater than the hydroxyl value, the slipperiness of the wax becomes insufficient, and image stains may occur due to adhesion of the toner to the fixing member. Further, since the wax has an acid group and an ester group at the same time, the wax can have an appropriate dispersion diameter in the toner, and the action of the wax can be effectively exerted. If either the acid group or the ester group is missing, the dispersion diameter of the wax in the toner becomes uneven, and the action of the wax may not work sufficiently.

The wax of the present invention is characterized by comprising a hydrocarbon wax. The hydrocarbon wax is excellent in the releasing action and the plasticizing action when it is moderately finely dispersed in the toner. In the present invention, the main chain of the wax is composed of carbon bonds, so that the acid group,
Each substituent such as a hydroxyl group and an ester group easily functions in the toner, and the fixing property and the offset resistance can be effectively improved. When other elements are contained in the main chain of the wax, for example, the presence of an oxygen-containing ether bond such as polyglycerin reduces the action and effect of the wax, and furthermore features of the present invention. The function of each of the substituents is hindered, and sufficient fixability and offset resistance cannot be obtained.

The wax in the present invention is obtained by converting an aliphatic hydrocarbon wax into alcohol to obtain a wax having desired properties, since the conversion of the acid group, hydroxyl group and ester group of the wax is easily controlled. preferable.

As the aliphatic hydrocarbon wax, the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 100 to 3000, preferably 200 to 2000, more preferably 250 to 1000 in terms of polyethylene. The saturated or unsaturated aliphatic hydrocarbon in the range of is preferably used.

In the present invention, the molecular weight distribution of the wax is
It is measured under the following conditions by gel permeation chromatography (GPC).

(GPC measurement conditions) Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation) Column: TSKgel GMHHR-H HT 7.8
cml. D × 30 cm L 2 columns (manufactured by Tosoh Corporation) Detector: RI for high temperature Temperature: 135 ° C. Solvent: o-dichlorobenzene (addition of 0.05% ionol) Flow rate: 1.0 ml / min Sample: 0.1% of sample is 0 .4ml injection

Measurement is performed under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. In addition, Mark-Hou
It is calculated by performing a conversion according to the wax such as a polyethylene conversion using a conversion formula derived from the win viscosity formula.

Examples of the aliphatic hydrocarbon wax include (A) a higher aliphatic unsaturated hydrocarbon having at least one double bond obtained by ethylene polymerization or olefination by pyrolysis of petroleum hydrocarbon; (B) an n-paraffin mixture obtained from a petroleum fraction, (C) a polyethylene wax obtained by an ethylene polymerization method, (D) one or more kinds of higher aliphatic hydrocarbons obtained by a Fischer-Tropsch synthesis method, and the like. It is preferably used.

As an example of the production of the wax in the present invention, for example, it is obtained by subjecting an aliphatic hydrocarbon wax to liquid phase oxidation with a molecular oxygen-containing gas in the presence of boric acid and boric anhydride. As the catalyst, a mixture of boric acid and boric anhydride can be used. The mixing ratio of boric acid and boric anhydride (boric acid / boric anhydride) is 1 in molar ratio.
, Preferably in the range of 1.2 to 1.7. If the proportion of boric anhydride is less than the above range, an excessive amount of boric acid causes an aggregation phenomenon, which is not preferable. If the proportion of boric anhydride is larger than the above range, powdery substances derived from boric anhydride are recovered after the reaction, and excess boric anhydride does not contribute to the reaction, which is not preferable from an economical viewpoint.

The amount of boric acid and boric anhydride to be used is 0.001 to 10 mol, preferably 0.1 to 10 mol, per mol of the aliphatic hydrocarbon as the raw material, when the mixture is converted into the amount of boric acid. ~ 1 mol is preferred.

As the molecular oxygen-containing gas to be blown into the reaction system, oxygen, air, or a wide range of those diluted with an inert gas can be used, but the oxygen concentration is preferably 1 to 30% by volume. More preferably, it is 3 to 20% by volume.

The liquid phase oxidation reaction is usually carried out without using a solvent, in a molten state of the raw material aliphatic hydrocarbon. The reaction temperature is from 120 to 280C, preferably from 150 to 250C. The reaction time is preferably 1 to 15 hours.

It is desirable that boric acid and boric anhydride are previously mixed and added to the reaction system. If only boric acid is added alone, it is not preferable because a dehydration reaction of boric acid or the like occurs. The addition temperature of the mixed solvent of boric acid and boric anhydride is 100 to 1
80 ° C. is good, preferably 110 to 160 ° C., and 1
If the temperature is lower than 00 ° C., the catalytic activity of boric anhydride is undesirably reduced due to moisture remaining in the system.

After the completion of the reaction, water is added to the reaction mixture, and the boric acid ester of the produced wax is hydrolyzed and purified to obtain a desired wax.

In the present invention, the acid value, hydroxyl value, ester value and saponification value of the wax are determined by the following methods.
The basic operation conforms to J1SK 0070.

<Measurement of acid value> ・ Equipment and apparatus Erlenmeyer flask (300 ml) Burette (25 ml) Water bath or hot plate ・ Reagent 0.1 kmol / m ³ hydrochloric acid 0.1 kmol / m ³ Potassium hydroxide ethanol solution Take 25 ml of 0.1 kmol / m ³ hydrochloric acid into an Erlenmeyer flask using a whole pipette, add a phenolphthalein solution, titrate with 0.1 kmol / m ³ potassium hydroxide ethanol solution, and determine the factor from the amount required for neutralization. Phenolphthalein solution Solvent (diethyl ether and ethanol (99.5) mixed at a volume ratio of 1: 1 or 2: 1. These are added with a few drops of phenolphthalein solution as an indicator immediately before use.) , 0.1 kmol / m ³ is neutralized with potassium hydroxide solution in ethanol.) measurement method (a) wax 1-20 The precisely weighed in an Erlenmeyer flask.
(B) 100 ml of a solvent and a few drops of a phenolphthalein solution as an indicator are added and shaken sufficiently on a water bath until the wax is completely dissolved. (C) Titration with an ethanol solution of 0.1 kmol / m ³ potassium hydroxide, and the end point is defined as the time when the light red color of the indicator continues for 30 seconds. Calculation A = 5.611 × B × f / S where A: acid value (mg KOH / g) B: amount of 0.1 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml) f: 0. Factor of 1 kmol / m ³ potassium hydroxide ethanol solution S: mass of wax (g) 5.611: formula weight of potassium hydroxide 56.11 × 1/1
0

<Measurement of hydroxyl value>-Apparatus and equipment Measuring cylinder (100 ml) Pipette (5 ml) Flat-bottom flask (200 ml) Glycerin bath-Reagent Acetylating reagent (25 g of acetic anhydride was added to flask 100)
and add pyridine to bring the total volume to 100 ml.
Shake well. Phenolphthalein solution 0.5kmol / m^ThreeEthanol solution of potassium hydroxide ・ Measurement method (a) 0.5-6.0 g of wax is precisely weighed in a flat bottom flask
Then, add 5 ml of acetylation reagent to this using a pipette.
Add. (B) Place a small funnel in the mouth of the flask and set the temperature to 95-1.
Dip the bottom about 1 cm in a glycerin bath at 00 ° C and heat
You. The temperature of the flask neck rises due to the heat of the glycerin bath.
To prevent peeling, use a cardboard disc with a round hole
Cover over the neck of the flask. (C) After 1 hour, remove the flask from the glycerin bath,
After cooling, add 1 ml of water from the funnel and shake to shake
Decompose. (D) Further, to complete the decomposition, the flask is again
Heat in a Lyserine bath for 10 minutes, allow to cool, and then add ethanol (9
5) Wash the funnel and flask wall with 5 ml. (E) Add a few drops of phenolphthalein solution as indicator
, 0.5kmol / m ^ThreePotassium hydroxide in ethanol
When titrating with liquid and the indicator's pale red color lasts for about 30 seconds
Is the end point. (F) Blank test is performed without wax (a) to (e)
I do. (G) If the sample is difficult to dissolve, add a small amount of pyridine.
Or add xylene or toluene to dissolve. Calculation A = [{(B−C) × 28.05 × f} / S] + D where A: hydroxyl value (mgKOH / g) B: 0.5 kmol / m used in blank test^ThreePotassium hydroxide
Of ethanol solution (ml) C: 0.5 kmol / m used for titration^ThreePotassium hydroxide
Amount of ethanol solution (ml) f: 0.5 kmol / m^ThreePotassium hydroxide in ethanol
Liquid Factor S: Mass of wax (g) D: Acid value 28.05: Formula weight of potassium hydroxide 56.11 × 1/2

<Measurement of ester value> It is calculated by the following equation.

(Ester value) = (saponification value) − (acid value)

<Measurement of saponification value> -Equipment and utensils Erlenmeyer flask (200-300 ml) Air cooler (External diameter 6-8 mm, glass tube 100 cm in length or reflux condenser, both in the mouth of Erlenmeyer flask Water bath, sand bath or hot plate (one that can be adjusted to a temperature of about 80 ° C) Bullet (50 ml) Pipette (25 ml) • Reagent 0.5 kmol / m ³ Hydrochloric acid 0.5 kmol / m ³ Hydroxide Potassium ethanol solution Phenolphthalein solution Measurement method (a) 1.5 to 3.0 g of wax is placed in an Erlenmeyer flask in 1 m.
Weigh accurately to the order of g. (B) Add 25 ml of 0.5 kmol / m ³ potassium hydroxide ethanol solution using a pipette. (C) An air cooler is attached to the Erlenmeyer flask, and the contents are occasionally shaken for 30 minutes while gently heating on a water bath, a sand bath or a hot plate for reaction. When heating, the heating temperature is adjusted so that the refluxing ethanol ring does not reach the upper end of the air cooler. (D) Immediately after the reaction is completed, cool down immediately, and spray a small amount of water or a mixed solution of xylene: ethanol = 1: 3 from above the air cooler before the contents solidify in agar-like state to wash the inner wall. After that, remove the air cooler. (E) Add 1 ml of a phenolphthalein solution as an indicator and titrate with 0.5 kmol / m ³ hydrochloric acid. The end point is defined as the time when the light red color of the indicator does not appear for about 1 minute. (F) Blank test is performed without wax (a) to (e)
I do. (G) If the sample is difficult to dissolve, dissolve it in advance using xylene or a xylene-ethanol mixed solvent.・ Calculation A = {(BC) × 28.05 × f} / S where A: saponification value (mgKOH / g) B: amount of 0.5 kmol / m ³ hydrochloric acid used in blank test (m
l) C: amount of 0.5 kmol / m ³ hydrochloric acid used for titration (m
l) f: Factor of 0.5 kmol / m ³ hydrochloric acid S: Mass of wax (g) 28.05: Formula weight of potassium hydroxide 56.11 × 1/2

In the present invention, when measuring the acid value, hydroxyl value, ester value and saponification value of the wax contained in the toner, the wax is separated from the toner and then measured according to the above-mentioned measuring method. Measurement may be performed.

The wax used in the present invention preferably has a melting point of 76 to 130 ° C., preferably 76 to 110 ° C. By using the wax having the melting point in the above range for the toner, the effect of the wax plasticizing the toner can be further improved, and the fixing property of the toner can be improved. Further, when the melting point of the wax is within the above range, when the fixing member is excessively heated, the wax easily oozes out of the toner, and the high-temperature offset resistance of the toner can be improved. The melting point of the wax is 76
When the temperature is lower than ℃, the blocking resistance of the toner may be deteriorated. When the melting point exceeds 130 ° C., the fixing performance of the toner may be adversely affected.

In the present invention, the melting point of the wax can be measured using a differential thermal analyzer (DSC measuring apparatus) and DSC-7 (manufactured by PerkinElmer) under the following conditions.

<Measurement Method of Melting Point of Wax> Sample: 0.5 to 2 mg, preferably 1 mg Measurement method: A sample is placed in an aluminum pan, and an empty aluminum pan is used as a reference. Temperature curve: Heating I (20 ° C to 180 ° C, heating rate 10 ° C
/ Min) Temperature drop I (180 ° C to 10 ° C, temperature drop rate 10 ° C / min) Temperature rise II (10 ° C to 180 ° C, temperature rise rate 10 ° C / mi)
n) The endothermic peak temperature measured at the temperature rise II in the above temperature curve is defined as the melting point.

The wax used in the present invention has a temperature of 25 ° C.
Is preferably 15 or less (preferably 12 or less, more preferably 10 or less) in order to enhance the charging performance of the toner and obtain higher developability even in a high-temperature and high-humidity environment. If the penetration of the wax at 25 ° C. is larger than 15, the blocking resistance of the toner may be deteriorated. In the present invention, the penetration of the wax is determined according to JIS K-2235-5.4.

In the present invention, the wax is preferably added to the toner in an amount of 0.2 to 20 parts by mass, preferably 0.5 to 15 parts by mass, per 100 parts by mass of the binder resin.
More preferably, it is used in the range of 1 to 15 parts by mass.

In the present invention, the wax is 120
The viscosity at 500 ° C. is 500 mPa · s or less, preferably 2 mPa · s.
00 mPa · s or less, more preferably 100 mPa · s
The following is preferred in that the melt viscosity of the toner is reduced and good fixability is achieved. If the viscosity at 120 ° C. exceeds 500 mPa · s, the fixability of the toner may be insufficient. In the present invention, the viscosity of the wax is determined according to JIS K-6862-7.2.

The wax used in the present invention has a softening point of 75 ° C. to 140 ° C., preferably 75 ° C. to 130 ° C., and more preferably 75 ° C. to 120 ° C. It is preferable in that it has good properties and blocking resistance. If the softening point of the wax is lower than 75 ° C., the blocking resistance and offset resistance of the toner may be reduced. If the softening point of the wax exceeds 140 ° C., the fixability of the toner may be insufficient.
In the present invention, the softening point of the wax is JISK-220.
It is determined by 7-6.4.

The wax in the present invention may be used in combination with known waxes generally used in toners, including those described in the description of the prior art. For example, paraffin wax and its derivatives, montan wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, etc. Includes block copolymers with graft monomers and graft-modified products.

These waxes are used in an amount of 0.2 to 20 parts by mass, preferably 0.5 to 1 part by mass, per 100 parts by mass of the binder resin.
It is used in an amount of 5 parts by mass, more preferably 1 to 15 parts by mass.

The kind of the binder resin used in the present invention includes styrene resin, styrene copolymer resin, polyester resin, polyol resin, polyvinyl chloride resin, phenol resin, natural modified phenol resin, and natural resin modified male. Examples include acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, cumarone indene resin, and petroleum resin.

Examples of comonomers for the styrene monomer of the styrene copolymer include styrene derivatives such as vinyltoluene, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, and acrylate 2- Acrylates such as ethylhexyl and phenyl acrylate; methacrylates such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate and octyl methacrylate; maleic acid; butyl maleate, methyl maleate and dimethyl maleate Dicarboxylic acid esters having a double bond such as: acrylamide, acrylonitrile, methacrylonitrile, butadiene; vinyl esters such as vinyl chloride, vinyl acetate, and vinyl benzoate; ethylene, propylene Emissions, such as ethylene-based olefin butylene; vinyl methyl ketone, such as vinyl vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl propionate ether. These vinyl monomers are used alone or in combination of two or more.

In the present invention, the toner or the binder resin
The molecular weight distribution by GPC using THF (tetrahydrofuran) as a solvent is measured under the following conditions.

Stabilize column in heat chamber at 40 ° C
At this temperature, and the column
Flow hydrofuran (THF) at a flow rate of 1 ml per minute,
About 100 μl of a THF solution of the sample is injected and measured. Trial
When measuring the molecular weight of a sample, the molecular weight distribution of the sample
Is made with several monodisperse polystyrene standards.
It is calculated from the relationship between the logarithmic value of the calibration curve and the count number.
As a standard polystyrene sample for preparing a calibration curve,
For example, Tosoh or Showa Denko has a molecular weight of 10
^Two-10⁷Use at least 10 markers
Suitably a quasi-polystyrene sample is used. To the detector
Uses an RI (refractive index) detector. As a column, city
Combine multiple polystyrene gel columns for sale
Is good. For example, Shodex GPC manufactured by Showa Denko
 KF-801,802,803,804,805,8
06,807,800P or Tosoh Corporation
TSKgel G1000H (H_XL), G2000H
(H_XL), G3000H (H _XL), G4000H
(H_XL), G5000H (H_XL), G6000H
(H_XL), G7000H (H_XL), TSKguardc
column can be mentioned.

A sample is prepared as follows.

After the sample was put in THF and left for several hours,
Shake well and mix well with THF (until the sample is no longer united) and let sit for at least 12 hours. At this time, THF
The time for which the sample is left inside is set to 24 hours or more. Thereafter, the sample processing filter (pore size 0.
45 to 0.5 μm, for example, Myshoridisk H-2
5-5 Tosoh Corp., and ExcloDisk 25CR available from Germanic Science Japan) can be used as a GPC measurement sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

[0069] The binder resin in the present invention may have an acid value. Examples of the monomer for adjusting the acid value of the binder resin include acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinyl acetic acid, isocrotonic acid, and angelic acid;
Or β-alkyl derivatives; fumaric acid, maleic acid, citraconic acid, alkenyl succinic acid, itaconic acid, mesaconic acid, dimethyl maleic acid, unsaturated dicarboxylic acids such as dimethyl fumaric acid and monoester derivatives or anhydrides thereof, and the like. A desired polymer can be produced by copolymerizing such a monomer alone or in combination with another monomer. Among them, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid for controlling the acid value.

More specifically, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate,
Monoesters of α, β-unsaturated dicarboxylic acids such as monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate, etc .; monobutyl n-butenylsuccinate, monomethyl n-octenylsuccinate, Monoesters of alkenyldicarboxylic acids such as monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate, monobutyl n-butenyladipate, and the like are included.

The carboxyl group-containing monomer as described above may be added in an amount of 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, based on 100 parts by mass of all the monomers constituting the binder resin.

The resin composition according to the present invention has a glass transition temperature (Tg) of 45 to 80 ° C., preferably 50 to 70 ° C., from the viewpoint of storage stability. If the Tg is lower than 45 ° C., it causes deterioration of the toner in a high-temperature atmosphere and offset during fixing. If the Tg exceeds 80 ° C., the fixability tends to decrease.

The polymerization method of the binder resin of the present invention includes a solution polymerization method, an emulsion polymerization method and a suspension polymerization method.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, the reaction heat can be easily adjusted, and the phase in which the polymerization is performed (oil phase composed of a polymer and a monomer)
And the aqueous phase are separate, so that the termination reaction rate is low, resulting in a high polymerization rate and a high degree of polymerization. Further, due to the relatively simple polymerization process and the fact that the polymerization product is fine particles, in the production of toner,
There is an advantage as a method for producing a binder resin for a toner because it is easy to mix with a colorant, a charge control agent and other additives.

However, the resulting polymer tends to be impure due to the added emulsifier, and operations such as salting out are required to remove the polymer. To avoid this inconvenience, suspension polymerization is convenient.

In the suspension polymerization, 100 parts by mass or less of the monomer (preferably 1 part by mass) is added to 100 parts by mass of the aqueous solvent.
(0 to 90 parts by mass). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, and calcium phosphate, and are generally used in an amount of 0.05 to 1 part by mass based on 100 parts by mass of the aqueous solvent. The polymerization temperature is suitably from 50 to 95 ° C., but is appropriately selected depending on the initiator used and the intended polymer.

The binder resin used in the present invention is preferably formed by using a polyfunctional polymerization initiator alone or in combination with a monofunctional polymerization initiator as exemplified below.

Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-
3,3,5-trimethylcyclohexane, 1,3-bis- (t-butylperoxyisopropyl) benzene,
2,5-dimethyl-2,5- (t-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2 -Di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate , Di-t-butylperoxytrimethyladipate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-t-
A polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule such as butylperoxyoctane and various polymer oxides;
And a functional group having a polymerization initiating function such as a peroxide group in one molecule such as diallyl peroxydicarbonate, t-butyl peroxymaleic acid, t-butyl peroxyallyl carbonate and t-butyl peroxyisopropyl fumarate And a polyfunctional polymerization initiator having both a polymerizable unsaturated group.

Of these, more preferred are 1,1
-Di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyase Rate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, and t-butylperoxyallyl carbonate.

These polyfunctional polymerization initiators are preferably used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder for a toner.
In particular, it is preferable to use the polyfunctional polymerization initiator together with a polymerization initiator having a half life of 10 hours lower than the decomposition temperature for obtaining a half life of 10 hours.

Specifically, benzoyl peroxide,
1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t
-Butylperoxy) valerate, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t
Organic peroxides such as -butyl peroxide; azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene;

These monofunctional polymerization initiators may be added to the monomer simultaneously with the above-mentioned polyfunctional polymerization initiator. However, in order to maintain the efficiency of the polyfunctional polymerization initiator properly,
It is preferable to add the compound after the half-life of the polyfunctional polymerization initiator has passed in the polymerization step.

These initiators are preferably used in an amount of 0.05 to 2 parts by mass based on 100 parts by mass of the monomer from the viewpoint of efficiency.

It is also preferable that the binder resin is crosslinked with a crosslinking monomer.

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Specific examples include aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by an alkyl chain (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4 -Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6
Hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds linked by an alkyl chain containing an ether bond (for example, diethylene glycol diacrylate, triethylene glycol) Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate); Diacrylate compounds linked by a chain containing, for example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propanediacryle DOO, polyoxyethylene (4) -
2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; further, polyester-type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)) ). As multifunctional crosslinking agents, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate Alternatives; triallyl cyanurate, triallyl trimellitate; and the like.

[0086] These cross-linking agents may be used in combination with other monomer components 10
It is preferable to use 0.00001 to 1 part by mass, preferably 0.001 to 0.05 part by mass with respect to 0 parts by mass.

Among these crosslinkable monomers, those which are preferably used from the viewpoint of toner fixability and anti-offset properties include aromatic divinyl compounds (particularly divinylbenzene), and a chain containing an aromatic group and an ether bond. Diacrylate compounds.

As other synthesis methods, a bulk polymerization method or a solution polymerization method can be used. However, in the bulk polymerization method, a polymer having a low molecular weight can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control. In this regard, the solution polymerization method easily obtains a polymer having a desired molecular weight under mild conditions by utilizing the difference in radical chain transfer depending on the solvent and adjusting the amount of the initiator and the reaction temperature. Is preferred. In particular, a solution polymerization method under a pressurized condition is also preferable from the viewpoint of minimizing the amount of the initiator used and minimizing the influence of the residual initiator.

The composition of the polyester resin used in the present invention is as follows.

Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol and 1,5-pentanediol. , 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
Hexanediol, hydrogenated bisphenol A, and bisphenol represented by formula (A) and derivatives thereof;

[0091]

Embedded image (Wherein R is an ethylene or propylene group, x,
y is an integer of 0 or more, and the average value of x + y is 0 to 10. A diol represented by the formula (B);

[0092]

Embedded image x 'and y' are integers of 0 or more, and the average value of x + y is 0 to 10. ).

As the divalent acid component, for example, phthalic acid,
Benzenedicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides and lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides and lower alkyl esters; n- Alkenyl succinic acids or alkyl succinic acids such as dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides and lower alkyl esters thereof; fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acids such as itaconic acid or anhydrides, lower acids And dicarboxylic acids such as alkyl esters; and derivatives thereof.

It is preferable to use a tri- or higher valent alcohol component and a tri- or higher valent acid component which serve as a crosslinking component.

The trihydric or higher polyhydric alcohol component includes
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,
3,5-trihydroxybenzene and the like.

The trivalent or higher polyvalent carboxylic acid component in the present invention includes, for example, trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid,
2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,2
5-hexanetricarboxylic acid, 1,3-cycarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-
Octanetetracarboxylic acid, empol trimer acid, and anhydrides and lower alkyl esters thereof;

[0097]

Embedded image (Wherein, X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having at least one side chain having 3 or more carbon atoms), and their anhydrides and lower alkyl esters. And polyvalent carboxylic acids and derivatives thereof.

The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%.
%, 60 to 40 mol% as an acid component, preferably 5%
It is preferably from 5 to 45 mol%.

It is preferable that the trivalent or higher polyvalent component accounts for 5 to 60 mol% of all the components. The polyester resin can also be obtained by commonly known condensation polymerization.

The toner of the present invention preferably contains a charge control agent.

The following compounds can be used for controlling the toner to be negatively charged.

For example, organic metal complexes and chelate compounds are effective, and examples thereof include monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

Among them, an azo metal complex represented by the following general formula (1) is preferable.

[0104]

Embedded image

In particular, the central metal is preferably Fe or Cr, the substituent is preferably a halogen, an alkyl group or an anilide group, and the counter ion is preferably hydrogen, an alkali metal, ammonium or aliphatic ammonium. Also, a mixture of complex salts having different counter ions is preferably used.

Alternatively, a basic organic acid metal complex represented by the following general formula (2) is also preferable as a charge control agent imparting negative chargeability.

[0107]

Embedded image

In particular, as the central metal, Fe, Cr, Si,
Zn or Al is preferable, and the substituent is an alkyl group,
Anilide groups, aryl groups and halogens are preferred, and the counter ion is preferably hydrogen, ammonium or aliphatic ammonium.

The following compounds control the toner to be positively charged.

Modified products such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate;
And onium salts thereof such as phosphonium salts, which are analogs thereof, and lake pigments thereof, triphenylmethane dyes and these lake pigments (as the lake-forming agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannin Acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.) metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate Diorganotin borates; guanidine compounds, imidazole compounds; These can be used alone or in combination of two or more. Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used. Also, the general formula (3)

[0111]

Embedded image Monomer of a monomer represented by: styrene described above,
Copolymers with polymerizable monomers such as acrylates and methacrylates can be used as positive charge control agents. In this case, these charge control agents also act as (all or part of) the binder resin.

In particular, compounds represented by the following formula (4) are preferred as the positive charge control agent of the present invention.

[0113]

Embedded image

As a method for incorporating the charge control agent into the toner, there are a method of adding it inside the toner and a method of adding it externally. The use amount of these charge control agents is determined by the type of the binder resin, the presence or absence of other additives, the toner manufacturing method including the dispersion method, and is not limited to a specific one. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the binder resin.

The toner of the present invention can be used as a magnetic toner by incorporating a magnetic material into the toner particles. in this case,
Magnetic materials can also serve as colorants. Examples of the magnetic material used for the magnetic toner include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, and antimony. , Beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, alloys with metals such as vanadium and mixtures thereof.

These magnetic materials have a number average particle size of 0.05.
To 1.0 μm, more preferably 0.1 to 0.5 μm. The magnetic material has a BET specific surface area of 2 to 40 m
² / g (more preferably 4 to 20 m ² / g) is preferably used. The shape is not particularly limited, and an arbitrary shape is used. As the magnetic characteristics, the magnetic field 795.
Under 8 kA / m, saturation magnetization is 10 to 200 Am ² / kg
(More preferably 70 to 100 Am ² / kg) and a residual magnetization of 1 to 100 Am ² / kg (more preferably 2 to 20 Am ² / kg).
Am ² / kg) and those having a coercive force of 1 to 30 kA / m (more preferably 2 to 15 kA / m) are preferably used. These magnetic materials are based on 100 parts by mass of the binder resin.
Used in an amount of 20 to 200 parts by mass. Preferably 40-1
Used in 50 parts by mass.

The number average diameter can be determined by measuring a photograph enlarged by a transmission electron microscope or the like with a digitizer or the like. The magnetic properties of the magnetic material can be measured using an "oscillating sample magnetometer VSM-3S-15" (manufactured by Toei Kogyo Co., Ltd.) under an external magnetic field of 795.8 kA / m. The specific surface area can be calculated according to the BET method by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device Autosoap 1 (manufactured by Yuasa Ionics) and using the BET multipoint method.

Other colorants that can be used in the toner of the present invention include any suitable pigments or dyes.
Pigments such as carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara,
Examples include phthalocyanine blue and indanthrene blue. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass, per 100 parts by mass of the binder resin is good. . Examples of the dye include an azo dye, an anthraquinone dye, a xanthene dye, and a methine dye. The dye is used in an amount of 0.1 to 2 with respect to 100 parts by mass of the binder resin.
The addition amount of 0 parts by mass, preferably 0.3 to 10 parts by mass is good.

It is preferable that an inorganic fine powder or a hydrophobic inorganic fine powder is externally added to the toner of the present invention. For example,
Examples thereof include silica fine powder, titanium oxide fine powder, and a hydrophobized product thereof. They are preferably used alone or in combination.

Examples of the silica fine powder include both dry silica produced by vapor-phase oxidation of a silicon halide and called fumed silica, and wet silica produced from water glass or the like. Dry silica having few silanol groups on the surface and inside and having no production residue is preferable.

Further, the silica fine powder is preferably subjected to a hydrophobic treatment. The hydrophobization treatment is provided by chemically treating with an organosilicon compound that reacts or physically adsorbs with the silica fine powder. As a preferred method, there is a method in which fine silica powder produced by vapor phase oxidation of a silicon halide compound is treated with a silane compound, or simultaneously with a silane compound, and treated with an organosilicon compound such as silicone oil.

Examples of the silane compound used in the hydrophobizing treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, and allylphenyldichlorosilane. , Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilanemercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, Dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinylte Tramethyldisiloxane, 1,
3-diphenyltetramethyldisiloxane is exemplified.

Examples of the organosilicon compound include silicone oil. Preferred silicone oils have a viscosity of about 30 to 1,000 mm at 25 ° C.
² / s is used. For example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil are preferred.

The silicone oil treatment may be performed by directly mixing the silica fine powder treated with the silane compound with the silicone oil using a mixer such as a Henschel mixer, or adding the silicone oil to the base silica. May be injected. Alternatively, the silicone oil may be dissolved or dispersed in an appropriate solvent, mixed with a base silica fine powder, and the solvent may be removed.

As a preferable hydrophobic treatment of the silica fine powder, there is a method of preparing by treating with dimethyldichlorosilane, then with hexamethyldisilazane, and then with silicone oil.

As described above, it is preferable to treat the silica fine powder with two or more silane compounds, and then treat with an oil, since the degree of hydrophobicity can be effectively increased.

The above-mentioned silica fine powder which has been subjected to a hydrophobizing treatment and further an oil treatment to the titanium oxide fine powder may be used.
Preferred as well as silica-based.

Additives other than silica fine powder or titanium oxide fine powder may be externally added to the toner of the present invention, if necessary.

For example, a charging auxiliary, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent for fixing with a hot roll,
These are resin fine particles and inorganic fine particles that function as a lubricant, an abrasive and the like.

The fine resin particles have an average particle size of 0.1.
Those having a thickness of from 03 to 1.0 μm are preferred. As the polymerizable monomer constituting the resin, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene derivatives; acrylic acid; methacrylic acid; methyl acrylate , Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Acrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, methacrylate Lil, phenyl methacrylate, dimethylaminoethyl methacrylate, such as methacrylic acid esters of diethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, and the like monomers acrylamide.

Examples of the polymerization method include suspension polymerization, emulsion polymerization, and soap-free polymerization. More preferably, particles obtained by soap-free polymerization are good.

Other fine particles include lubricants such as Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride (in particular, polyvinylidene fluoride); abrasives such as cerium oxide, silicon carbide, and strontium titanate ( Among them, strontium titanate is preferred); fluidity-imparting agents such as titanium oxide and aluminum oxide (especially hydrophobic ones are particularly preferred);
Conductivity imparting agents such as carbon black, zinc oxide, antimony oxide, and tin oxide are exemplified. Further, small amounts of white fine particles and black fine particles having a polarity opposite to that of the toner may be used as a developing property improver.

The resin fine particles, inorganic fine powder or hydrophobic inorganic fine powder mixed with the toner is used in an amount of 0.1 to 5 parts by mass (preferably 0.1 to 3 parts by mass) based on 100 parts by mass of the toner. Is good.

The toner of the present invention exerts a sufficient effect when the weight average particle diameter is preferably 2.5 to 10 μm, and is preferable.

The weight average particle size and the particle size distribution of the toner are measured by using a Coulter counter method. For example, a Coulter Multisizer (manufactured by Coulter Inc.) can be used. The electrolyte is 1% Na using primary grade sodium chloride.
Prepare a Cl aqueous solution. For example, ISOTON R-II
(Manufactured by Coulter Scientific Japan) can be used. As a measuring method, the electrolytic aqueous solution 100 to 1
0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) is added as a dispersant in 50 ml,
Further, 2 to 20 mg of a measurement sample is added. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles of 2.00 μm or more were measured by using the measuring device with a 100 μm aperture as an aperture. Calculate the volume distribution and the number distribution. Then, the weight-based weight average particle diameter (D ₄ ) obtained from the volume distribution according to the present invention is calculated. As a channel,
2.00 to less than 2.52 μm; 2.52 to 3.17 μm
3.17 to less than 4.00 μm; 4.00 to 5.0
Less than 4 μm; 5.04 to less than 6.35 μm;
Less than 8.00 μm; 8.00 to less than 10.08 μm; 1
0.08 to less than 12.70 μm; 12.70 to 16.0
1 .0 μm or less; 16.0 to less than 20.20 μm;
20 to less than 25.40 μm; 25.40 to 32.00 μm
Less than m; 13 channels of 32.00 to less than 40.30 μm are used.

The toner of the present invention can be used as a two-component developer in combination with a carrier. As the carrier used in the two-component developing method, conventionally known carriers can be used. Specifically, particles having an average particle diameter of 20 to 300 μm formed of a metal such as iron, nickel, cobalt, manganese, chromium, rare earth, or an alloy or an oxide thereof, which have been oxidized or not oxidized, are used as carrier particles. You.

The surface of the carrier particles is made of a styrene resin,
A resin to which a substance such as an acrylic resin, a silicone resin, a fluorine resin, or a polyester resin is adhered or coated is preferable.

To produce the toner according to the present invention, the above-mentioned toner constituent materials are sufficiently mixed by a ball mill or other mixer, and then kneaded well using a heat kneader such as a hot roll, kneader, or extruder. Then, after cooling and solidifying, it is preferable to obtain a toner by mechanical pulverization and classification.Otherwise, a predetermined material is mixed with a monomer to constitute a binder resin to form an emulsified suspension. A method of producing a polymerized toner by polymerizing to obtain a toner, or a method of including a predetermined material in a core material and / or a shell material in a so-called microcapsule toner comprising a core material and a shell material, comprising a binder resin solution After dispersing the material, a method of obtaining a toner by spray drying can be applied. Further, if necessary, desired additives are sufficiently mixed by a mixer such as a Henschel mixer to produce the toner according to the present invention.

For example, as a mixer, Henschel mixer (manufactured by Mitsui Mining); super mixer (manufactured by Kawata); ribocorn (manufactured by Okawara Seisakusho); Nauter mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); Ledige mixer (manufactured by Matsubo), and kneading machines include KRC kneader (manufactured by Kurimoto Iron Works); bus co-kneader (manufactured by Buss); TEM Mold extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); knee Decks (manufactured by Mitsui Mining Co., Ltd.); MS-type pressure kneader, nider ruder (manufactured by Moriyama Seisakusho); Banbury mixer (manufactured by Kobe) Tokorosha, Ltd.) and the like. Examples of the pulverizer include a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS-type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic), a cross jet mill (manufactured by Kurimoto Iron Works), and ulmax ( SK Jet ・
O-Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); and Turbo Mill (manufactured by Turbo Kogyo). Classifiers include Classile, Micron Classifier, Spedd Classifier (Seishin Enterprise); Turbo Classifier (Nissin Engineering); Micron separator, Turboflex (ATP), TSP separator (Hosokawa Micron) Elbow jet (manufactured by Nippon Steel Mining), dispersion separator (manufactured by Nippon Pneumatic), and YM microcut (manufactured by Yaskawa Shoji). Ultrasonic (Koei Sangyo Co., Ltd.); Resona Sieve, Gyro Shifter (Tokuju Kosakusho Mori); Vibrasonic System (Dalton); Sonic Clean (Shinto) Turbo Screener (manufactured by Turbo Industries); Microshifter (manufactured by Makino Sangyo); circular vibrating sieve.

[0140]

Although the basic configuration and features of the present invention have been described above, the present invention will be specifically described below based on embodiments. However, this does not limit the embodiment of the present invention at all. Parts in the examples are parts by mass.

<Synthesis Example of Wax> (Synthesis Example 1 of Wax) 1000 g of Fischer-Tropsch wax (number average molecular weight 720) was put into a glass cylindrical reactor as a raw material, and nitrogen gas was blown in a small amount (3 liter / min). The temperature was raised to 140 ° C. Mixed catalyst of boric acid / boric anhydride = 1.4 (molar ratio) 23.7
After adding 6 g (0.33 mol), while blowing air (21 l / min) and nitrogen (18 l / min),
The reaction was performed at 180 ° C. for 2.5 hours. After completion of the reaction, an equal amount of warm water (95 ° C.) was added to the reaction mixture, and the reaction mixture was hydrolyzed to obtain wax 1. The hydroxyl value of wax 1 is 4
9.0 mg KOH / g, ester value is 11.8 mg KO
H / g, acid value 7.1 mgKOH / g, melting point 90 ° C,
The penetration was 6, the viscosity was 13 mPa · s, and the softening point was 93 ° C. Table 1 shows the synthesis conditions and physical properties of Wax 1.

(Wax Synthesis Example 2) 1000 g of polyethylene wax (number average molecular weight 1126) as a raw material
Was used in the same manner as in Wax Synthesis Example 1 except that the amount of the boric acid / boric anhydride mixed catalyst added and the reaction time were changed. Table 1 shows the synthesis conditions and physical properties of Wax 2.

(Wax Synthesis Example 3) Fischer-Tropsch wax (number average molecular weight 711) 1 as a raw material
Wax 3 was obtained in the same manner as in Wax Synthesis Example 1 except that 000 g was used, and the amount of the boric acid / boric anhydride mixed catalyst added and the reaction time were changed. Table 1 shows the synthesis conditions and physical properties of Wax 3.

(Wax Synthesis Example 4) α-
Wax 4 was prepared in the same manner as in Wax Synthesis Example 1 except that 1000 g of olefin (number average molecular weight 1633) was used, and the amount of boric acid / boric anhydride mixed catalyst added and the reaction time were changed.
I got Table 1 shows the synthesis conditions and physical properties of Wax 4.

(Wax Synthesis Example 5) The same procedure as in Wax Synthesis Example 1 was carried out except that 1000 g of paraffin wax (number average molecular weight 380) was used as a raw material and the amount of boric acid / boric anhydride mixed catalyst added and the reaction time were changed. Wax 5
I got Table 1 shows the synthesis conditions and physical properties of Wax 5.

(Wax Synthesis Example 6) Microcrystalline wax (number average molecular weight 362) 10 as a raw material
Wax 6 was obtained in the same manner as in Wax Synthesis Example 1 except that 00g was used and the amount of the boric acid / boric anhydride mixed catalyst added and the reaction time were changed. Table 1 shows the synthesis conditions and physical properties of Wax 6.

(Wax Synthesis Example 7) The same procedure as in Wax Synthesis Example 1 was carried out except that 1000 g of paraffin wax (number average molecular weight 469) was used as a raw material, and the amount of boric acid / boric anhydride mixed catalyst added and the reaction time were changed. Wax 7
I got Table 1 shows the synthesis conditions and physical properties of the wax 7.

(Wax Synthesis Example 8) The same procedure as in Wax Synthesis Example 1 was carried out except that 1000 g of paraffin wax (number average molecular weight 322) was used as a raw material, and the amount of boric acid / boric anhydride mixed catalyst and the reaction time were changed. Wax 8
I got Table 1 shows the synthesis conditions and physical properties of the wax 8.

(Wax Synthesis Example 9) The same procedure as in Wax Synthesis Example 1 was carried out except that 1000 g of polyethylene wax (number average molecular weight 908) was used as a raw material and the amount of boric acid / boric anhydride mixed catalyst and the reaction time were changed. Thus, wax 9 was obtained. Table 1 shows the synthesis conditions and physical properties of the wax 9.

(Wax Synthesis Example 10) The catalyst was 14.53 g (0.33 mol) of metaboric acid, and the reaction time was 1.5 times.
A wax 10 was obtained in the same manner as in the wax synthesis example 1 except that the time was changed. Table 1 shows the synthesis conditions and physical properties of wax 10.
Shown in

[0151]

[Table 1]

[Example 1] Styrene-butyl acrylate copolymer 100 parts Magnetic iron oxide 100 parts Monoazo iron complex 2 parts Wax 1 14 parts

The above mixture was melt-kneaded with a twin-screw extruder heated to 130 ° C., the cooled kneaded material was coarsely pulverized with a hammer mill, and the coarsely pulverized material was finely pulverized with a jet mill. The powder was classified with a fixed wall air classifier to produce a classified powder. Further, the obtained classified powder is strictly classified and removed by a multi-segmentation classifier utilizing a Coanda effect (an elbow jet classifier manufactured by Nittetsu Mining Co., Ltd.) at the same time to remove the weight average particle diameter (D ₄ ) A negatively chargeable magnetic toner of 6.8 μm was obtained.

A developer 1 was prepared by mixing 100 parts by mass of this magnetic toner and 1.2 parts by mass of hydrophobic silica fine powder with a Henschel mixer.

Examples 2 to 7 and Comparative Examples 1 to 3 Developers 2 to 10 were obtained in the same manner as in Example 1 except that the waxes used were changed to the waxes 2 to 10.

[Comparative Example 4] The wax used was wax 1
Developing agent 11 was obtained in the same manner as in Example 1 except that 1 (polyglycerin partially esterified product; melting point: 67 ° C., penetration: 10).

Next, the prepared developers 1 to 11 were evaluated by the following methods. Table 2 shows the evaluation results.
Shown in

Image output test : The above toner was placed in a process cartridge, and a laser beam printer L manufactured by Canon was used.
BP-3260 with A4 horizontal feed from 32 sheets / min to 50 sheets / min
The total pressure between the heating roller and the pressure roller of the fixing device was set to 441 N (45 kgf). The process speed at this time was 235 mm / sec.

(1) Image Density 20,000 sheets are printed out on ordinary paper for copying machines (75 g / m ² ) under normal temperature and normal humidity (23 ° C., 60% RH), and the images at the start and end The concentration was evaluated.
The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth) with respect to the printout image of a white background portion having a document density of 0.00.

(2) Fog 20,000 sheets were printed out on ordinary paper for copying machines (75 g / m ² ) under normal temperature and normal humidity (23 ° C., 60% RH), and the fog at the end was evaluated. Was. Fog was calculated from a comparison between the whiteness of the transfer paper measured by a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness on transfer after printing solid white.

(3) Evaluation of image black spots caused by toner adhesion to fixing member: 20,000 sheets of ordinary paper for copying machines (75 g / m ² ) in a low-temperature and low-humidity environment (temperature 15 ° C., 10% RH) After printing, the pressure roller and the image were visually evaluated. ◎ Black spots are not seen. ○ The toner adheres to the fixing roller, but does not appear on the image. B: Black spots at one or two points are observed on the image. × Three or more black spots are seen on the image.

Low-temperature fixability and high-temperature offset resistance : The above toner was placed in a process cartridge, and a laser beam printer LBP-3260 manufactured by Canon Inc. was transferred to A3 by A4 horizontal feed.
Remodeled from 2 sheets / minute to 50 sheets / minute, and furthermore, the surface temperature of the heating roller of the heating / pressing roller fixing device was set to 120 to 250 ° C.
The same conditions as those of the above-mentioned image output tester were set except that the modification was made so that it could be changed from the outside to the outside.
In H), the image sample was printed out.

(4) Low-temperature fixability An image fixed by applying a load of 4.9 kPa and using soft thin paper
, And the reduction rate (%) of the image density before and after the rubbing is 10%.
% As the lowest fixing temperature.
Was. In addition, it is common for copiers that have severe fixation as test paper.
Paper (90g / m ^Two)It was used.

(5) High-temperature offset resistance A sample image having an image area ratio of about 5% is printed out.
The evaluation was based on the degree of dirt on the image. The highest temperature at which no stain on the image occurred. The test paper used was plain paper for a copying machine (60 g / m ² ) in which offset was likely to occur.

Blocking resistance test : About 10 g of the toner was put in a 100 cc polycop, left at 50 ° C. for 3 days, and evaluated visually.凝集 No aggregates were observed. ○ Aggregates are seen, but easily collapse. △ Aggregates can be seen, but collapse when shaken. X: Aggregates can be grasped and do not collapse easily.

Example 8 100 parts polyester resin 4 parts carbon black 2 parts monoazo iron complex 2 parts Wax 1 4 parts

The above mixture was melt-kneaded with a twin-screw extruder heated to 130 ° C., and the cooled kneaded material was coarsely pulverized by a hammer mill, and the coarsely pulverized material was finely pulverized by a jet mill. The powder was classified with a fixed wall air classifier to produce a classified powder. Further, the obtained classified powder is strictly classified and removed by a multi-segmentation classifier utilizing a Coanda effect (an elbow jet classifier manufactured by Nittetsu Mining Co., Ltd.) at the same time to remove the weight average particle diameter (D ₄ ) A negatively chargeable magnetic toner of 6.8 μm was obtained.

A developer 12 was prepared by mixing 100 parts by mass of this toner and 1.2 parts by mass of hydrophobic silica fine powder with a Henschel mixer.

Next, the prepared developer 12 was evaluated for the fixing property and the offset resistance test in the same manner as in the above-mentioned method, using an image obtained by an image forming test described later. The image formation test was performed by the following method. Table 2 shows the evaluation results.

Image output test : The above toner was placed in a process cartridge, and a color printer LBP-2 manufactured by Canon was used.
040 (hot roll fixing method; process speed 117m)
m / sec), and 300
Evaluation was performed when 0 sheets were printed out. Table 2 shows the results.

[0171]

[Table 2]

[0172]

According to the present invention, there is provided a toner which is highly satisfactory in low-temperature fixing property and high-temperature offset resistance, has excellent blocking resistance, does not cause toner adhesion to a fixing member, and maintains high developability. can do.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tsuneo Nakanishi 3-30-2 Shimomaruko, Ota-ku, Tokyo Within Canon Inc. (72) Inventor Katsuhisa Yamazaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside (72) Inventor Kaori Hiratsuka 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Hirohide Tanigawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F Term (reference) 2H005 AA06 AB02 CA13 CA14 DA06 DA10 EA03 EA10

Claims (6)

[Claims] 1. A is a toner comprising a binder resin, a colorant and a hydrocarbon wax least, the wax is a hydroxyl value (H _V) is 5~150mgKOH / g, an ester value (E _V) is 1 a ~50mgKOH / g, the toner which is characterized in that the relationship is H _V> E _V. 2. The wax has an acid value (A _V ) of 1 to 30.
2. The toner according to claim 1, wherein mg KOH / g, and a relationship with a hydroxyl value (H _V ) is H _V > A _V. 3. The toner according to claim 1, wherein the wax has a melting point of 76 to 130 ° C. 4. The toner according to claim 1, wherein the wax is a wax obtained by converting an aliphatic hydrocarbon wax into alcohol. 5. The wax has an ester value (E _V ) of 1
2. The composition according to claim 1, wherein the amount is from 15 to 15 mgKOH / g.
5. The toner according to any one of items 1 to 4. 6. The wax has an acid value (A _V ) of 1 to 10.
The amount is mgKOH / g.
The toner according to any one of the above.