JPH1138670A - Electrophotographic developer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer having sufficient flowability and satisfactory electrostatic charge kick-off characteristics by incorporating a combination of silica surface-treated with silicone oil with titanium dioxide surface-treated with a fluorine-contg. silane coupling agent as an additive into a wax-contg. color toner. SOLUTION: The developer consists of a color toner consisting essentially of a bonding resin, a colorant, wax, an electrostatic charge controlling agent and an additive and a carrier. The additive is a combination of silica surface- treated with silicone oil with titanium dioxide surface-treated with a fluorine- contg. silane coupling agent. The quantity of electric charges of the carrier and the matrix toner not contg. the additive at the time of stirring is -15 to +5 μc/g and that of the carrier and the toner contg. the additive is -20 to -35 μc/g. The carrier is obtd. by coating the surfaces of spherical magnetic particles with silicone resin contg. a dispersed aminosilane coupling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a developer for developing an electrostatic image for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like.

[0002]

2. Description of the Related Art In recent years, the development of hard copy technology using an electrophotographic system has been rapidly expanding from black and white to full color, and the full color market has been particularly expanding. Color image formation by full-color electrophotography generally reproduces all colors using three primary color toners of three colors, yellow, magenta, and cyan, or four colors including black. In the general method, first, an electrostatic latent image is formed on a photoconductive layer by passing light from an original through a color separation light transmission filter having a complementary color relationship with the color of the toner.
Next, the toner is held on a support through development and transfer steps. Next, the above-described steps are sequentially performed a plurality of times, and while the registration is being performed, the toner is superimposed on the same support, and the final full-color image is obtained by performing the fixing only once. In a color electrophotography method in which such development is performed a plurality of times and a plurality of toner images of different colors are superimposed on the same support as a fixing step, the fixing property that the color toner should have is extremely important. Element. That is, the fixed color toner is required to suppress irregular reflection due to toner particles as much as possible and have appropriate glossiness and luster.
Further, the color toner must be transparent and have a wide color reproducibility so as not to hinder the toner layers of different color tones under the toner layer.

On the other hand, a fixing device used for fixing a color toner uses a roller made of a material having excellent surface releasability, but in most cases, the roller surface is coated with oil. However, the application of a large amount of oil to enhance the releasability has problems such as oil contamination of transfer paper, cost increase, and space for a tank for storing oil is required, and the fixing device becomes large.

In order to improve the releasability of the fixing with toner, it is necessary to control the molecular weight distribution of the binder resin used in the toner and to disperse wax in the toner. This eliminates the need to apply oil to the fixing roller. On the other hand, in the case of color toner, the binder resin melts at a fixed fixing temperature and requires sufficient color development by color superimposition.
It is necessary to lower the softening point of the binder resin as compared with black and white copier toner, and therefore it is necessary to lower the molecular weight of the binder resin. Therefore, there is a very low molecular weight component in the toner, and in the case of a toner containing wax, the fluidity (powder fluidity) of the toner itself is affected by the effect of the low melting point wax present on the toner surface. Greatly worsens. Further, in order to obtain higher image quality, the particle size of the toner tends to be reduced, which also causes deterioration of fluidity. Deterioration of the fluidity of the toner is a factor of deteriorating the toner transportability, developing performance, transferability, and the like.

On the other hand, in color toners and developers, it is generally said that the area of a color original is larger than that used in a black and white copier, and the amount of developer used is smaller than that in a black and white copier. The supplied toner contributes to the development in a short time. Therefore, it is necessary that the supplied toner instantaneously comes into contact with the carrier to obtain a sufficient charge amount. However, for the reasons described above, the fluidity is poor, and at the present time, toners and developers capable of obtaining a sufficient charge amount instantaneously have not been obtained.

For example, Japanese Unexamined Patent Publication (Kokai) No. 59-34539 discloses that a silica fine powder produced by vapor phase oxidation of a silicon halide compound is treated with a silane coupling agent and has a hydrophobicity of 30 to 80%. JP-A-61-277964 describes a developer characterized by having silica fine powder treated with silicone oil and having a hydrophobicity of 90% or more. ,
Although these are excellent in fluidity of the toner, the rising properties of charging are insufficient, and it is difficult to completely prevent background stain.

JP-A-58-60754 discloses a developer characterized in that silica fine powder synthesized by a wet method contains silica fine powder hydrophobized with silicone oil. And JP-A-59-522.
Japanese Patent Application Laid-Open No. 55-55366 discloses a toner containing fine powder of titanium oxide hydrophobized with an alkyl trialkoxysilane, and Japanese Patent Application Laid-Open No. 5-53366 discloses a toner comprising a silane coupling agent having a fluorine atom. It is described that the treated titanium oxide particles are externally added to the toner.However, the fluidity of the toner is insufficient, and the replenished toner contacts the carrier in the developer in a short time. Without this, it is difficult to completely prevent background contamination.

[0008]

SUMMARY OF THE INVENTION In view of the above prior art, an object of the present invention is to provide a wax-containing color toner which has sufficient fluidity and good charge rising characteristics.
An object of the present invention is to provide a developer which does not cause background stain.

[0009]

Means for Solving the Problems The object of the present invention is to provide (1) a developer comprising a color toner comprising at least a binder resin, a colorant, a wax, a charge controlling agent and an external additive, and a developer comprising a carrier. (2) A carrier used for the developer, wherein the external additive comprises silica surface-treated with silicone oil and titanium oxide surface-treated with a fluorinated silane coupling agent. And the charge amount of the parent toner not containing the external additive during stirring is -15 to +5 (μc / g), and the charge amount of the toner containing the external additive is -20 to -35 (μc / g) (3) “the developer according to the above (1), wherein a salicylic acid derivative metal salt is used as the charge controlling agent”; (3) “the developer according to the above (1),” 4) "The carrier is spherical magnetic The developer according to item (1), wherein the surface of the particles is coated with a silicone resin in which an aminosilane-based coupling agent is dispersed.

Hereinafter, the contents of the present invention will be described in detail. The present inventors have studied the toner and developer used in the developing method for obtaining a color image in electrophotography, and as a result, by using the color toner and the developer having the configuration of the present invention, the charge amount of the toner can be reduced. The rising was good, and it was possible to prevent the occurrence of background soiling.

That is, as described above, in the toner containing the wax, the fluidity of the toner is insufficient, and the ability of stirring the replenished toner to the carrier is insufficient, so that sufficient charging characteristics are obtained. It becomes difficult,
Uncharged or weakly charged toners tend to cause phenomena such as background staining and scattering.

In order to prevent these problems, the replenished toner contacts the carrier in a short period of time (with weak stirring), the toner in contact with the carrier is instantaneously charged (has a good rise), It is necessary that the toner replenished to the carrier does not stay and is sequentially developed, and that the staying toner does not spend on the surface of the carrier.

According to the present invention, in a color toner containing a wax, silica surface-treated with silicone oil and titanium oxide surface-treated with a fluorine-containing silane coupling agent are combined and contained as external additives. It has been found that the toner has good charge rising characteristics. Although the reason is not clear, it has been clarified that the combination of these external additives improves all of the above, and that the generation of background stains is prevented. Here, the silica that has been surface-treated with silicone oil indicates the following.

First, the silica used in the present invention is generally produced by a wet method or a dry method. In particular, a so-called fumed silica produced by a dry method (vapor phase oxidation of a silicon halide compound) is used. What is called from the viewpoint of fluidity is preferable. This is manufactured by a conventionally known technique. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

[0015]

Embedded image SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl In the production process, for example, a compound of silica and another metal oxide is obtained by using another metal halide such as aluminum chloride or titanium chloride together with a silicon halide. It is also possible to obtain fine powders, which are also included. The particle size is 0.001 as the average primary particle size.
It is preferable to use a silica fine powder in the range of from 0.002 to 0.2 .mu., Particularly preferably from 0.002 to 0.2 .mu.m.

Commercially available silica fine powder produced by vapor phase oxidation of a silicon halide compound preferably used in the present invention includes, for example, those commercially available under the following trade names. AEROSIL (Nippon Aerosil) 130 AEROSIL (Nippon Aerosil) 200 AEROSIL (Nippon Aerosil) 300 AEROSIL (Nippon Aerosil) 380 AEROSIL (Nippon Aerosil) TT 600 AEROSIL (Nippon Aerosil) MOX 80 AEROSIL (Japan Aerosil) MOX170 AEROSIL (Nippon Aerosil Co., Ltd.) COK 84 Ca-O-SiL (CABOT Co.) M-5 Ca-O-SiL (CABOT Co.) MS-7 Ca-O-SiL (CABOT Co.) MS-75 Ca- O-SiL (CABOT Co.) HS-5 Ca-O-SiL (CABOT Co.) EH-5 Wacker HDK N20 (WACKER-CHFMIEGMBH) V1S Wacker HDK N20 (WACKER-CHFMIEGMBH) N20E Wacker HDK N20 (WACKER-CHFMIEGMBH) T30 Wacker HDK N20 (WACKER-CHFMIEGMBH) T40

The silicone oil used in the present invention is not particularly limited, but may be a dimethylpolysiloxane type represented by the general formula (1), a methylhydrogenpolysiloxane type represented by the general formula (2), The methylphenylpolysiloxane type represented by (3) can be used.

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image Further, if necessary, alkyl modification, amino modification,
Epoxy modification, epoxy / polyether modification, carboxyl modification, mercapto modification, alcohol modification, fluorine modification and the like may be performed.

As a method of hydrophobizing silica fine powder with silicone oil, a method of dissolving silicone oil in a solvent, dispersing the silica fine powder in the solvent, and air-drying or filtering and drying, is used. To contact the silicone oil vapor to adsorb the silicone oil, and a method of directly mixing the silica fine powder and the silicone oil. Further, the processing amount of the silicone oil is 0.5 to 3 parts per 100 parts by weight of the silica fine powder.
About 0 parts by weight is appropriate. Further, the amount of the treated silica with respect to the toner is 0.05 to 5 parts per 100 parts by weight of the toner.
A suitable amount is 0.1 parts by weight, preferably 0.1 to 3 parts by weight. Further, the titanium oxide surface-treated with the fluorine-containing silane coupling agent has the following content.

The titanium oxide fine particles used in the present invention include those manufactured by a sulfuric acid method and a chlorine method, and all of rutile type, anatase type, amorphous type and a mixed type thereof can be used. Specific examples of the titanium oxide fine particles include P-25 (manufactured by Degussa); IT-S, IT-P
B, IT-PC (all manufactured by Idemitsu Kosan); R-82
0, R-830, R-680, CR-50, CR-6
0, A-100, A-220 (all manufactured by Ishihara Sangyo Co., Ltd.); JA-1, JA-2, JR, JRNC, JR60
0E, MT-150W, MT-500B, MT-600
B (all manufactured by Teica); STT-30A (manufactured by Titanium Industries) and the like. The particle size of the titanium oxide fine particles used is suitably in the range of 0.01 to 1 μm, particularly preferably 0.01 to 0.5 μm.

The following are specific examples of the fluorine-containing silane coupling agent. CF ₃ (CH ₂ )
₂ SiCl ₃ , CF ₃ (CF ₂ ) ₅ SiCl ₃ , CF ₃ (CF ₂ )
₅ (CH ₂ ) ₂ SiCl ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ SiC
l ₃ , CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , CF
₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) Cl ₂ , CF ₃ (CF ₂ ) ₂ S
i (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂ ,
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₅
CONH (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃ , CF ₃ (CF ₂ ) ₄ CO
O (CH ₂ ) ₂ Si (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ S
i (OCH ₃ ) ₃ , CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (CH ₃ ) (O
CH ₃ ) ₂ , CF ₃ (CF ₂ ) ₇ SO ₂ NH (CH ₂ ) ₃ Si (OC _{2
H 5) 3, CF 3 (} CF 2) 8 (CH 2) 2 Si (OCH 3) 3,

A conventionally known method is used for treating the surface of the titanium oxide particles with the fluorinated silane coupling agent. Specifically, the above-mentioned titanium oxide fine particles are previously heated to 100 to 150 ° C. under vacuum, stored in a desiccator, and treated to remove water. For example, a method of reacting dehydrated titanium oxide fine particles with the above-mentioned fluorinated silane coupling agent in toluene and subjecting the OH groups on the titanium oxide surface to a hydrophobic treatment is exemplified. Further, the treatment amount of the fluorinated silane coupling agent is suitably about 5 to 50 parts by weight based on 100 parts by weight of the titanium oxide fine powder. The amount of the treated titanium oxide to the toner is suitably 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the toner. An example of the production of titanium oxide surface-treated with a fluorinated silane coupling agent is shown below.

Production Example 1 150 parts of dehydrated toluene and 5 parts of silica (manufactured by Nippon Aerosil Co., Ltd .; Aerosil 200) were dried at 110 ° C. for 24 hours in a round bottom flask equipped with a magnetic stirrer and a trap. 5 parts of CF ₃ (CF ₂ ) ₂ Si (OCH ₃ )
₃ , and 0.5 part of acetic acid was further added as a buffer. The resulting suspension was refluxed at 50-60 ° C. for 7 hours, cooled to room temperature, and then filtered by suction. Subsequently, the residue was washed with toluene and dried at 110 ° C. for 4 hours. afterwards,
Suction filtration, then suction filtration with ethanol, 110 ° C
For 4 hours, and pulverized in an agate mortar to obtain a white powdery substance.

Production Example 2 Five parts of titanium oxide (manufactured by Teica; MT-500B) dried at 110 ° C. for 24 hours in a round-bottom flask equipped with a magnetic stirrer and a trap were mixed with 150 parts of dehydrated toluene and 1 part. .5 parts of CF ₃ (CF ₂ ) ₇ CH ₂ CH ₂ Si (OC
H ₃ ) ₃ was added, and 0.5 part of acetic acid was further added as a buffer. The resulting suspension is refluxed at 50-60 ° C. for 7 hours,
After cooling to room temperature, it was filtered with suction. Subsequently, the residue was washed with toluene and dried at 110 ° C. for 4 hours. Then, suction filtration is performed, and then suction filtration is performed using ethanol.
It was dried at 10 ° C. for 4 hours and pulverized in an agate mortar to obtain a white powdery substance.

Production Example 3 Five parts of titanium oxide (STT-30A, manufactured by Titanium Industry Co., Ltd.) dried at 110 ° C. for 24 hours in a round-bottomed flask equipped with a magnetic stirrer and a trap were mixed with 150 parts of dehydrated toluene. 1.5 parts of CF ₃ (CF ₂ ) ₂ Si (OCH ₃ ) ₃
Was added, and 0.5 part of acetic acid was further added as a buffer. The resulting suspension was refluxed at 50-60 ° C. for 7 hours, cooled to room temperature, and then filtered by suction. Subsequently, the residue was washed with toluene and dried at 110 ° C. for 4 hours. Thereafter, the mixture was subjected to suction filtration, then suction filtration with ethanol, dried at 110 ° C. for 4 hours, and pulverized in an agate mortar to obtain a white powdery substance.

Further, the charge amount of the carrier used in the developer of the present invention and the base toner containing no external additive during stirring is -1.
When the charge amount of the toner containing the external additive is -20 to -35 (μc / g) at 5 to +5 (μc / g), the level of the background stain is further improved. By obtaining these characteristics, the external additive strongly adheres electrostatically to the base toner,
It is considered that the toner itself has a uniform charge amount. In order to obtain these charge amounts, the charge amount is appropriately selected depending on the composition of the binder resin, the charge control agent, the processing material of the external additive, and the configuration of the carrier. The charge amount was measured by placing a carrier 57g used as a developer and 3g of toner in a cylindrical stainless steel pot (100cc), stirring the sample at 88 rpm for 10 minutes, and then using a blow-off device. Measured.

In particular, it is preferable to use a metal salt of a salicylic acid derivative as a charge control agent in order to obtain stable charge rising characteristics. The compound is

[0030]

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

In addition, the present compound is a compound of CLark, J, L,
Kao, H (1948) J. Amer. Chem. So
c. 70, 2151. For example, a zinc salt can be obtained by adding and mixing 2 mol of salicylic acid sodium salt (including the sodium salt of salicylic acid derivative) and 1 mol of zinc chloride in a solvent, heating, and stirring. This metal salt is a white crystal and does not show coloring even when dispersed in a toner binder. Even when the metal salt is other than a zinc salt, it can be produced according to the above method. The compounding amount of this compound is 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight, based on 100 parts by weight of the binder resin. Specific examples of the present compound include the following.

[0032]

[Table 1-1]

[0033]

[Table 1-2]

Further, in order to obtain a particularly stable charge rising characteristic, a carrier obtained by coating the surface of spherical magnetic particles with a silicone resin in which an aminosilane coupling agent is dispersed is used as a carrier. The object of the invention is achieved. Examples of the spherical magnetic particles include ferrite and magnetite, and those having an average particle size of 30 to 100 μm are selected.

The silicone resin may be a straight silicone resin having an organosiloxane bond, and a commercially available product is KR-27 manufactured by Shin-Etsu Chemical Co., Ltd.
1, KR-255, Dow Corning Toray Silicone SR-2410, SR-2406, SR-241
1. TRS-127B, TRS-1 manufactured by Toshiba Silicone Co., Ltd.
44 and the like, and a catalyst or the like may be added as necessary. As the modified silicone resin, a modified silicone resin such as an alkyd resin, a polyester resin, an epoxy resin, a polyurethane resin, and an acrylic resin can be used. As commercial products, KR-206 (modified by alkyd resin) manufactured by Shin-Etsu Chemical Co., Ltd. KR-9706 (modified with acrylic resin), ES-1001N (modified with epoxy resin), Toray
Dow Corning Silicone's SR-2101 (modified with alkyd resin) and the like. Further, a straight silicone resin is preferable, and a methyl silicone resin is particularly preferable in terms of coating strength. The aminosilane-based coupling agent can be represented by the following general formula.

[0036]

Embedded image (However, R ₆ is an alkylene group having 1 to 4 carbon atoms, a phenylene group, R ₇ and R ₈ are an alkyl group having 1 to 2 carbon atoms, R ₉ , R _9
10 is a hydrogen atom, a methyl group, an ethyl group, a phenyl group, an aminomethyl group, an aminoethyl group or an aminophenyl group,
n = 2 or 3. The aminosilane-based coupling agent reacts strongly with the base resin in the silicone resin, and firmly adheres to the resin. In particular, uniform and good charging characteristics can be obtained. Among the above, aminosilane coupling agents in which R ₆ is an alkylene group having 3 carbon atoms, R ₇ and R ₈ are alkyl groups having 2 carbon atoms, and R ₉ and R ₁₀ are hydrogen atoms are sufficient for the purpose of the present invention. To achieve. As the binder resin used in the color toner of the present invention, various types selected from transparency, glossiness, fixability, chargeability, and the like required for the color toner are used. Resins are preferred.

As the polyester resin, there are various types, and the following are preferable in order to maintain the characteristics required for the color toner.

[0038]

Embedded image (Wherein, R ¹¹ is an alkylene group having 2 to 4 carbon atoms,
x and y are positive integers, and the average value of the sum is 2 to 16. )

[0039]

Embedded image

[0040]

Embedded image (In the formula, R ¹² and R ¹³ are a saturated or unsaturated hydrocarbon group having 4 to 20 carbon atoms.) (I) The diol component represented by the formula, and (B) a divalent or higher polyvalent carboxylic acid (II) or (II) selected from the group consisting of an anhydride thereof and a lower alkyl ester thereof.
I) A polyester resin obtained by condensation polymerization of an acid component containing a divalent carboxylic acid represented by the formula or an anhydride thereof, or trimellitic acid or an acid component also containing an anhydride thereof. In addition, as a residual component of (b),
Phthalic acid, isophthalic acid, terephthalic acid, maleic acid,
Compounds such as fumaric acid and their anhydrides and their lower alkyl esters can be used. Examples of the compound represented by the formula (II) or (III) include succinic acid derivatives such as n-dodecenyl succinic acid, n-dodecyl succinic acid, n-butyl succinic acid, iso-dodecenyl succinic acid, and iso-octyl succinic acid. In particular, the fixability at low temperatures as a toner is sufficient, and the gloss is further improved.

Examples of the diol represented by the above formula (I) include polyoxypropylene (2,2) -2,2
-Bis (4-hydroxyphenyl) propane, polyoxyester (2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2
-Bis (4-hydroxyphenyl) propane, polyoxypropylene (16) -2,2-bis (4-hydroxyphenyl) propane, and the like.

It should be noted that a bifunctional or higher polyhydroxy compound as described below may be used in the diol component in an amount of about 5 mol% or less. Ethylene glycol, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, or etherified polyhydroxyl compounds thereof. The polyester resin is usually prepared by mixing a polyol component and a polycarboxylic acid component in an inert gas atmosphere at 180 to 2 times.
It can be produced by condensation polymerization at a temperature of 50 ° C.

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

The epoxy resin used in the present invention is preferably obtained by bonding a bisphenol such as bisphenol A or bisphenol F with epichlorohydrin. Epoxy resin is a bisphenol A type epoxy resin having at least two kinds of bisphenol A type epoxy resins having different number average molecular weights in order to obtain stable fixing characteristics and gloss, the number average molecular weight of the low molecular weight component is 360 to 2000, and the high molecular weight component is It is preferable that the number average molecular weight is 3,000 to 10,000. Further, it is preferable that the low molecular weight component is 20 to 50 wt% and the high molecular weight component is 5 to 40 wt%. When there are too many low molecular weight components, or when the molecular weight is lower than 360, glossiness may be too high and storage stability may be deteriorated. When the amount of the high molecular weight component is too large, or when the molecular weight is higher than 10,000, the gloss may be insufficient or the fixability may be deteriorated.

As the compound used in the present invention,
Examples of the alkylene oxide adduct of a dihydric phenol include the following. Examples include ethylene oxide, propylene oxide, butylene oxide, and a reaction product of a mixture thereof with a bisphenol such as bisphenol A or bisphenol F. The obtained adduct may be glycidylated with epichlorohydrin or β-methylepichlorohydrin before use. Particularly, a diglycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following formula (VI) is preferable.

[0046]

Embedded image Further, n and m are the numbers of repeating units, each being 1 or more, and n + m = 2 to 6. )

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

In order to obtain a polyol resin having an epoxy resin part and an alkylene oxide part in the main chain of the present invention, various raw material combinations are possible. For example,
Dihalide or diisocyanate, diamine, dithiol, epoxy resin of both terminal glycidyl group and alkylene oxide adduct of dihydric phenol of both terminal glycidyl group,
It can be obtained by reacting with a polyhydric phenol or dicarboxylic acid. Of these, the reaction with dihydric phenol is most preferable in terms of reaction stability. It is also preferable to use a polyhydric phenol or a polycarboxylic acid together with a dihydric phenol within a range not causing gelation. Here, the amount of the polyhydric phenols and polycarboxylic acids is 15 to the total amount.
% Or less, preferably 10% or less.

The compound used in the present invention having two or more active hydrogens which react with the epoxy group in the molecule includes 2
And polyhydric phenols, polyhydric phenols, and polyhydric carboxylic acids. Examples of the dihydric phenol include bisphenols such as bisphenol A and bisphenol F. As polyhydric phenols, ortho-cresol novolaks, phenol novolaks, and tris (4-
(Hydroxyphenyl) methane, 1- [α-methyl-α-
(4-hydroxyphenyl) ethyl] benzene. Examples of polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid,
Examples include phthalic acid, terephthalic acid, trimellitic acid, and trimetic anhydride. When these polyester resins and polyol resins have a high crosslinking density, it is difficult to obtain transparency and glossiness. Preferably, the polyester resin and the polyol resin are non-crosslinked or weakly crosslinked (THF; tetrahydrofuran: 5% or less insoluble matter). Is preferred. Further, the resin is not limited to these types of resins, and any known resin may be used in combination as needed.

For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene and their substituted products; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer Polymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-
Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer,
Styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl Ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid Styrene copolymers such as copolymers and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, Epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin.

Further, as the wax used in the present invention, various waxes can be used. In particular, when the wax incompatible with the binder resin is an ester-based or olefin-based wax, the offset resistance is particularly improved. It was found that the performance was improved. Since these waxes are incompatible with the binder resin and are uniformly dispersed, they exhibit anti-offset properties at the time of fixing the toner, and especially when a polyester resin or a polyol resin is used as the binder resin, the effect is improved. Is high. Here, the ester wax refers to a wax having an ester bond, such as candelilla wax, carnauba wax, natural wax such as rice wax, and montan wax.
Examples of the olefin-based wax include polyethylene wax, polypropylene wax and the like.

Next, dyes and pigments capable of obtaining yellow, magenta, cyan, and black toners can be used as the colorant. For example, carbon black, lamp black, ultramarine blue, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G, lake, chaco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, etc. Any conventionally known dyes and pigments, such as the dyes and pigments described above, can be used alone or in combination. The amount of these colorants to be used is generally 1 to 30% by weight, preferably 1.5 to 20% by weight, based on the binder resin.

It is preferable to use a charge control agent for imparting charge to the toner and to obtain a stable charge amount.
As the charge control agent in this case, it is preferable to add a transparent to white substance that does not impair the color tone of the color toner and stabilize and impart the toner to negative or positive polarity. Specifically, quaternary ammonium salts, imidazole metal complexes and salts, etc. are used as the positive polarity, and salicylic acid metal complexes and salts as the negative polarity,
Organic boron salts, calixarene-based compounds and the like are used.

The particle diameter of the toner of the present invention is preferably about 3 to 10 μm in terms of volume average particle diameter. If the particle diameter is smaller than this, it may cause background contamination during development and may deteriorate the fluidity. In some cases, toner replenishment and cleaning properties may be impaired. Further, when the particle diameter is larger than this, dust in an image, deterioration of resolution, and the like may cause a problem.

For the purpose of improving the fluidity of the toner in combination with the silica or titanium oxide used in the present invention as an external additive, different kinds of hydrophobic silica or titanium oxide,
Further, it is possible to add alumina and the like. In addition, fatty acid metal salts (such as zinc stearate and aluminum stearate) and polyvinylidene fluoride may be added as necessary.

[0056]

The present invention will be described below in more detail with reference to examples. However, the present invention is not limited to these. The parts in the examples represent parts by weight. Example 1 Preparation of toner and binder resin Polyester resin (softening point 92 ° C) 70 parts Styrene-acrylic resin (softening point 120 ° C) 30 parts Wax Microwax (melting point 81 ° C) 4 parts Charge control agent Fluorine-containing 4 2 parts of quaternary ammonium salt compound ・ Colorant 5 parts of pigment for yellow toner (Disazo yellow pigment: CI Pigment Yellow 17) 5 parts of pigment for magenta toner (Quinacridone magenta pigment: CI Pigment Red 122) 2.5 parts of pigment for cyan toner (copper phthalocyanine) Cyan pigment: CI Pigment Blue 15) 7 parts of pigment for black toner (carbon black) The above materials were mixed for each color with a Henschel mixer, and were melt-kneaded by two rolls heated to 100 to 110 ° C. After the kneaded product was allowed to cool naturally, it was coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then a base colored particle of each color was obtained using an air classifier. In addition, the volume average particle diameter of each color base colorant particle was as follows. (The volume average particle diameter was measured using a Coal Counter Model TA-II manufactured by Coulter Electronics Co., Ltd.) Yellow toner: 7.5 μm Magenta toner: 7.3 μm Cyan toner: 7.6 μm Black toner: 7.7 μm

Further, the following external additives were added to 100 parts by weight of each of the base colored particles using a Henschel mixer. 0.5 part of silica (100 parts of colloidal silica fine powder # 200 (manufactured by Nippon Aerosil Co., Ltd.) and 25 parts of dimethyl silicone oil (KF-96, 100 cs (manufactured by Shin-Etsu Chemical Co., Ltd.)) diluted with a solvent and a Henschel mixer And dried and then heat treated at 260 ° C.) Titanium oxide 0.5 part (prepared in Production Example 1)

Preparation of carrier : Core material: 100 parts of Cu-Zn ferrite (average particle size: 45 μm) Coating material: Silicon resin (SR-2411, solid content: 20% by weight, manufactured by Toray Dow Corning Silicone Co., Ltd.) was used in a fluidized bed. The core material was coated with 1.2 parts by weight, and baked at 210 ° C. for 2 hours to obtain a carrier coated with the above resin.

Preparation of Developer 4 wt% of the obtained toner and 96 wt% of the carrier were mixed by a turbuler mixer to obtain a developer of each color. The obtained developer was set on a Ricoh pretail 300, and a portion of the toner attached to the photoreceptor corresponding to the non-image portion was pasted on a printer bag, and the peeled printer bag was pasted on a Ricoh type 6200 paper. The density was measured with a Spectro densitometer manufactured by X-rite, and the difference from the density of only PRINTACH was defined as the density of the background soil on the photoreceptor. Table 2 shows the quality evaluation results.

Example 2 Preparation of toner and binder resin Polyester resin (softening point 94 ° C.) 40 parts Polyester resin (softening point 118 ° C.) 60 parts Wax Paraffin wax (melting point 71 ° C.) 4 parts Charge control agent Fluorine-containing 1.5 parts of quaternary ammonium salt compound Colorant Same as in Example 1 was treated in the same manner as in Example 1 to obtain mother colored particles. The volume average particle diameter of each color base colorant particle was as follows. Yellow toner: 7.5 μm Magenta toner: 7.7 μm Cyan toner: 7.6 μm Black toner: 7.8 μm

Further, the following external additives were added to 100 parts by weight of each of the base colored particles using a Henschel mixer. 0.6 parts of silica 100 parts of colloidal silica fine powder # 200 (manufactured by Nippon Aerosil Co., Ltd.) is treated with 25 parts of a fluorine-modified silicone oil (FL-100, 450cs (manufactured by Shin-Etsu Chemical Co., Ltd.)) diluted with a solvent and dried. And heat-treated at 260 ° C. 0.6 parts of titanium oxide (prepared in Production Example 1)

Preparation of carrier -Core material: 100 parts of Cu-Zn ferrite, (spherical, average particle diameter: 50 µm)-Coating material: 1.0 part of silicone resin (same as in Example 1) treated in the same manner as in Example 1. And got a career.

[0063]Creating developer  5% by weight of toner and 95% by weight of carrier
The same treatment as in Example 1 was carried out to obtain a developer. The resulting developer
Evaluation was performed in the same manner as in Example 1. Table 2 shows the quality evaluation results.
You.

Example 3 Preparation of Toner / Binder Resin 100 parts of polyester resin (softening point: 96 ° C.) 5 parts: wax: 5 parts of ester-based wax (melting point: 83 ° C.): charge control agent: salicylic acid derivative metal salt (shown in Compound Example 1) 2 parts Colorant Same as in Example 1 was treated in the same manner as in Example 1 to obtain base colored particles. The volume average particle diameter of each color base colorant particle was as follows. Yellow toner: 7.3 μm Magenta toner: 7.6 μm Cyan toner: 7.2 μm Black toner: 7.9 μm

Further, the following external additives were added to 100 parts by weight of each of the base colored particles using a Henschel mixer. 0.7 parts of silica 100 parts of colloidal silica fine powder # 130 (manufactured by Nippon Aerosil Co., Ltd.) are treated with 30 parts of olefin-modified silicone oil (KF-415 (manufactured by Shin-Etsu Chemical Co., Ltd.)) diluted with a solvent and dried. And heat-treated at 260 ° C. 0.4 parts of titanium oxide (prepared in Production Example 2)

Preparation of Carrier・ Core material: 100 parts of Li-ferrite (spherical, average particle diameter: 50 μm) ・ Coating material: 1.2 parts of silicone resin (same as in Example 1) was treated in the same manner as in Example 1, Got a career.

Preparation of Developer 6 wt% of the obtained toner and 94 wt% of carrier were treated in the same manner as in Example 1 to obtain a developer. The obtained developer was evaluated in the same manner as in Example 1. Table 2 shows the quality evaluation results.

Example 4 Preparation of Toner / Binder Resin Polyol Resin (Softening Point: 108 ° C.) 100 parts Wax Ester wax (melting point: 83 ° C.) 6 parts Charge control agent Salicylic acid derivative metal salt 2.5 parts (compound specific) (Shown in Example No. (2)) Colorant Same as in Example 1 was treated in the same manner as in Example 1 to obtain base colored particles. The volume average particle diameter of each color base colorant particle was as follows. Yellow toner: 7.1 μm Magenta toner: 7.8 μm Cyan toner: 7.4 μm Black toner: 7.6 μm

Further, the following external additives were added to 100 parts by weight of each of the base colored particles using a Henschel mixer. 0.4 part of silica 100 parts of colloidal silica fine powder # 200 (manufactured by Nippon Aerosil Co., Ltd.) is treated with 25 parts of dimethyl silicone oil (KF-96, 100 cs (manufactured by Shin-Etsu Chemical Co., Ltd.)) diluted with a solvent and dried. And heat-treated at 260 ° C. 0.7 parts of titanium oxide (prepared in Production Example 3)

Preparation of Carrier Core Material Magnetite, (spherical shape, average particle diameter 50 μm) 100 parts Coating material γ-aminopropyl based on the solid content of silicone resin (same as in Example 1; solid content 20%) 20% by weight of methotyldimethoxysilane was mixed, and 1.0 part of the core material was treated in the same manner as in Example 1 to obtain a carrier.

Preparation of Developer 7 wt% of the obtained toner and 93 wt% of carrier were treated in the same manner as in Example 1 to obtain a developer. The obtained developer was evaluated in the same manner as in Example 1. Table 2 shows the quality evaluation results.

Example 5 Preparation of Toner / Binder Resin 100 parts of polyester resin (softening point 109 ° C.) 100 parts ・ Wax 5 parts of polyethylene wax (melting point 80 ° C.) 2 parts of charge controlling agent salicylic acid derivative metal salt (Compound specific example No. (Shown in (4)) Colorant Same as in Example 1 was treated in the same manner as in Example 1 to obtain base colored particles. The volume average particle diameter of each color base colorant particle was as follows. Yellow toner: 7.5 μm Magenta toner: 7.5 μm Cyan toner: 7.3 μm Black toner: 7.6 μm

Further, the following external additives were added to 100 parts by weight of each of the base colored particles using a Henschel mixer. 0.7 parts of silica 100 parts of colloidal silica fine powder # 130 (manufactured by Nippon Aerosil Co., Ltd.) are treated with 20 parts of α-methylstyrene-modified silicone oil (KF-410 (manufactured by Shin-Etsu Chemical Co., Ltd.)) after solvent dilution. Dry and heat treated at 260 ° C. 0.7 parts of titanium oxide (prepared in Production Example 5)

Preparation of carrier・ Core material Magnetite, (spherical shape, average particle diameter 40 μm) 100 parts ・ Coating material γ-aminopropyl based on the solid content of silicone resin (same as in Example 1; solid content 20%) Triethoxysilane was mixed at 25% by weight, and 1. Nine parts were treated in the same manner as in Example 1 to obtain a carrier.

Preparation of Developer 5 wt% of the obtained toner and 95 wt% of carrier were treated in the same manner as in Example 1 to obtain a developer. The obtained developer was evaluated in the same manner as in Example 1. Table 2 shows the quality evaluation results.

Comparative Example 1 Preparation of Toner and Binder Resin Polyol Resin (Softening Point: 111 ° C.) 100 parts ・ Wax Paraffin Wax (melting point: 70 ° C.) 5 parts ・ Charge Control Agent Fluorine-containing quaternary ammonium salt compound 2 parts ・ Colorant The same procedures as in Example 1 were carried out in the same manner as in Example 1 to obtain base colored particles. The volume average particle diameter of each color base colorant particle was as follows. Yellow toner: 7.4 μm Magenta toner: 7.6 μm Cyan toner: 7.6 μm Black toner: 7.3 μm

Further, the following external additives were added to 100 parts by weight of each of the base colored particles using a Henschel mixer. 0.5 part of silica 100 parts of colloidal silica fine powder # 200 (manufactured by Nippon Aerosil Co., Ltd.) are treated with 20 parts of dimethyl silicone oil (KF-96, 100 cs (manufactured by Shin-Etsu Chemical Co., Ltd.)) diluted with a solvent and dried. Heat-treated at 260 ° C. 0.5 part of titanium oxide 100 parts of titanium oxide fine powder (P-25 (manufactured by Nippon Aerosil Co., Ltd.)), 20 parts of octyltrimethoxysilane diluted with a solvent, treated, dried, and heat-treated at 150 ° C.

Preparation of carrier・ Core material 100 parts of Cu—Zn ferrite (average particle diameter 50 μm) ・ Coating material 0.8 parts of silicone resin (the same as in Example 1) was treated in the same manner as in Example 1 to prepare a carrier. Obtained.

Preparation of Developer 5 wt% of the obtained toner and 95 wt% of the carrier were treated in the same manner as in Example 1 to obtain a developer. The obtained developer was evaluated in the same manner as in Example 1. Table 2 shows the quality evaluation results.

Comparative Example 2 Preparation of Toner / Binder Resin Polyol Resin (Softening Point: 108 ° C.) 100 parts ・ Wax Ester Wax (melting point: 83 ° C.) 6 parts ・ Charge Control Agent Salicylic acid derivative metal salt 2.5 parts (compound specifics) (Shown in Example No. (2)) Colorant Same as in Example 1 was treated in the same manner as in Example 1 to obtain base colored particles. The volume average particle diameter of each color base colorant particle was as follows. Yellow toner: 7.4 μm Magenta toner: 7.4 μm Cyan toner: 7.6 μm Black toner: 7.8 μm

Further, the following external additives were added to 100 parts by weight of each of the base colored particles using a Henschel mixer. 0.7 parts of silica 100 parts of colloidal silica fine powder # 200 (manufactured by Nippon Aerosil Co., Ltd.) treated with 20 parts of hexamethyldisilazane diluted with a solvent, dried, and heat-treated at 200 ° C. Titanium oxide 0.6 part Prepared in Production Example 3.

Preparation of Carrier Core Material 100 parts of Cu-Zn ferrite (average particle diameter 45 μm) Coating material 1.0 part of silicone resin (same as in Example 1) was treated in the same manner as in Example 1 to prepare a carrier. Obtained.

Preparation of Developer The obtained toner (6 wt%) and the carrier (94 wt%) were treated in the same manner as in Example 1 to obtain a developer. The obtained developer was evaluated in the same manner as in Example 1. Table 2 shows the quality evaluation results.

Comparative Example 3Creating toner  ・ Binder resin 100 parts of polyester resin (softening point 110 ° C) ・ 5 parts of wax polypropylene wax (melting point 118 ° C) 5 parts ・ Charge controlling agent 1.5 parts of fluorine-containing quaternary ammonium salt compound ・ Colorant The same treatment as in Example 1 was performed to obtain base colored particles. Each color
The volume average particle size of the parent colorant particles is as follows.
Was. Yellow toner: 7.2 μm Magenta toner: 7.3 μm Cyan toner: 7.4 μm Black toner: 7.5 μm

Further, the following external additives were added to 100 parts by weight of each of the base colored particles using a Henschel mixer. 0.4 parts of silica (the same as that shown in Comparative Example 2) 0.4 parts of titanium oxide (the same as that shown in Comparative Example 1)

Preparation of carrier -Core material 100 parts of magnetite (spherical, average particle diameter 40 µm)-Coating material 1.3 parts of silicone resin (same as in Example 1) was treated in the same manner as in Example 1, and the carrier was treated. Obtained.

Preparation of Developer 5 wt% of the obtained toner and 95 wt% of the carrier were treated in the same manner as in Example 1 to obtain a developer. The obtained developer was evaluated in the same manner as in Example 1. Table 2 shows the quality evaluation results.

[0088]

[Table 2-1]

[0089]

[Table 2-2]

[0090]

[Table 2-3]

[0091]

As is apparent from the detailed and specific description, the developer of the present invention comprises a color toner and a carrier comprising at least a binder resin, a colorant, a wax, a charge control agent and an external additive. A developer containing silica as the external additive, and titanium oxide surface-treated with a fluorinated silane-based coupling agent. In this case, sufficient fluidity and charge rising characteristics are good, and the occurrence of background contamination is prevented. Further, the charge amount of the carrier used for the developer and the base toner not containing the external additive at the time of stirring is -15 to +5 ( μc / g), and the charge amount of the toner containing the external additive is −20 to −35 (μc / g).
g), it has a good charge rising property, and further has an effect of preventing the occurrence of background stains.
By using a salicylic acid derivative metal salt as the charge control agent, the charge rising characteristics are further improved, the occurrence of background contamination can be further prevented, and further, the carrier is formed on the surface of the spherical magnetic particles. By being coated with a silicone resin in which an aminosilane-based coupling agent is dispersed, an extremely excellent effect that charging start-up characteristics are further improved and generation of background stains can be further prevented is exhibited.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Mitsuteru Kato 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Tomomi Suzuki 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Inside the company Ricoh

Claims (4)

[Claims] 1. A color toner comprising at least a binder resin, a colorant, a wax, a charge control agent and an external additive, and a developer comprising a carrier, wherein silica and a fluorine-containing surface-treated with a silicone oil are used as the external additive. A developer comprising a combination of titanium oxide surface-treated with a silane coupling agent. 2. A charge amount of a carrier used for the developer and a base toner containing no external additive during stirring is -15 to +5 (μm).
c / g), the charge amount of the toner containing the external additive is -20 to-
The developer according to claim 1, wherein the developer is 35 (μc / g). 3. The developer according to claim 1, wherein a salicylic acid derivative metal salt is used as the charge control agent. 4. The carrier according to claim 1, wherein the surface of the spherical magnetic particles is coated with a silicone resin having an aminosilane coupling agent dispersed therein.
The developer according to item 1.