JP2003066650A - Electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide electrostatic charge image developing toners which can provide high-grade images with an electrostatic charge image developing device of a wide range from a low speed to a high speed and are excellent in offset resistance, fixability, etc., in a heat roll fixing method. SOLUTION: The electrostatic charge image developing toners containing the polyester resin obtained by reacting (A) a polybasic acid compound of >=1 kind selected from the group consisting of bivalent or higher valence polybasic acids, acid anhydrides and their lower alkyl esters and (B) >=1 kind of diol component including an aliphatic diol [provided that the compounds having the bisphenol skeleton expressed by following general formula (1): (where, R<1> and R<2> are the same or different and denote ethylene groups or propylene groups; (n) and (m) denote the same or different and denote an integer from 0 to 6 and m+n denotes an integer from 0 to 7) are precluded] as a binder resin and an aromatic zirconium sulfate compound as a charge control agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an excellent property such that a high-quality image can be provided in a wide range of electrostatic image developing devices from low speed to high speed because the charge rises quickly and the charge stability is excellent. And a toner for developing an electrostatic charge image.

[0002]

2. Description of the Related Art In copying machines and printers utilizing the principle of electrophotography, electrostatic charges are applied to a photoconductor composed of an inorganic photoconductor such as selenium or an organic photoconductor such as polyvinylcarbazole or phthalocyanine. A developing method is employed in which a latent image is formed and a pre-charged dry toner is supplied to the latent image to form a visible image.

Dry toner used for developing an electrostatic latent image is a magnetic one-component system in which magnetic powder such as iron powder is internally added, or a non-magnetic one-component system in which iron powder is not used as a carrier, It is roughly classified into a two-component system in which toner particles and magnetic powder are mixed and used. In the magnetic one-component system, friction is caused by mutual friction between toner particles, and in the non-magnetic one-component system, charging is performed by strong friction when the toner particles slip between the developing sleeve and the charging member pressed against the developing sleeve. In the case of the system, the toner particles are mixed and stirred with the magnetic iron powder, and the surfaces of the toner particles are charged by mutual friction generated therebetween. Generally, the image quality of electrostatic printing is determined by the charge rising property of toner particles, the stability with time of charging,
It greatly depends on the amount of charge. Therefore, a method of internally adding a positive or negative charge imparting charge control agent (CCA) is adopted in the production of toner particles for the purpose of controlling these charge characteristics and always using them in a stable state. ing.

Conventionally, Japanese Patent Publication No. 2-16916 discloses an azo metal chelate complex as a charge control agent for imparting a negative charge to a toner. However, since the azo metal chelate complex is colored, it is not suitable for color toners, and further, it is decomposed or deteriorated due to mechanical shock or temperature / humidity conditions at the time of kneading the toner, and the original function of the charge control agent is deteriorated. was there.

On the other hand, chelate complexes of salicylic acid and its derivatives or metal salts of salicylic acid derivatives are disclosed in Japanese Patent Publication No.
-060183 (Zinc complex salt type), Japanese Patent Publication No. 8-01
No. 0360 (Aluminum complex salt type), JP 2000
-227675, JP2000-227676, JP2000-227678, and JP200.
0-258961 and Japanese Patent Laid-Open No. 2000-258962.
JP-A No. 2000-330338 (above, zirconium complex salt or zirconium salt-based) and the like. These are colorless or light-colored compounds themselves, and are often applied as negatively chargeable charge control agents for color toners because of their excellent charge build-up property and charge amount. There are still challenges.

Particularly, in the case of a non-magnetic one-component type copying machine, as described above, since the toner particles pass through the gap between the charging member and the developing sleeve, the charging is carried out.
When the toner particles are recycled and repeatedly rubbed, the surface of the toner particles is abraded along with it, and at the same time, the charge control agent (CCA) distributed on the surface often drops to some extent. Therefore, as one of the required characteristics of the charge control agent internally added to the toner of this system, abrasion resistance, that is, stability with time of charging is strongly demanded. In this respect, a salicylic acid chelate complex or a salicylic acid metal salt is required. Is not sufficiently satisfied when applied to a charge control agent for a non-magnetic one-component developer. In addition, there is a problem that these are all quite expensive.

Further, in recent years, the non-magnetic one-component developing system is 6 m / min or more, and the two-component developing system is two or more.
The printing speed of the machine is increasing, such as the developing speed of 0 m / min or more. Along with that, not only wear resistance in high-speed development and stability over time with charging are required, but
It is required to prevent the generation of toner particles that are not properly charged or that are charged to the opposite polarity, so that the toner does not scatter inside the machine or stains during printing to deteriorate print quality. Such required characteristics are required not only for the toner used in the non-magnetic one-component developing method but also for the toner for two-component developer, but in the conventional charge control agent as described above, Such characteristics required for high-speed development are not sufficiently satisfied.

Further, JP-A-7-56393 describes a toner containing a phthalimide compound having a carboxyl group as a negatively chargeable charge control agent. However, the phthalimide structure itself having a carboxyl group does not have any remarkable effect on the charging characteristics (particularly, the charge rise and the charge amount), and it is difficult to apply it as a negatively chargeable charge control agent.

As described above, at present, no charge control agent which is colorless or light-colored and has excellent charging characteristics and which is inexpensive and versatile has not yet been found.

On the other hand, various resins have been used as binder resins for toners. Among them, polyesters using a bisphenol A alkylene oxide adduct as a diol component because of their excellent toughness and fixability. Resin is widely used. However,
Bisphenol A and its derivatives have come to be concerned about harmfulness as an environmental hormone, and recently, a binder resin which does not use this is required.

[0011]

Therefore, the present invention is environmentally friendly and is capable of providing high-quality images in a wide range of electrostatic charge image developing devices from low speed to high speed, and stains at high speed development. Image can be obtained, the scattering of toner in the developing device can be reduced, a stable image can be obtained from the initial use of the developer to the end, and even when a colorant other than black is used, the charge control agent can be used. It is an object of the present invention to provide a toner for developing an electrostatic charge image, which does not change in hue and is excellent in offset resistance and fixability. Another object of the present invention is to provide a toner for developing a negatively chargeable electrostatic image which solves the above problems.

[0012]

Means for Solving the Problems As a result of intensive studies aimed at achieving the above object, the present inventors have found that a polyester resin obtained without using bisphenol A and its derivative and a fine and uniform dispersion in the polyester resin. The present invention has been completed by finding that the above problems can be solved by a toner for developing an electrostatic charge image containing an aromatic zirconium sulfonate compound as an essential component.

That is, the present invention relates to a toner for developing an electrostatic charge image, which comprises a binder resin and a charge control agent as essential components, wherein the binder resin is (A) a dibasic or higher polybasic acid, an acid anhydride, or a mixture thereof. One or more polybasic acid compounds selected from the group consisting of lower alkyl esters and one or more diol components containing (B) an aliphatic diol [however, the following general formula (1)

[Chemical 9] (1) (In the formula, R ¹ and R ² are the same or different and represent an ethylene group or a propylene group, m and n are the same or different and represent an integer of 0 to 6, and m + n is 0 to 7; A compound having a bisphenol skeleton represented by an integer) is included in the charge control agent, and the charge control agent contains a charge control agent containing an aromatic zirconium sulfonate compound. A toner for developing a charge image is provided.

According to the present invention, by adopting such a configuration,
The following effects are achieved. It is an environmentally friendly toner that does not contain bisphenol A and its derivatives, which are feared to act as environmental hormones. A polyester resin containing an aliphatic diol as a main component is a sharp melt and has a good affinity with paper, so that it has excellent low-temperature fixability and fix strength. Because the charge rises quickly and has excellent charge stability,
High-quality images can be provided in a wide range of electrostatic image developing devices from low speed to high speed. Since the aromatic zirconium sulfonate compound is finely and uniformly dispersed in the polyester resin, the negative polarity polyester toner, which tends to increase in amount, has a very small amount of reverse polarity and low charge components, and an image with less fog can be obtained. Also,
Toner scattering in the developing device can be reduced. The charge control agent used in the present invention is colorless CCA,
The toner for developing an electrostatic charge image of the present invention using the same does not change the hue even when combined with a highly transparent polyester resin and a colorant other than black, and has a high charge imparting power. Is suitable as

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polyester resin used in the present invention comprises at least one polybasic acid compound selected from the group consisting of dibasic or higher polybasic acids, acid anhydrides and lower alkyl esters thereof, and a fatty acid. It is obtained by reacting with a group-based diol component as a main component by a method such as dehydration condensation. Examples of the divalent polybasic acid and acid anhydride include phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, adipic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, Examples thereof include hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, malonic acid, glutaric acid, azelaic acid, sebacic acid, and other dicarboxylic acids, and acid anhydrides thereof. Further, as the lower alkyl ester thereof, an alkyl residue is
Preferably, it has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
The following are listed. Such lower alkyl ester is
It can be obtained by esterifying the above divalent polybasic acid or acid anhydride with a lower alcohol.

Among the above, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and the like are particularly preferable. In particular,
Naphthalenedicarboxylic acid, and / or its acid anhydride,
And / or its lower alkyl esters are preferably used. Specifically, dimethyl naphthalate, diethyl naphthalate, dibutyl naphthalate and the like are more preferable examples. It is necessary to use 1 mol% or more of the total acid components of the naphthalenedicarboxylic acids, and more preferably 5 mol% or more.

The monomer containing a naphthalene ring structure is effective in increasing the Tg of the resin and improves the heat-resistant cohesiveness of the resin. In particular, in a system mainly containing a soft aliphatic diol as an alcohol component, it is possible to suppress a decrease in the Tg of the resin, and it is possible to obtain low temperature fixability by using the aliphatic diol and heat cohesiveness due to naphthalenedicarboxylic acid. A resin having both can be obtained.

Examples of the aliphatic diol component include ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, and the like. For example, diols such as polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide random copolymer diol, ethylene oxide-propylene oxide block copolymer diol, ethylene oxide-tetrahydrofuran copolymer diol, and polycaprolactone diol are used. You can also

Of the above, cyclohexanedimethanol is preferably used. Cyclohexane dimethanol needs to be used in an amount of 5 mol% or more of the total alcohol component, and more preferably 10 mol% or more.

The monomer containing a cyclohexane ring structure is effective in increasing the Tg of the resin and improves the heat-resistant cohesiveness of the resin. In particular, in a system using a soft acyclic aliphatic diol as the alcohol component, it is possible to suppress a decrease in Tg of the resin.

Further, in the present invention, 20% by weight or less of the total diol component may be used together with the aromatic diol within the range that does not affect the performance. Examples of the aromatic diol include catechol, resorcinol, hydroquinone and the like. However, compounds having the bisphenol skeleton represented by the above general formula (1) are excluded. Examples of the aromatic diol to be removed include bisphenol A, polyoxyethylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene-
(2.0) -2,2-bis (4-hydroxyphenyl)
Propane, polyoxypropylene- (2.0) -2,2
-Bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.2) -polyoxyethylene-
(2.0) -2,2-bis (4-hydroxyphenyl)
Propane, polyoxypropylene- (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.
4) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane and derivatives thereof.

Examples of the trivalent or higher polyvalent monomer that can be used in the present invention include trifunctional or higher aromatic carboxylic acids such as trimellitic acid, trimellitic anhydride, pyromellitic acid, and pyromellitic dianhydride. Or a derivative thereof; or sorbitol, 1,2,3,6-hexanetetraol, 1,4-sorbitan, pentaerythritol, 1,
2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol,
Tri- or higher functional alcohols such as 2-methyl-1,2,4-butanetriol, trimethylolethane and trimethylolpropane; or ethylene glycol diglycidyl ether, hydroquinone diglycidyl ether,
N, N-diglycidylaniline, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, pentaerythritol tetraglycidyl ether,
Bisphenol F type epoxy resin, bisphenol S type epoxy resin, cresol novolac type epoxy resin,
Phenolic novolac type epoxy resin, polymer or copolymer of vinyl compound having epoxy group, epoxidized resorcinol-acetone condensate, partially epoxidized polybutadiene, semi-dry or dry fatty acid ester epoxy compound, etc. An epoxy compound may be used. When a polyepoxy compound is used, the low-temperature fixability is further improved by using a monoepoxy compound together. Examples of the monoepoxy compound include phenylglycidyl ether, alkylphenylglycidyl ether, alkylglycidyl ether, alkylglycidyl ester, glycidyl ether of alkylphenol alkylene oxide adduct, α-olefin oxide, monoepoxy fatty acid alkyl ester, and the like.

The polyester resin used in the present invention can be obtained, for example, by carrying out a dehydration condensation reaction or a transesterification reaction in the presence of a catalyst using the above raw material components. The reaction temperature and reaction time at this time are not particularly limited, but usually 2 to 2 at 150 to 300 ° C.
4 hours. As the catalyst for carrying out the above reaction, for example, tetrabutyl titanate, zinc oxide, stannous oxide, dibutyltin oxide, dibutyltin dilaurate and the like can be appropriately used. The compounding ratio (molar ratio) of the polybasic acid compound and the diol component is 8/10 to 10/8, especially 9
/ 10 to 10/9 is preferable. A linear polyester resin can be obtained by reacting a divalent polybasic acid compound with a diol component. Further, when a divalent or trivalent or more polybasic acid compound is reacted with a polyhydric alcohol or the like, a branched or network polyester resin is obtained.

When a linear polyester resin is used as the binder resin of the present invention, the weight average molecular weight of the resin is preferably 2 × 10 ³ to 1 × 10 ⁶ , and more preferably 4 × 10 ^{3 to} 3. It is × 10 ⁴ . Since the linear polyester has a good melting property at the time of fixing and is excellent in transparency, it is excellent in the color developability at the time of color superposition and the projected image of the OHP sheet becomes clear.

When a branched or crosslinked polyester resin is formed by using a polyvalent carboxylic acid having a valence of 3 or more, a polyhydric alcohol or a polyvalent epoxy compound together, the offset resistance at high temperature is improved and an oilless heat roll fixing system is used. Suitable for When the branched or crosslinked polyester resin is used alone as the binder resin, the number average molecular weight of the resin is 2 × 1.
0 ^{3 to} 6 × 10 ³ , the weight average molecular weight is 3 × 10 ^{4 to} 5 × 1
0 ⁵ , the THF insoluble content is preferably 0% to 40%, the number average molecular weight is 2.5 × 10 ^{3 to} 5.5 × 10 ³ , the weight average molecular weight is 5 × 10 ⁴ to 4 × 10 ⁵ , The THF insoluble content is more preferably 40% or less.

Furthermore, when a plurality of polyester resins having different viscosities are used in combination, a toner having further excellent fixing property at low temperature and hot offset resistance at high temperature can be obtained. This is because the low-viscosity resin in the binder resin is mainly responsible for cold offset resistance and low-temperature fixability, and the high-viscosity resin is mainly responsible for hot offset resistance and toughness. In this case, the resin may be blended so that the toner can obtain a desired performance, and in order to obtain a good low-temperature fixability, the Mn of THF-soluble component of the toner is 2,000 to.
Desirably within the range of 5,000, 2,500
More preferably, it is within the range of 4,500.

To obtain good hot offset resistance, the Mw of THF-soluble matter in the toner is 50,000.
Is preferably about 600,000, and is preferably 80,000.
More preferably, it is about 500,000. If the desired melt viscosity is obtained, the THF insoluble content of the toner is not so much problem, but in the THF insoluble content, a charge control agent,
Considering that wax, colorants, etc. are difficult to disperse, which may lead to toner scattering or scumming due to uneven charging,
It is preferably 20% or less. T10 ⁵ fixability at low temperatures include the 90 to 160 ° C. of the toner, and the offset resistance is more preferable because good. Furthermore, 95-15
Particularly preferably, it is 5 ° C.

The acid value is preferably 1 to 30 mgKOH / g, more preferably 1 to 20 mgKOH / g. The hydroxyl value is 10 to 100 mg KO.
H / g is preferred, and 10-60 mg KOH /
More preferably, it is g. When the acid value and the hydroxyl value are in the above ranges, the moisture resistance of the toner becomes good, which is preferable.

In the present invention, it is preferable to use, as the binder resin, two or more kinds of polyester resins having different melt viscosities. As a result, it melts at a relatively low temperature during fixing, forms a uniform layer after fixing, has excellent fixability and offset resistance, and a good image with no fluctuation in image density during continuous printing can be obtained. It is very clear and has excellent transparency.

In the present invention, a charge control agent containing an aromatic zirconium sulfonate compound is used. As the aromatic zirconium sulfonate compound, a compound obtained by reacting a sulfonate amine salt, a sulfonic acid, or a sulfonate with a zirconium compound such as zirconium oxychloride and basic zirconium carbonate,
Although not particularly limited, an aromatic zirconium sulfonate compound represented by the following general formula (2) is preferable.

[0031]

[Chemical 10] (2)

In the general formula (2), n represents an integer of 1-8. A represents a group represented by the following general formula (3), general formula (4), general formula (5), general formula (6), or general formula (7).

[0033]

[Chemical 11] (3)

[0034]

[Chemical 12] (4)

[0035]

[Chemical 13] (5)

[0036]

[Chemical 14] (6)

[0037]

[Chemical 15] (7)

In the general formula (3), R ₁ and R ₂ are each independently a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, an alicyclic hydrocarbon group such as a cyclohexyl ring, or an aryl group. Represents an aromatic hydrocarbon group. The alkyl group has 1 to 1 carbon atoms
The range of 10 is preferable, and the alicyclic hydrocarbon group has 3 to 10 carbon atoms.
The range of 6 is preferable, and the aromatic hydrocarbon group has 6 to 1 carbon atoms.
A range of 0 is preferred. Alkyl group, alicyclic hydrocarbon group,
Each aromatic hydrocarbon group may have a substituent such as an alkyl group, an aralkyl group, a halogen group, a carboxyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group.

In the general formula (4), the general formula (5) or the general formula (6), R ₃ is a hydrogen atom, an alkyl group such as a methyl group or an ethyl group, a halogen group such as an aralkyl group, a chloro group or a fluorine group. Represents a carboxyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. The alkyl group preferably has 1 to 10 carbon atoms, and the aralkyl group preferably has 7 to 10 carbon atoms. Of these, an alkyl group such as a methyl group, a halogen group such as a chloro group, and a carboxyl group are preferable.

In the general formula (7), R ₄ represents an aryl group or an arylimino group, and R ₅ represents a hydrogen atom or an alkyl group such as a methyl group or an ethyl group. The alkyl group preferably has 1 to 10 carbon atoms.

Among them, the following general formula (8)

[Chemical 16] (8) (In the formula, R ₆ represents a hydrogen atom or a carboxyl group, and n
Represents an integer of 1 to 8. Most preferably, the aromatic zirconium sulfonate compound represented by

The aromatic zirconium sulfonate compound used in the charge control agent used in the present invention is synthesized in advance using the corresponding sulfonic acid amine salt or the corresponding sulfonic acid as a precursor, and then added to an aqueous solution of the compound, for example. It can be easily produced by reacting a zirconium oxychloride or a zirconium compound such as basic zirconium carbonate.

The sulfonic acid amine salt, which is the precursor of the aromatic zirconium sulfonate compound used in the charge control agent used in the present invention, comprises sulfanilic acid and the corresponding dicarboxylic acid anhydride in the presence of a tertiary amine. It can be easily synthesized by reacting in a mixed solvent system of an aromatic hydrocarbon such as xylene and N, N′-dimethylacetamide while azeotropically removing water produced by the dehydration reaction.

The dicarboxylic acid anhydride used for the synthesis of the sulfonic acid amine salt which is the precursor of the aromatic zirconium sulfonate compound is, for example, phthalic anhydride, trimellitic anhydride, pyromellitic acid monoanhydride, 4- Chlorophthalic anhydride, 4-fluorophthalic anhydride, tetrachlorophthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrahydrotrimellitic anhydride,
Hexahydro trimellitic anhydride, succinic anhydride, hymic acid anhydride, hettic anhydride and the like can be mentioned.

The dicarboxylic acid anhydride used in the synthesis of the sulfonic acid amine salt involved in the synthesis of the aromatic zirconium sulfonate compound used in the charge control agent used in the present invention does not necessarily have to be selected in the reaction. Two or more kinds may be mixed and reacted.

Further, the aromatic zirconium sulfonate compound or the sulfonate which is a precursor of the compound is preliminarily prepared by gradually adding the corresponding acid halide or isocyanate compound to the sulfanilate aqueous solution. It can also be easily produced by synthesizing and reacting the precursor aqueous solution with a zirconium compound such as zirconium oxychloride.

Examples of the acid halide used in the synthesis of the sulfonate which is the precursor of the aromatic zirconium sulfonate compound include benzoyl chloride, benzoyl bromide, 4-methylbenzoyl chloride, 4-chlorobenzoyl chloride and 4-fluoro. Examples thereof include benzoyl chloride and 4-methoxybenzoyl chloride.

Further, examples of the isocyanate compound used for synthesizing the sulfonate which is a precursor of the aromatic zirconium sulfonate compound include phenyl isocyanate, p-toluene isocyanate, 4-methoxyphenyl isocyanate and the like.

Furthermore, a compound of zirconium aromatic sulfonate
As the zirconium compound used as a raw material for synthesizing the product, 4
For the valent compound, for example, ZrCl_Four, ZrBr_Four, ZrF
_Four, ZrI_FourZirconium halide compounds such as Zr
(OCH_Three)_Four, Zr (OC _TwoH₅)_FourTetra al, etc.
Coroxyzirconium compound, Zr (SO_Four)_TwoInorganic such as
Zirconium acid compound, Zr (OH) (OCH_Three)_Three,
Zr (OH) Cl_Three, Zr (OH)_TwoCl_TwoEqual partial base
Examples of the organic salt and divalent compound include ZrOCl_Two, ZrO
(NO_Three)_Two, ZrO (CO_Three), ZrO (SO_Four),
ZrO (HSO _Four)_Two, ZrO (CH_ThreeCOO)_Two, Z
Inorganic or organic oxyzirconium such as rOCl (OH)
Mu salt and the like.

Typical examples of the aromatic zirconium sulfonate compound used in the charge control agent used in the present invention include compounds represented by Compound-1 to Compound-23.

[0051]

[Chemical 17] Compound-1

[0052]

[Chemical 18] Compound-2

[0053]

[Chemical 19] Compound-3

[0054]

[Chemical 20] Compound-4

[0055]

[Chemical 21] Compound-5

[0056]

[Chemical formula 22] Compound-6

[0057]

[Chemical formula 23] Compound-7

[0058]

[Chemical formula 24] Compound-8

[0059]

[Chemical 25] Compound-9

[0060]

[Chemical formula 26] Compound-10

[0061]

[Chemical 27] Compound-11

[0062]

[Chemical 28] Compound-12

[0063]

[Chemical 29] Compound-13

[0064]

[Chemical 30] Compound-14

[0065]

[Chemical 31] Compound-15

[0066]

[Chemical 32] Compound-16

[0067]

[Chemical 33] Compound-17

[0068]

[Chemical 34] Compound-18

[0069]

[Chemical 35] Compound-19

[0070]

[Chemical 36] Compound-20

[0071]

[Chemical 37] Compound-21

[0072]

[Chemical 38] Compound-22

[0073]

[Chemical Formula 39] Compound-23

Among them, the aromatic zirconium sulfonate compounds represented by Compound-1, Compound-2, Compound-8, Compound-9, Compound-13 and Compound-14 are particularly preferable.

In the present invention, the method of internally adding the charge control agent to the toner is not particularly limited, but, for example, the aromatic zirconium sulfonate compound used as the charge control agent of the present invention is pre-ground and, if necessary, After further classifying, the pulverized product may be mixed and melt-kneaded with a toner resin, a colorant and other toner constituent components.

When the charge control agent used in the present invention is internally added to the toner, it is preferably added in an amount of 0.1 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the toner resin. Is particularly preferred. If the proportion of the charge control agent used is less than 0.1 parts by weight, the rising property at the time of charging tends to deteriorate and the toner tends to scatter.
On the other hand, when the proportion of the charge control agent used is more than 15 parts by weight, the charge amount of the toner when frictionally charged tends to increase excessively, which is not preferable.

Further, the electrostatic charge image developing toner of the present invention may be used in combination with other charge control agents within a range that does not impair the performance of the charge control agent and the purpose of use of the toner, and it is also possible to use reverse charge. By using a charge control agent of
It is also possible to adjust the chargeability of the toner. The charge control agent of the present invention is preferably used as a charge control agent for negatively chargeable toners, but when combined with a charge control agent having an opposite chargeability,
It can also be used as a part of the charge control agent for the positively chargeable toner.

As the charge control agent that can be used in combination with the aromatic zirconium sulfonate compound used in the present invention, conventionally known charge control agents can be used. For example, as a positive charge control agent, a nigrosine dye, a triphenylmethane dye, a quaternary ammonium salt, a resin containing a quaternary ammonium group and / or an amino group, or the like is used as a negative charge control agent, a trimethylethane dye, or a metal of salicylic acid. Complex salts, metal complex salts of benzylic acid, copper phthalocyanine, perylene, quinacridone, azo pigments, metal complex salt azo dyes, heavy metal-containing acid dyes such as azochrome complex, calixarene type phenolic condensates, cyclic polysaccharides,
A resin containing a carboxyl group and / or a sulfonyl group and the like are used as necessary.

In particular, when the electrostatic image developing toner of the present invention is used as a color toner, it is desirable to use a colorless compound as the charge control agent used together. Examples of the colorless negatively chargeable charge control agent include “Bontron E-84” manufactured by Orient Chemical Co. as a metal (Zn) complex compound of salicylic acid, and “LR-147” manufactured by Nippon Carlitt as a metal complex compound of benzylic acid. "LR-29
7 "and the like are preferable. The colorless positive charge control agent is TP-302, TP-41 having a quaternary ammonium salt structure.
5, TP-610; (Hodogaya Chemical Co., Ltd.), Bontron P-
51; (manufactured by Orient Kagaku), Copy Charge PSY
(Clariant Japan) and the like are preferable. Since the aromatic zirconium sulfonate compound used in the present invention is a colorless charge control agent, it is preferably used as a charge control agent for color toner, and since it is a negative charge control agent, other charge control agents are used. When used in combination with a control agent, it is preferably a negative charge control agent.

In the present invention, a release agent can be used. As the release agent, known polypropylene wax, polyethylene wax, modified polyolefin wax, higher fatty acid ester, Fischer-Tropsch wax,
Graft polymerization wax, higher aliphatic alcohol, amide wax, natural wax and the like can be used.

The release agent used here can have the same effect even if the production method is different, as long as it has the same chemical structure. There are various types of wax products such as fine powder, granules, beads, and pellets, but the average particle size is 1 mm or less, more preferably 0.
It is preferably 5 mm or less, and particularly preferably 0.1 mm or less.

The natural wax is a releasing agent derived from plants and animals, and examples thereof include carnauba wax, candelilla wax, rice wax, scale insect wax, and lanolin. By refining and pulverizing these release agents, the dispersibility in the binder resin is further improved. These mold release agents provide good performance even if they are used as they are, but those which have been chemically deodorized or deoxidized can obtain even better performance. The natural wax has an acid value of about 2 to 40 in catalog value due to its structure or free acid, but it is desirable that these values are low for the same reason as in the case of resin.

The higher fatty acid ester can be obtained by purifying a natural product or a synthetic product of carboxylic acids and alcohols. Further, the release agent may have a plurality of ester groups in the structure, or may be a mixture of compounds having different ester groups. The higher fatty acid ester obtained by synthesis is, for example, behenyl behenate, a monoester compound such as stearyl behenate, a montanic acid ester,
Examples include diester compounds such as 1,4-butanedibehenyl and 1,4-butanedistearyl, triester compounds, tetraester compounds such as pentaerythritol, and the like. Those having high purity and a low acid value can be obtained. It is suitable as a release agent. Examples of commercially available synthetic higher fatty acid esters include WEP-5, WEP-6 (NOF Corporation), Hoe-Wax E, F, OP (Clariant Corporation) and the like.

The higher aliphatic alcohol can be obtained by refining natural products or reducing oils and fats under pressure.
A wax containing a higher aliphatic alcohol as a main component can be obtained by oxidizing a polyolefin wax such as Fischer-Tropsch wax or polyethylene wax. Commercially available higher aliphatic alcohols include behenyl alcohol derived from natural products, Unilin 425, Unilin 550 (Petrolite Co., Ltd.), N
PS-9210, OX-1949, Paracor 5070
(Nihon Seiwa Co., Ltd.) and the like.

As the polyolefin wax, polyethylene wax, polypropylene wax, Fischer-Tropsch wax, paraffin wax, ethylene-
Examples include α-olefin copolymers. For example, commercially available polyethylene waxes include high wax 800P, 400P, 200P, 100P, NL1.
00, NL200, NL500 (Mitsui Chemicals, Inc.), H
oe-WAX PE130, PE190, PE520
(Clariant Co., Ltd.), Sun Wax LEL-
250 (Sanyo Kasei Co., Ltd.) and the like use Viscol 330P, 550P, 660 as polypropylene wax.
P (Sanyo Chemical Co., Ltd.), high wax NP055, N
P105, NP505, NP805 (Mitsui Chemicals, Inc.), Hoe-Wax PP230 (Clariant, Inc.) and the like. As Fischer-Tropsch wax, H-1, A-1 (Sazol Co., Ltd.), FT
100 (Nippon Seiwa Co., Ltd.) and the like, HNP-9, SP-160 (Nippon Seiwa Co., Ltd.) and the like as paraffin waxes, and High Wax 720P and 410P as an ethylene-α-olefin copolymer. , 420P (Mitsui Chemicals, Inc.) and the like.

As the modified polyolefin wax, high wax 405MP, 4051E (Mitsui Chemicals, Inc.), OX-0414, OX-0416 (Nippon Seiwa Co., Ltd.) )) Etc., or high wax 1140H, 1160H graft-modified with styrene monomer
(Mitsui Chemicals, Inc.) and the like.

Among the above, the releasing agent containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component has good dispersibility in the polyester resin, and has good releasing property and sliding resistance. preferable. When higher fatty acid ester wax and / or aliphatic alcohol is added to the toner for developing electrostatic image, the hot offset resistance and fixing strength are better than those of polyolefin wax such as polypropylene wax and polyethylene wax in the same amount. Is obtained.

The release agents may be used alone or in combination, and by containing 0.1 to 15 parts by weight, preferably 1 to 5 parts by weight with respect to the binder resin, good fixing offset performance can be obtained. can get. If the amount is less than 0.1 parts by weight, the offset resistance tends to be impaired, and if the amount is more than 15 parts by weight, the fluidity of the toner tends to deteriorate, and the spent carrier is generated due to the adhesion to the carrier surface.
The charging characteristics of the toner are likely to be adversely affected.

Colorants may be used in the present invention. Well-known coloring agents can be used.
Examples of the black colorant include carbon blacks such as furnace black, channel black, acetylene black, thermal black and lamp black, which are classified according to the manufacturing method, or C.I. I. Pigment Black 1
No. 1 iron oxide pigment, C.I. I. Pigment Bla
Examples of the iron-titanium oxide-based pigment of ck 12 and phthalocyanine-based cyanine black BX. It is also possible to use a plurality of pigments other than black to create a black color.

As a blue colorant, phthalocyanine type C.I. I. Pigment Blue 1, 2, 15: 1,
15: 2,15: 3,15: 4,15: 6,15,1
6, 17: 1, 27, 28, 29, 56, 60, 63 and the like. As the bluish colorant, preferably C.I.
I. Pigment Blue 15: 3 (generic name phthalocyanine blue G), 15 (phthalocyanine blue R), 16 (metal-free phthalocyanine blue), 60 (indanthrone blue), most preferably,
C. I. Pigment Blue 15: 3, 60.

As a yellow colorant, for example,
C. I. Pigment Yellow 1, 3, 4,
5, 6, 12, 13, 14, 15, 16, 17, 18,
24, 55, 65, 73, 74, 81, 83, 87, 9
3,94,95,97,98,100,101,10
4,108,109,110,113,116,11
7,120,123,128,129,133,13
8,139,147,151,153,154,15
5,156,168,169,170,171,17
2,173,180,185 and the like, and preferably C.I. I. Pigment Yellow 12 (generic name disazo yellow AAA), 13 (disazo yellow
AAMX), 17 (Disazo Yellow AAOA), 9
7 (Fast Yellow FGL), 110 (Isoindolinone Yellow 3RLT), and 155 (Sandrin Yellow 4G), 180 (Benzimidazolone), most preferably C.I. I. Pigment Ye
low 17, 155, 180.

Further, the red colorant is, for example, C.I.
I. Pigment Red 1, 2, 3, 4, 5,
6,7,8,9,10,12,14,15,17,1
8, 22, 23, 31, 37, 38, 41, 42, 4
8: 1, 48: 2, 48: 3, 48: 4, 49: 1,4
9: 2, 50: 1, 52: 1, 52: 2, 53: 1, 5
4,57: 1,58: 4,60: 1,63: 1,63:
2, 64: 1, 65, 66, 67, 68, 81, 83,
88, 90, 90: 1, 112, 114, 115, 12
2,123,133,144,146,147,14
9,150,151,166,168,170,17
1,172,174,175,176,177,17
8,179,185,187,188,189,19
0,193,194,202,208,209,21
4,216,220,221,224,242,24
3, 243: 1, 245, 246, 247 and the like, and preferably C.I. I. Pigment Red 4
8: 1 (generic name barium red), 48: 2 (calcium red), 48: 3 (strontium red), 4
8: 4 (manganese red), 53: 1 (lake red), 57: 1 (brilliant carmine 6B), 122
(Quinacridone magenta 122) and 209 (dichloroquinacridone red), most preferably C.I. I. Pigment Red 57: 1, 122 and 209.

The content of the colorant is preferably 1 part by weight to 20 parts by weight with respect to 100 parts by weight of the electrostatic image developing toner. It is more preferably 1 part by weight to 10 parts by weight, and particularly preferably 1 part by weight to 5 parts by weight. These colorants may be used either individually or in combination of two or more.

The electrostatic image developing toner of the present invention may contain additives other than a binder resin, a release agent, a charge control agent and a colorant. For example, metal soaps, lubricants such as zinc stearate and the like, abrasives such as cerium oxide and silicon carbide, and magnetic powders such as magnetite and ferrite can be used.

The toner for developing an electrostatic image of the present invention can be obtained by an extremely general production method, not by a specific production method. For example, the resin, the colorant, and the charge control agent can be obtained by melt-kneading at a melting point (softening point) or higher of the resin, pulverizing and classifying.

Specifically, for example, the above resins, colorants,
The components such as the release agent and the charge control agent are uniformly mixed in advance by a Henschel mixer or the like before melt kneading. The conditions of this mixing are not particularly limited, but the mixing may be performed in several stages so as to obtain the desired uniformity. The colorant and charge control agent used here are
Flushing treatment may be performed in advance so that the resin may be uniformly dispersed in the resin, or a master batch obtained by melt-kneading the resin with a high concentration may be used.

The above mixture is mixed by a kneading means such as a two-roll, a three-roll, a pressure kneader, or a twin-screw extruder. At this time, the colorant and the like may be uniformly dispersed in the resin, and the conditions of the melt-kneading are not particularly limited, but usually 80 to 180 ° C. and 30 seconds to 2 hours are preferable.

Further, if necessary, coarse pulverization is carried out for the purpose of reducing the load in the fine pulverization process and improving the pulverization efficiency. The apparatus and conditions used for coarse pulverization are not particularly limited, but it is common to coarsely pulverize to a particle size of 3 mm mesh pass or less by a rotoplex, palpelizer or the like.

Then, a method of finely pulverizing with an air pulverizer such as a mechanical pulverizer such as a turbo mill and a kryptron, a spiral jet mill, a counter jet mill, a collision plate jet mill, and classifying with a wind classifier and the like is used. Can be mentioned. Equipment for fine pulverization and classification, conditions are desired particle size,
The particle size distribution and particle shape may be selected and set.

Other methods for producing the toner for developing an electrostatic image of the present invention are disclosed by emulsion polymerization method, suspension polymerization method, JP-A-5-66600, JP-A-8-62891 and the like. There is a phase inversion emulsification method. The phase inversion emulsification method is to generate a discontinuous phase of Water in Oil by adding an aqueous medium (water or a liquid medium containing water as a main component) to a mixture of a binder resin, a colorant and the like and an organic solvent, Oil in Water by adding more water
By inversion into a discontinuous phase of, and further adding an aqueous medium to form a suspension in which the mixture floats as particles (droplets) in the aqueous medium, and then removing the organic solvent. It is a method for producing toner particles.

The volume average particle size of the particles constituting the toner is
Although not particularly limited, it is preferably adjusted to usually 5 to 15 μm.

In the present invention, various additives (referred to as external additives) can be used for surface modification of the toner such as improvement of fluidity of toner and improvement of charging characteristics. Examples of the external additive that can be used in the present invention include silicon dioxide, titanium oxide, aluminum oxide, cerium oxide, zinc oxide, tin oxide,
Inorganic fine powder such as zirconium oxide and those surface-treated with a hydrophobic treatment agent such as silicone oil and silane coupling agent, polystyrene, acryl, styrene acryl, polyester, polyolefin, cellulose, polyurethane, benzoguanamine, melamine, nylon, Resin fine powders such as silicon, phenol, and vinylidene fluoride are used.

Of these, silicon dioxide (silica) whose surface is hydrophobized with various polyorganosiloxanes, silane coupling agents and the like can be particularly preferably used. Examples of such products include those marketed under the following trade names.

AEROSIL R972, R974, R
202, R805, R812, RX200, RY20
0, R809, RX50, RA200HS, RA20
OH (Japan Aerosil Co., Ltd.) WACKER HDK H2000, H2050EP
HDK H3050EP, HVK2150 (Wacker Chemicals East Asia Co., Ltd.) Nipsil SS-10, SS-15, SS-2
0, SS-50, SS-60, SS-100, SS-5
0B, SS-50F, SS-10F, SS-40, SS
-70, SS-72F, (Nippon Silica Industry Co., Ltd.) CABOSIL TG820F (Cabot Specialty Chemicals, Inc.)

The particle diameter of the external additive is preferably 1/3 or less of the diameter of the toner, and particularly preferably 1/10 or less. In addition, these external additives have different average particle sizes of 2
You may use together 1 or more types. In the non-magnetic one-component developing toner, by using a large particle size and a small particle size together, the toner fluidity and development durability are improved, and sticking to the blade of the developing machine and prevention of fog are prevented. It is preferable because long-term stability of charging during running can be obtained. The proportion of the external additive used is 100 parts by weight of the toner,
The amount is 0.05 to 5% by weight, preferably 0.1 to 3% by weight.

When the electrostatic image developing toner of the present invention is used in a two-component developing system, the following carriers can be used. As the core agent of the carrier, iron powder, magnetite, ferrite, etc., which are used in the usual two-component development method, can be used, but among them, the true specific gravity is low, the resistance is high, the environmental stability is excellent, and it is easy to form a spherical shape so that it has fluidity. Ferrite or magnetite, which has a good value, is preferably used. The shape of the core agent may be spherical, amorphous or the like, and may be used without any particular problem. The average particle size is generally 10 to 500 μm, but 30 to 100 for printing high resolution images.
μm is preferred.

Examples of coating resins for coating these core agents include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether polyvinyl ketone, vinyl chloride. / Vinyl acetate copolymer, styrene / acrylic copolymer, straight silicone resin consisting of organosiloxane bond or its modified product, fluororesin, (meth) acrylic resin, polyester, polyurethane, polycarbonate, phenol resin, amino resin, melamine resin , Benzoguanamine resin, urea resin, amide resin, epoxy resin, acrylic polyol resin and the like can be used. Among these,
In particular, a silicone resin, a fluororesin, and a (meth) acrylic resin are excellent in charging stability and coating strength and can be used more preferably. That is, the resin-coated carrier used in the present invention uses ferrite or magnetite as the core agent,
It is preferable that the resin-coated magnetic carrier is coated with at least one resin selected from silicone resin, fluororesin, and (meth) acrylic resin.

The two-component developer using the toner for developing an electrostatic charge image of the present invention can be used at a normal developing speed, but especially at a developing speed of 20 m / min or more which is a high speed developing method.
Furthermore, it can be suitably used for a high speed machine of 30 m / min or more. In particular, even with a high speed machine of 45 m / min or more, fog does not occur, and printing can be performed for a long time with uniform image density.

The toner for developing an electrostatic charge image of the present invention is
It is developed and fixed on the recording medium by a known and commonly used method, and it is preferable to adopt a heat roll fixing method as the fixing method. As the heat roll, there is used one in which the surface of a cylindrical body that can be heated to a temperature at which toner can be melted and fixed is coated with a coating resin having both releasability and heat resistance, such as silicone resin or fluororesin. In the heat roll fixing method, the toner is fixed by passing the print medium between the two rolls having at least one heat roll as described above and pressed by an appropriate pressure.

The remarkable technical effect of the toner for developing an electrostatic charge image of the present invention is exerted in the developing and fixing apparatus in which the toner is developed at a higher speed and heat roll fixing is performed. As the recording medium in the present invention, any known and commonly used recording medium can be used, and examples thereof include papers such as plain paper and resin-coated paper, and synthetic resin films and sheets such as PET film and OHP sheet.

As the non-magnetic one-component developing method, there is a contact-type non-magnetic one-component developing method in which a developing sleeve carrying a developer is brought into contact with a photosensitive drum having an electrostatic latent image for development. However, the toner for non-magnetic single-component development of the present invention allows the toner to pass between the developing sleeve and the charging member pressed against the developing sleeve, and the toner is triboelectrically charged so that the toner formed on the surface of the photoconductor is electrostatically charged. It can be particularly effectively used for a contact type non-magnetic one-component developing method for developing an electrostatic latent image.

When the toner for developing an electrostatic charge image of the present invention is used in a developing device of a non-magnetic one-component developing system, it can be used at an ordinary developing speed, but especially at a developing speed of 6 m / min or more which is a developing process of high speed processing. Furthermore, it can be suitably used for a high-speed machine of 7 m / min or more. In particular, even with a high speed machine of 9 m / min or more, fog does not occur, and printing can be performed for a long time with uniform image density.

[0113]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. An example of synthesizing the binder resin used for preparing the toner is shown below.

(Resin (1); Synthesis of linear polyester) -Terephthalic acid: 664 parts by weight-Ethylene glycol: 54 parts by weight-Propylene glycol: 152 parts by weight-Neopentyl glycol: 150 parts by weight Stirrer of the above materials Put it in a 2 liter four-necked flask equipped with a condenser, a thermometer and under a nitrogen gas stream.
Part by weight of tetrabutyl titanate was added, and the reaction was carried out at 240 ° C. for 15 hours under normal pressure while removing water produced by dehydration condensation. Thereafter, the pressure was sequentially reduced and the reaction was continued at 5 mmHg. The reaction was followed by the softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 105 ° C. As for the molecular weight of the obtained polyester, when the number average molecular weight is Mn and the weight average molecular weight is Mw,
It was Mn: 3600 and Mw: 7830. T10 ⁵ :
115 ° C, acid value: 6.8, T in DSC measurement method
It was g: 58.2 ° C.

(Resin (2): Synthesis of linear polyester) -Terephthalic acid: 664 parts by weight-Propylene glycol: 152 parts by weight-Cyclohexanedimethanol: 145 parts by weight-Neopentyl glycol: 150 parts by weight The above materials are stirred. Place in a 2-liter four-necked flask equipped with a vessel, condenser, and thermometer, and under a nitrogen gas stream, 4
While adding tetrabutyl titanate in parts by weight and removing water generated by dehydration condensation, the reaction was carried out at 200 ° C. for 20 hours under normal pressure. Thereafter, the pressure was sequentially reduced and the reaction was continued at 5 mmHg. The reaction was followed by the softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 80 ° C. The molecular weight of the obtained polyester is M
It was n: 1870 and Mw: 4410. T10 ⁵ : 9
2 ° C, acid value: 6.8, Tg in DSC measurement method: 4
It was 7.3 ° C.

(Resin (3): Synthesis of cross-linked polyester resin) -Terephthalic acid: 498 parts by weight-Ethylene glycol: 75 parts by weight-Diethylene glycol: 32 parts by weight-Neopentyl glycol: 180 parts by weight-Epiclone N-695 (large) Nippon ink chemical industry products,
Phenol novolac type epoxy resin): 12.6 parts by weight Cardura E (Shell Japan product, alkyl glycidyl ester): 15 parts by weight The above materials were placed in a 2 liter four-necked flask equipped with a stirrer, condenser and thermometer. Under nitrogen gas flow, 4
Tetrabutyl titanate (g) was added, and the reaction was carried out at 240 ° C. for 10 hours under normal pressure while removing water produced by dehydration condensation. After that, the pressure was sequentially reduced and the reaction was continued at 30 mmHg. The reaction was followed by the softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 105 ° C. The obtained polyester resin has Mn:
3,200, Mw: 212,400, THF insoluble matter 0.
8%, T10 ⁵ : 112 ° C., acid value: 2.3, Tg: 5
It was 4.1 ° C.

(Resin (4): Synthesis of crosslinked polyester resin) -Terephthalic acid: 664 parts by weight-Neopentyl glycol: 120 parts by weight-Ethylene glycol: 150 parts by weight-Propylene glycol: 61 parts by weight-Epiclone 830 (Dainippon) Ink Chemical Industries, bisphenol F type epoxy resin): 19.3 parts by weight, Cardura E: 20 parts by weight The above materials were placed in a 2 liter four-necked flask equipped with a stirrer, condenser, and thermometer, and under a nitrogen gas stream. Four
g of tetrabutyl titanate was added, and the reaction was carried out at 240 ° C. for 12 hours under normal pressure while removing water produced by dehydration condensation. After that, the pressure was sequentially reduced and the reaction was continued at 30 mmHg. The reaction was followed by the softening point according to ASTM E28-517, and was terminated when the softening point reached 165 ° C. The obtained polyester resin has Mn:
6,650, Mw: 634,700, THF insoluble matter 0.
^{9%, T10 5: 177 ℃} , acid value: 9.3, Tg: 6
It was 7.2 ° C.

(Resin (5); Synthesis of branched polyester) -Terephthalic acid: 664 parts by weight-Ethylene glycol: 150 parts by weight-Neopentyl glycol: 166 parts by weight-Trimethylolpropane: 80 parts by weight Place in a 2-liter four-necked flask equipped with a condenser and thermometer, and under a nitrogen gas stream, 4
A part by weight of tetrabutyl titanate was added, and the reaction was carried out at 240 ° C. for 10 hours under normal pressure while removing water produced by dehydration condensation. Thereafter, the pressure was sequentially reduced and the reaction was continued at 5 mmHg. The reaction was followed by the softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 120 ° C. The branched polyester resin obtained is M
n: 4320, Mw: 221000, T10 ⁵ : 135
C., acid value 3.3, Tg 60 by DSC measurement method.
It was 2 ° C.

(Resin (6); Synthesis of branched polyester resin) -Terephthalic acid: 664 parts by weight-Ethylene glycol: 120 parts by weight-Polyoxypropylene- (2.2) -2.2-bis (4-hydroxyphenyl) ) Propane: 688 parts by weight, trimethylolpropane: 80 parts by weight The above materials were placed in a 2 liter four-necked flask equipped with a stirrer, a condenser, and a thermometer and placed under a nitrogen gas stream for 4 days.
A part by weight of tetrabutyl titanate was added, and the reaction was carried out at 240 ° C. for 10 hours under normal pressure while removing water produced by dehydration condensation. Thereafter, the pressure was sequentially reduced and the reaction was continued at 5 mmHg. The reaction was followed by the softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 120 ° C. The branched polyester resin obtained is M
n: 4200, Mw: 192200, T10 ⁵ : 132
C., acid value 7.9, Tg 62.
It was 3 ° C.

The resin obtained in each synthesis example was put in tetrahydrofuran (THF) and left standing for 12 hours. The solution obtained was filtered to measure the molecular weight of the THF-soluble component.

For the analysis, the gel permeation chromatography (GPC) method was used, and the molecular weight was calculated from the calibration curve prepared with standard polystyrene. GPC device: Tosoh Corp. HLC-8120 GPC column: Tosoh Corp. TSK Guardcolu
mn SuperH-H TSK-GEL SuperHM-M 3 connection concentration: 0.5 wt% Flow rate: 1.0 ml / min The THF insoluble content is 1 g of sample powder on a cylindrical filter paper, and refluxed for 8 hours with THF as a solvent in a Soxhlet extractor. It was calculated from the residue on the filter paper after that. Melt viscosity characteristics are constant load extrusion type thin tube rheometer (CFT manufactured by Shimadzu Corporation)
-500 C), piston cross-sectional area 1 cm ² , cylinder pressure 0.98 MPa, die length 1 mm, die hole diameter 1
mm, measurement start temperature 50 ° C, temperature rising rate 6 ° C / mi
n, and the sample weight was 1.5 g. T10 ⁵ represents the temperature when the viscosity of the viscosity-temperature curve by the constant load extrusion type capillary rheometer is 10 ⁵ poise.

Further, the synthesis examples of the charge control agent are shown below.

(Synthesis Example 1: Charge Control Agent (Compound-1))
Synthetic) Reflux condenser, thermometer, decanter and agitator
In a three-necked four-necked flask with a capacity of 3 L
Talic acid 197 g, sulfanilic acid 231 g, xylene 7
20 g and 220 g of N, N'-dimethylacetamide,
135 g of triethylamine was charged. Then stir
While heating the contents up to the reflux temperature,
Water does not form while azeotropically removing water with xylene.
The imidization reaction was continued until the temperature became low. After the reaction is complete, it precipitates
The particulate compound is filtered under reduced pressure and the pressure is reduced at 80 ° C for 2 hours.
It was dried to obtain 528 g of a precursor. IR absorption of the precursor
Collection spectrum: 1720 cm^-1(Imide C = O), 1
380, 1240, 1160 cm ^-1(Above sulfonic acid
SO_Two), 2710 cm^-1(NH⁺)

Then, this compound was charged again into a 3-liter four-necked flask, dissolved by heating in 900 g of deionized water, and the pH was adjusted to about 7 with diluted ammonia water, and then a zirconium salt aqueous solution prepared beforehand (zirconium oxychloride. 8
429 g of the hydrate was dissolved in 950 g of deionized water, then a colloidal aqueous solution partially hydrolyzed with 753 g of 3% ammonia water) was added dropwise, and the resulting suspension was filtered, washed with water, and dried with an atmospheric hot air dryer. Thus, 560 g of compound-1 was obtained. Theoretical amount: (C ₁₄ H ₈ NO ₅ S) ₄ Zr ₄ O ₄ (OH) ₄ Calculated value: C 39.4%, S 7.5%, Zr
21.4% Experimental value: C 38.0%, S 7.2%, Zr
20.8%

Synthesis Example 2 Synthesis of Charge Control Agent (Compound-2) Synthesis Example 1 except that 256 g of trimellitic anhydride was used in place of phthalic anhydride in Synthesis Example 1 except that the precursor was synthesized. In the same manner as in (1), 616 g of compound-2 was obtained. IR absorption spectrum of the precursor: 1720 cm
^-1 (imide C = O), 1710 cm ^-1 (COO
H), 1370, 1220, 1160 cm ^-1 (or more sulfonic acid SO ₂ ), 2740 cm ^-1 (NH ⁺ ) Theoretical formula amount: (C ₁₅ H ₈ NO ₇ S) ₄ Zr ₄ O ₄ (OH) ₄ Calculated value: C 38.3%, S 6.8%, Zr
19.4% Experimental value: C 37.3%, S 6.6%, Zr
19.0%

(Synthesis Example 3: Synthesis of Charge Control Agent (Compound-8)) In Synthesis Example 1, zirconium oxychloride octahydrate 343 g was partially hydrolyzed with 452 g of 3% aqueous ammonia as an aqueous zirconium salt solution. 520 g of Compound-8 was obtained in the same manner as in Synthesis Example 1 except that the compound was used. Theoretical formula _{weight: (C 14 H 8 NO 5} S) 5 Zr 4 O 4 (OH) 3 Calculated: C 42.2%, S 8.0% , Zr
18.3% Experimental value: C 40.7%, S 7.7%, Zr
18.2%

(Synthesis Example 4: Synthesis of Charge Control Agent (Compound-9)) In Synthesis Example 2, an aqueous solution of zirconium salt in which 343 g of zirconium oxychloride octahydrate was partially hydrolyzed with 452 g of 3% ammonia water was used. 576g of compound-9 was obtained like synthetic example 2 except having used it. Theoretical formula _{weight: (C 15 H 8 NO 7} S) 5 Zr 4 O 4 (OH) 3 Calculated: C 40.7%, S 7.2% , Zr
16.5% Experimental value: C 39.7%, S 7.0%, Zr
16.7%

(Synthesis Example 5: Charge Control Agent (Compound-13)
Synthesis of Synthetic Example 1 491 g of Compound-13 in the same manner as in Synthetic Example 1 except that as the zirconium salt aqueous solution, 286 g of zirconium oxychloride octahydrate partially hydrolyzed with 252 g of 3% ammonia water was used. Obtained. Theoretical formula _{weight: (C 14 H 8 NO 5} S) 6 Zr 4 O 4 (OH) 2 Calculated: C 44.3%, S 8.4% , Zr
16.0% Experimental value: C 42.8%, S 8.1%, Zr
16.4%

(Synthesis Example 6: Charge Control Agent (Compound-14)
Synthesis of Synthesis Example 2 In the same manner as in Synthesis Example 2, except that 286 g of zirconium oxychloride octahydrate, which was partially hydrolyzed with 252 g of 3% aqueous ammonia, was used as the aqueous solution of zirconium salt, 550 g of Compound-14 was synthesized. Obtained. Theoretical amount: (C ₁₅ H ₈ NO ₇ S) ₆ Zr ₄ O ₄ (OH) ₂ Calculated value: C 42.5%, S 7.6%, Zr
14.4% Experimental value: C 41.2%, S 7.4%, Zr
14.9%

(Comparative Synthesis Example 1) In the same manner as in Synthesis Example 2, except that 124 g of aniline was used in place of sulfanilic acid and triethylamine was not added, 297 g of the following compound-24 was obtained. (JP-A-7-
056393, additional test of Example 28) IR absorption spectrum of the compound: 1720 cm ⁻¹ (imide C═O), 1
710 cm ^-1 (COOH)

[0131]

[Chemical 40] Compound-24

Theoretical amount: C ₁₅ H ₉ NO ₄ Calculated value: C 67.4%, N 5.2% Experimental value: C 67.1%, N 5.0%

Example 1 <Preparation of Toner> Resin (1): 92 parts by weight Magenta R: 4 parts by weight (Fastogen Super Magenta R "Dainippon Ink and Chemicals")
-Viscole 550PD: 2 parts by weight-Compound-1: 2 parts by weight The above materials were mixed by a Henschel mixer and kneaded by a biaxial kneader. The kneaded material thus obtained was pulverized and classified to obtain a toner base material having a volume average particle diameter of 8.1 μm.

-Toner base material: 100 parts by weight-Silica "NAX50" manufactured by Nippon Aerosil: 0.5 parts by weight (average particle diameter of primary particles; 30 nm) -Silica "RY200" manufactured by Nippon Aerosil: 0.5 parts by weight (Average particle size of primary particles; 12 nm) was mixed with a Henschel mixer and then sieved to obtain a toner of Example 1.

Similarly, toner 2 was prepared according to the formulation shown in Table-1.
(Example 2) -15 (Example 15) and 16-18 (Comparative Examples 1-3) were obtained.

[0136]

[Table 1] Carnauba wax: Natural wax WEP-5: Higher fatty acid ester WEP-5 NOF PPWAX: Polypropylene wax VISCOL 550P
Sanyo Kasei TYHG: TONER YELLOW HG Clariant KET B.111: KET BLUE 111 Dainippon Ink and Chemicals Inc. Magenta R: Fastogen Super Magenta R Dainippon Ink and Chemicals Mogul L: Cabot Specialty Chemicals Inc. Carbon Black E-84: Orient Chemical Co., Ltd. 3,5-di-
t-Butylsalicylic acid / zinc-based chelate compound) TN-105: Hodogaya Chemical Co., Ltd., zirconium salt-based CC
A

<Preparation of developer> Four parts of the toners obtained in Examples 1 to 10 and Comparative Examples 1 to 3 and 96 parts of a carrier "Ferrite Carrier F-150" manufactured by Powdertech Co., Ltd. were frictionally mixed to perform two-component development. The agent was adjusted.

<Fixing Offset Test> With respect to the two-component developers using the toners obtained in the above Examples and Comparative Examples, the fixing start temperature, the hot offset start temperature and the printing test were conducted as follows. (Offset generation temperature) A belt-shaped unfixed image sample having a width of 2 cm and a length of 20 cm was prepared on an A4 paper by a commercial copying machine remodeling machine, and the roll temperature was changed using a heat roll fixing unit set under the following fixing conditions. Then, fixing was carried out, and the presence or absence of the hot offset phenomenon was confirmed.

[0139] The offset start temperature was a temperature at which the offset phenomenon was visually observed by observing the fixed image sample. The results are shown in Table-2.

(Fixing start temperature) Images obtained by fixing in different roll temperatures obtained in the offset resistance test were used. Mending tape (Sumitomo 3M, 81
0) was adhered at a constant pressure, and then peeled from a constant direction at a constant speed. The image residual ratio was determined by the formula calculated by the following formula. The image density is Macbeth image densitometer RD
It was measured at -918. Image remaining ratio = image density after peeling test / image density before peeling test Image remaining ratio of 80% or more is set to a level at which there is no practical problem, and the lowest temperature at which the image remaining ratio of 80% or more is set as the fixing start temperature. The results are shown in Table-2.

[0141]

[Table 2]

<Printing Test of Two-Component Developer> A printing test was conducted on the two-component developers obtained in the above Examples and Comparative Examples as follows.

(Printing Test) A commercially available laser beam printer (with an OPC photosensitive member) was used to evaluate the printing quality, the amount of charge, and the amount of toner scattering in the apparatus after continuous printing of 10,000 sheets. The charge amount is measured by a blow-off charge amount measuring device, and the image density is Macbeth densitometer RD-918.
The background stain was obtained by subtracting the density before printing from the density of the white background. Also, the amount of toner scattering is
The stain around the developing device was visually observed. The results are shown in Table-3.

[0144]

[Table 3]

* "Evaluation of background stain" ○: Less than 0.01, △: 0.01
~ Less than 0.03, ×: 0.03 or more * “Toner scattering amount” ◯: Almost no scattering, Δ: Slightly scattered stains, ×: Severe scattering occurred

<Printing test of non-magnetic one-component developer> A printer (Ricoh printer using the commercially available non-magnetic one-component developing method) is used.
The dedicated toner was removed from a cartridge of "IPSIO Color 2000" manufactured by K.K., and the washed toner was filled with the toner obtained in each of Examples and Comparative Examples, and 10000 sheets were continuously printed. The state in which the toner layer on the developing sleeve was uniform and no defects were generated was judged as ◯, and the case where uneven portions such as stripes were generated was judged as x. In addition, the condition that the toner does not spill from the developing sleeve mounted on the cartridge (toner dropping) or scatter around the developing device (toner scattering) to contaminate the inside of the machine is ○, a small amount of toner dropping or toner scattering is recognized. The state in which the toner was scattered was judged to be Δ, and the state in which a large amount of toner was dropped or the toner was scattered was judged to be ×. The image density and the background stain of the printed matter were measured with a Macbeth densitometer RD-918.
The background stain was obtained by subtracting the white paper density before printing from the white background density after printing. ○ when the difference is less than 0.01
When 0.01 to less than 0.03, it was designated as Δ, and when 0.03 or more, it was designated as x. The results are shown in Table-4.

[0147]

[Table 4]

[0148]

The toner for developing an electrostatic charge image of the present invention is excellent in charging characteristics, anti-offset property and fixing property, so that a high quality image can be obtained in a copying machine or printer having various developing speeds from low speed to high speed. Can be provided.
In particular, an image with less background stain can be obtained even during high-speed development, toner scattering and spillage in the developing device can be reduced, and a stable image can be obtained from the beginning to the end of development. Furthermore, since the charge control agent used in the present invention is almost colorless, it is possible to obtain a clear color image with good color reproducibility even when used as a charge control agent for color toners.

Claims (4)

[Claims] 1. A toner for developing an electrostatic charge image comprising a binder resin and a charge control agent as essential components, wherein the binder resin comprises (A) a dibasic or higher polybasic acid, an acid anhydride and a lower alkyl ester thereof. 1 selected from the group
At least one diol component containing at least one polybasic acid compound and (B) an aliphatic diol, provided that the following general formula (1) (1) (In the formula, R ¹ and R ² are the same or different and represent an ethylene group or a propylene group, m and n are the same or different and represent an integer of 0 to 6, and m + n is 0 to 7; A compound having a bisphenol skeleton represented by an integer) is included in the charge control agent, and the charge control agent contains a charge control agent containing an aromatic zirconium sulfonate compound. Toner for charge image development. 2. The zirconium aromatic sulfonate compound
The thing is the general formula (2), [Chemical 2] (2) [In formula, A is general formula (3), general formula (4), general formula
(5), general formula (6), general formula (7), [Chemical 3] (3) [Chemical 4] (4) [Chemical 5] (5) [Chemical 6] (6) [Chemical 7] (7) (In the formula, R₁, R_TwoAre independently hydrogen atom and carbon number
1-10 alkyl group, alicyclic hydrocarbon having 3-6 carbon atoms
A group or an aromatic hydrocarbon group having 6 to 10 carbon atoms, R
_ThreeIs a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and 7 carbon atoms
An aralkyl group of 10, a halogen group, a carboxyl group,
Alkoxycarbonyl group or aryloxycarboni
Represents a radical, R_FourIs an aryl group or an arylimino group
Represents R ₅Is a hydrogen atom or an alkane having 1 to 10 carbon atoms.
Represents a kill group. ) Represents a group represented by
For developing an electrostatic charge image according to claim 1.
toner. 3. The zirconium aromatic sulfonate compound has the general formula (8): (8) (In the formula, R ₆ represents a hydrogen atom or a carboxyl group, and n
Represents an integer of 1 to 8. ) The toner for developing an electrostatic charge image according to claim 1. 4. The toner for developing an electrostatic charge image according to claim 1, wherein the binder resin contains two or more kinds of polyester resins.