JP2002131971A - Electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner having good fixing and anti-offsetting properties in a wide temperature range and suitable for a heat roll fixing system, and also to provide an electrostatic charge image developing color toner excellent in color reproducibility and transparency, having stable electrostatic charge behavior even in continuous printing and giving a good image of high image quality. SOLUTION: In the electrostatic charge image developing toner, a resin binder is a polyester resin consisting essentially of (A) a polybasic acid compound selected from among di- or higher-valent polybasic acids and/or acid anhydrides and/or their lower alkyl esters and (B) an aliphatic polyol having >=2 OH groups, a releasing agent is a wax based on a higher fatty acid ester compound and/or an aliphatic alcohol compound and an electrostatic charge controlling agent is a zirconium complex or salt of formula 1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image used in an electrophotographic method, an electrostatic recording method, or an electrostatic printing method.

[0002]

2. Description of the Related Art In a two-component developing method in electrophotography, a carrier shares functions such as agitating, transporting, and charging a developer, and the function separation between the carrier and the toner is clear. For this reason, the two-component developing method is widely used because it is relatively easy to control the charge of the toner and can cope with high speed operation.

Recently, a color toner in which a cyan pigment, a magenta pigment, a yellow pigment or other chromatic pigments are dispersed in a binder has been used, and full-color or mono-color copying using these color toners has been used. Machines and printers have been developed.

[0004] Such a color toner does not cause color turbidity by exhibiting vivid coloration of an image after printing and exhibiting excellent transparency in color superposition in multicolor printing. Having clear color reproducibility, or projecting a color image obtained by transferring and fixing on an overhead projector (hereinafter referred to as OHP) sheet and projecting it on a screen to produce clear colors without turbidity. Color reproduction characteristics are required.

As a method for fixing a toner image, a heat roll fixing method is widely and generally used, and good fixing property and offset resistance at that time are also important characteristics required for the toner. . In recent copiers and printers, the processing speed has been increased, so that the fixing temperature has become lower and the fixing time has become shorter. Furthermore, in order to simplify the machine structure and facilitate maintenance, an oil-less fixing method that does not apply offset prevention oil to the heat roller for fixing has been developed. Demands are growing.

Various studies have been made on toners used in the two-component developing method to satisfy these required characteristics. In particular, the selection of the charge control agent and the release agent is important, and it is necessary to select a molecular design and a material according to the characteristics of the carrier used together with the toner. As the charge control agent, various skeleton charge control agents such as various salicylic acid metal complexes, quaternary ammonium salts, trimethylethane dyes, and metal complex salt azo dyes have been studied. Further, as the release agent, low molecular weight polypropylene or polyethylene wax has been mainly studied. For example, republished patent WO99 / 28729 proposes a toner using a novel salicylic acid-based zirconium complex or salt as a charge control agent. Further, in an example of the publication, a black toner using the charge control agent, a low molecular weight polypropylene wax, and carbon black is reported.

However, the toner sufficiently satisfies the fixing performance and the anti-offset performance in a wide temperature range from a low temperature range to a high temperature range, has good compatibility with a carrier, and reaches a target charge amount immediately after mixing, and No toner capable of maintaining the charge level has been found. In particular, recently, copiers and printers for high-speed color printing utilizing the features of the two-component developing system have been developed, and no toner for high-speed color printing suitable for such machines has been found.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner for developing an electrostatic image suitable for a heat roll fixing system, which shows good fixing / offset characteristics in a wide temperature range.

Another object of the present invention is to provide a color electrostatic image which is excellent in color reproducibility and transparency, exhibits a stable charging behavior even in continuous printing, and provides a good high-quality image. An object of the present invention is to provide a developing toner.

[0009]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention.

That is, the present invention provides a toner comprising a binder resin, a colorant, a release agent and a charge control agent, wherein the binder resin comprises: (A) divalent or more A polybasic acid compound selected from the group consisting of polybasic acids and / or acid anhydrides and / or lower alkyl esters thereof; (B) a polyester resin containing a dihydric or higher aliphatic polyhydric alcohol as a main component; A toner for developing an electrostatic image, wherein the mold agent is a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component, and the charge control agent is a zirconium complex or salt represented by the following general formula 1. To provide. <General formula 1>

[0011]

Embedded image Wherein R ₁ is a quaternary carbon, methine, methylene,
N may include a heteroatom of N, S, O, or P; Y represents a cyclic structure connected by a saturated bond or an unsaturated bond;
₂ and R ₃ are each independently an alkyl group, an alkenyl group, an alkoxy group, an aryl group or an aryloxy group which may have a substituent, an aralkyl group or an aralkyloxy group, a halogen group, hydrogen, a hydroxyl group, a substituent Which may have an amino group, a carboxyl group, a carbonyl group, a nitro group,
R ₄ represents hydrogen or an alkyl group; t is an integer of 0 to 1 to 12; m is an integer of 1 to 20; n is an integer of 0 to 1 to 20; Is an integer from 0 to 1 to 4, p is an integer from 0 to 1 to 4, q is an integer from 0 to 1 to 3, r is an integer from 1 to 20, and s is 0 or an integer from 1 to 20. )

The polybasic acid compound (A) used in the present invention selected from dibasic or higher polybasic acids and / or acid anhydrides and / or lower alkyl esters thereof includes, for example, phthalic anhydride, terephthalic acid , Isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, adipic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, malonic acid, Glutaric acid, azelaic acid, a dicarboxylic acid such as sebacic acid or a derivative thereof or an esterified product thereof is also a trifunctional or higher polycarboxylic acid such as trimellitic acid, trimellitic anhydride, pyromellitic acid, and pyromellitic anhydride. An acid or its derivative or its esterified product is mentioned.

Examples of the dihydric or higher aliphatic polyhydric alcohol (B) include, for example, 1,4-cyclohexanedimethanol, ethylene glycol, diethylene glycol,
Triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide random copolymer diol, ethylene oxide-propylene oxide block copolymer Diol, ethylene oxide-
Diols such as tetrahydrofuran copolymer diol, polycaprolactone diol, and sorbitol,
1,2,3,6-hexanetetraol, 1,4-sorbitan, pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl -1,
Examples include trifunctional or higher polyhydric alcohols such as 2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trimethylolbenzene.

The aliphatic alcohol component (B) which reacts with the carboxylic acid compound (A) includes neopentyl glycol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, and trimethylolethanetriol. Epoxy compounds such as glycidyl ether and pentaerythritol tetraglycidyl ether can also be used.

In the present invention, for example, an aromatic diol exemplified below can be used in combination with the aliphatic polyhydric alcohol. The aromatic diol that can be used in the present invention is polyoxyethylene- (2.0)
-2,2-bis (4-hydroxyphenyl) propane and its derivatives, 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 its derivatives.

Further, aromatic epoxy compounds such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, cresol novolak type epoxy resin, and phenol novolak type epoxy resin may be used as necessary. it can.

In the present invention, the flexibility of the molecular chain in the polyester resin is improved by using the aliphatic polyhydric alcohol, and when used as a two-component developer by mixing with the carrier, the stress applied to the carrier in the developing device is reduced. This has the effect of relaxing and preventing the resin coating phase on the carrier surface from peeling off, and as a result, the effect of extending the life of the developer can be obtained.

Further, the softening of the polyester main chain improves the fixability at low temperatures. Further, for the purpose of improving the fixing / offset performance, adding a wax to the toner is a commonly used means. In the polyester resin using the aliphatic polyhydric alcohol in the present invention, particularly, wax is used. Has good compatibility, and the fixing performance at low temperatures and the offset resistance are further improved.

Therefore, it is necessary to use the above aromatic diol within a range that does not impair the gist of the present invention. The amount of the aromatic diol used is 30 to the total alcohol component.
Desirably, it is at most mol%. More preferably 20
Mol% or less.

As the carboxylic acid component used in the present invention, naphthalenedicarboxylic acid and / or dimethylnaphthalate, diethylnaphthalate, dibutylnaphthalate and the like as lower alkyl esters thereof are more preferably used. It is necessary that these compounds use 1 mol% or more of the total acid component, and more preferably 5 mol%.
That is all.

A monomer containing a naphthalene ring structure is effective in increasing the Tg of the resin, and improves the heat-resistant cohesion of the resin. Particularly in a system mainly using a soft aliphatic diol as an alcohol component, a decrease in Tg of the resin can be suppressed. A resin having both of them can be obtained.

The polyester resin in the present invention can be obtained, for example, by conducting a dehydration condensation reaction or a transesterification reaction using the above-mentioned raw material components (A) and (B) in the presence of a catalyst. The reaction temperature and reaction time at this time are
Although not particularly limited, usually 150 to 300 ° C.
For 2 to 24 hours.

As a catalyst for carrying out the above reaction, for example, tetrabutyl titanate, zinc oxide, stannous oxide, dibutyltin oxide, dibutyltin dilaurate, paratoluenesulfonic acid and the like can be appropriately used.

The polyester resin used in the present invention preferably has a glass transition temperature (Tg) of 50 ° C. or higher, and particularly preferably has a Tg of 55 ° C. or higher. When the Tg is 50 ° C. or lower, a blocking phenomenon (thermal aggregation) tends to occur when the toner is stored, transported, or exposed to a high temperature inside a developing device of a machine.

The softening point of the polyester resin used in the present invention is 90 ° C. or higher, especially 90 ° C. to 1 ° C.
It is preferably in the range of 80 ° C, more preferably 95%.
C. to 160.degree. When the softening point is lower than 90 ° C., the toner is liable to cause agglomeration, and when storing or printing, trouble tends to occur.

Further, as a full-color toner,
When color reproducibility at the time of color superposition or transparency when fixed on an OHP sheet is required, the softening point of the polyester resin is preferably in the range of 90 ° C to 130 ° C, more preferably , 95 ° C to 120 ° C.
The acid value of the polyester resin of the present invention is 20 mgK
OH / g or less is preferable in that the moisture resistance of the toner becomes good.

As the coloring agent that can be used in the present invention, well-known coloring agents can be mentioned. Examples of the black colorant include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black classified according to the production method.

As an example of a chromatic colorant, a phthalocyanine C.I. I. Pigme
nt Blue 15-3, an indanthrone C.I. I.
Pigment Blue 60 and the like are quinacridone-based C.I. I. Pigment Red
122, azo C.I. I. Pigment Red 2
2, C.I. I. Pigment Red 48: 1, C.I.
I. Pigment Red 48: 3, C.I. I. Pig
Ment Red 57: 1, etc., and an azo-based C.I. I. Pigment Yellow 12,
C. I. Pigment Yellow 13, C.I. I.
Pigment Yellow 14, C.I. I. Pigm
ent Yellow 17, C.I. I. Pigment
Yellow 97, C.I. I. Pigment Yellow
ow 155, isoindolinone-based C.I. I. Pigm
ent Yellow 110, a benzimidazolone C.I. I. Pigment Yellow 151, C.I.
I. Pigment Yellow 154, C.I. I. P
and the like.

[0029] The content of the colorant is 100
It is preferably in the range of 1 part by weight to 20 parts by weight based on parts by weight. These colorants can be used alone or in combination of two or more.

The release agent used in the present invention is a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component. Such a release agent is preferable because it has good dispersibility in the polyester resin of the present invention, and has good release properties and slidability. When these waxes are added to the toner, better hot offset resistance and fixing strength can be obtained as compared with the same amount of polyolefin wax such as polypropylene wax and polyethylene wax.

Further, a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component acts not only as a release agent for preventing an offset phenomenon at the time of heat roll fixing, but also in a large number of sheets for a long time. Also in printing, for example, when used as a two-component developer toner, it gives a stable charge to the toner without adhering to the carrier surface and enables printing of high-quality and high-definition images without generation of scattering toner etc. And Further, when a color toner is used together with a chromatic colorant, a color toner having excellent transparency as compared with a hydrocarbon wax such as a polypropylene wax can be obtained. The color toner having such characteristics is used for printing on an OHP sheet, which is required to have a transparent and vivid projected image, and for printing an intermediate color having good color reproducibility by printing two or more colors in an overlapping manner. Are suitable.

Examples of the wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component include carnauba wax, montan ester wax, rice wax, scale insect wax, lanolin wax or compounds represented by the following general formulas 2 to 6: There is. <General formula 2>

Embedded image (R1 and R2 are a hydrocarbon group having 1 to 40 carbon atoms,
At least one of them represents a chain hydrocarbon group having 12 or more carbon atoms. )

<General formula 3>

Embedded image (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.)

<General formula 4>

Embedded image (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.)

<General formula 5>

Embedded image (R1 is a hydrocarbon group having 12 to 40 carbon atoms. R2 is a hydrocarbon group having 1 to 40 carbon atoms. A + b = 4, a represents an integer of 1 to 4, and b represents an integer of 0 to 3. Represents.)

<General formula 6>

Embedded image (R1, R2 and R3 are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which is a chain hydrocarbon group having 12 or more carbon atoms, and a and c are integers of 0 to 2,
a + c = 2. b is an integer from 1 to 4, and d is 1
Or 2. Furthermore, e = d-1. )

The following compounds are specific examples of the wax represented by the above general formula.

<Wax 1>: Specific example of general formula 2

Embedded image

<Wax 2>: Specific example of general formula 3

Embedded image

<Wax 3>: Specific example of general formula 4

Embedded image

<Wax 4>: Specific example of general formula 5

Embedded image

<Wax 5>: Specific example of general formula 6

Embedded image

<Wax 6>: Specific example of general formula 6

Embedded image

As the carnauba wax, it is preferable to use a free fatty acid-type carnauba wax from which free fatty acids have been removed by purification. The acid value of the free fatty acid type carnauba wax is preferably 8 or less, more preferably 5 or less. The free fatty acid-type carnauba wax becomes finer crystals than the conventional carnauba wax, and the dispersibility in the polyester resin is improved. The montan ester wax is refined from a mineral, and becomes fine crystals like the carnauba wax by refining, so that the dispersibility in the polyester resin is improved.

The montan ester wax preferably has an acid value of 30 or less. Rice wax is obtained by refining rice bran wax, and has an acid value of 13
The following is preferred.

The scale insect wax can be obtained by dissolving the waxy component secreted by the larva of the scale insect (also known as lobster) in, for example, boiling water, separating the upper layer, cooling and solidifying, or repeating this. The scale insect wax purified by such a means is white in a solid state, has an extremely sharp melting point, and is suitable as a toner wax in the present invention. The acid value is reduced to 10 or less due to purification, and is preferably 5 or less for toner.

Lanolin wax is obtained by purifying and dehydrating a waxy substance adhering to wool's wool, and preferably has an acid value of 8 or less, more preferably 5 or less.

Examples of the release agent mainly containing an aliphatic alcohol compound include those mainly containing a higher alcohol obtained by an oxidation reaction of paraffin, olefin or the like. Examples of the release agent containing an aliphatic alcohol as a main component include “Unilin 425”, “Unilin 550” (both by Petrolite), “NPS-9210”,
“PARACOL 5070” (Nippon Seiro Co., Ltd.) and the like.

Of the above specific examples, carnauba wax having an acid value of 8 or less, <i> the wax wax </ i>, and <wax 4>, which is a tetrabehenic acid ester of pentaerythritol, are the most preferred waxes that can be used in the present invention.

The wax of the present invention has a melting point of 65.
Those in the range of ゜ C to 130 ° C. have a large contribution to the offset resistance and are particularly preferable.

The wax may be used alone or in combination, and good fixing offset performance can be obtained by adding 0.3 to 15 parts by weight, preferably 1 to 5 parts by weight, to the binder resin. If the amount is less than 0.3 parts by weight, the offset resistance is impaired. If the amount is more than 15 parts by weight, the fluidity of the toner is deteriorated. This adversely affects the charging characteristics of the toner.

Incidentally, synthetic waxes such as polyamide wax, graft polymerization wax, modified polyolefin wax, polypropylene wax and polyethylene wax can be used in combination with the wax in the present invention.

In the present invention, a compound represented by the following general formula 1 is used as a charge control agent. <General formula 1>

Embedded image Wherein R ₁ is a quaternary carbon, methine, methylene,
N may include a heteroatom of N, S, O, or P; Y represents a cyclic structure connected by a saturated bond or an unsaturated bond;
₂ and R ₃ are each independently an alkyl group, an alkenyl group, an alkoxy group, an aryl group or an aryloxy group which may have a substituent, an aralkyl group or an aralkyloxy group, a halogen group, hydrogen, a hydroxyl group, a substituent Which may have an amino group, a carboxyl group, a carbonyl group, a nitro group,
R ₄ represents hydrogen or an alkyl group; t is an integer of 0 to 1 to 12; m is an integer of 1 to 20; n is an integer of 0 to 1 to 20; Is an integer from 0 to 1 to 4, p is an integer from 0 to 1 to 4, q is an integer from 0 to 1 to 3, r is an integer from 1 to 20, and s is 0 or an integer from 1 to 20. As the charge control agent of the present invention, compounds having various structures can be suitably used without departing from the general formula 1. However, the compounds having the following structures have higher charge-giving ability, charge stability, and transparency. It can be suitably used.

<Charge control agent 1>

Embedded image

<Charge Control Agent 2>

Embedded image

<Charge control agent 3>

Embedded image

The amount of the compound to be used is in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. With this range, sufficient charging performance can be obtained without a decrease in toner resistance.

As the charge control agent that can be used in combination with the compound of the general formula 1, a conventionally known charge control agent can be used. For example, a nigrosine dye, a triphenylmethane dye, a quaternary ammonium salt, a resin containing a quaternary ammonium group and / or an amino group as a positive charge control agent, a trimethylethane dye, a metal of salicylic acid as a negative charge control agent Complex salts, metal complex salts of benzylic acid, copper phthalocyanine, perylene, quinacridone, azo pigments, metal complex salt azo dyes, acid dyes containing heavy metals such as azochrome complexes, calixarene-type phenolic condensates, cyclic polysaccharides, carboxyl groups And / or a resin containing a sulfonyl group, and the like, if necessary.

In particular, when the toner of the present invention is used as a color toner, it is preferable to use a colorless compound as the charge control agent to be used in combination. Examples of the colorless negatively chargeable charge control agent include “Bontron E-8” manufactured by Orient Chemical Co., Ltd. as a metal (Zn) complex compound of salicylic acid.
"4" is a metal complex compound of benzylic acid such as "LR-147" or "LR-297" manufactured by Nippon Carlit.
As colorless positive charge control agents, TP-302, TP-415, and TP-610 having a quaternary ammonium salt structure;
(Hodogaya Chemical), Bontron P-51; (Orient Chemical), Copy Charge PSY (Clariant Japan), and the like. Since the charge control agent of the general formula 1 used in the present invention is a negative charge control agent, it is preferably a negative charge control agent when other charge control agents are used in combination.

In the present invention, various additives (referred to as external additives) can be used for modifying the surface of the toner, such as improving the fluidity and charging characteristics of the toner. 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 powders such as zirconium oxide and those obtained by surface-treating them with a hydrophobic agent such as silicone oil or silane coupling agent, polystyrene, acrylic, styrene acrylic, polyester, polyolefin, cellulose, polyurethane, benzoguanamine, melamine, nylon, Resin fine powders such as silicon, phenol, vinylidene fluoride, and Teflon (registered trademark) are used.

Among these, silicon dioxide (silica) whose surface has been subjected to a hydrophobic treatment with various polyorganosiloxanes, silane coupling agents and the like can be particularly preferably used. As such a product, for example, there is a product commercially available under the following trade names.

AEROSIL R972, R974, R202, R805, R812, RX200, RY200, R809, RX50, RA200HS, RA200H (Nippon Aerosil Co., Ltd.) WACKER HDK H2000, H2050EP HDK H3050EP, HVK2150 (Wacker Chemicals East Asia) Nipsil SS-10, SS-15, SS-20, SS-50, SS-60, SS-100, SS-50B, SS-50F, SS-10F, SS-40, SS-70, SS-72F, ( Nippon Silica Industry Co., Ltd.) CABOSIL TG820F (Cabot Specialty Chemicals, Inc.)

The particle size of the external additive is desirably 1/3 or less of the diameter of the toner, particularly preferably 1/10 or less. In addition, these external additives have different average particle diameters.
More than one species may be used in combination. The ratio of the external additive used is toner 1.
The amount is 0.05 to 5% by weight, preferably 0.1 to 3% by weight, based on 00 parts by weight.

In the toner of the present invention, other additives may be contained inside the toner particles. As an example, a lubricant such as metal soap and zinc stearate can be used, and as an abrasive, for example, cerium oxide and silicon carbide can be used.

When a part or all of the coloring agent is replaced with magnetic powder, it can be used as a magnetic one-component developing toner. As the magnetic powder, a ferromagnetic metal such as iron, cobalt, and nickel, or an alloy or compound powder such as magnetite, hematite, or ferrite is used. As these magnetic powders, those subjected to a hydrophobic treatment with an organic silicon or a titanium compound or the like, if necessary, are preferably used. The content of the magnetic powder is 15 to
70% by weight is good.

The toner composition of the present invention can be obtained by an extremely general manufacturing method irrespective of a specific manufacturing method. For example, a resin, a colorant, and a charge controlling agent are mixed with each other at the melting point (softening point) of the resin. Point) After melt-kneading as described above, it can be obtained by pulverizing and classifying.

Specifically, for example, the resin and the colorant are mixed by a kneading means such as a two-roll, three-roll, pressure kneader, or a twin-screw extruder. At this time, the colorant or the like may be uniformly dispersed in the resin, and the conditions for the melt-kneading are not particularly limited, but are usually 80 to 18
30 seconds to 2 hours at 0 ° C. The coloring agent may be previously subjected to a flushing treatment so as to be uniformly dispersed in the resin, or a master batch melt-kneaded with the resin at a high concentration.

Then, after cooling, the mixture is finely pulverized by a pulverizer such as a jet mill and classified by an air classifier or the like. The average particle size of the particles constituting the toner is not particularly limited, but is usually adjusted to be 5 to 15 μm. Usually, fine particles (hereinafter, referred to as an external additive) having a smaller particle size than the toner base are mixed with the toner base obtained in this manner using a mixer such as a Henschel mixer.

The toner of the present invention can be used as a two-component developer by mixing with a magnetic carrier. In this case, the surface of the magnetic carrier is desirably coated with a resin. By coating the surface with the resin, the charge of the developer is stabilized.

As a carrier for producing a two-component developer using the toner of the present invention, an iron powder carrier, a magnetite carrier, and a ferrite carrier used in a usual two-component developing system can be used. A ferrite or a magnetite carrier having high resistance, excellent environmental stability, and easy to form into a sphere and having good fluidity is preferably used. The shape of the carrier can be used without any particular problem, such as a spherical shape and an irregular shape. The average particle size is generally 10
The thickness is preferably from 500 to 500 μm, but is preferably from 30 to 80 μm for printing a high-resolution image.

Also, a coated carrier obtained by coating these carriers with a resin can be suitably used. Examples of the coated resin include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, and the like.
Polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether polyvinyl ketone, vinyl chloride / vinyl acetate copolymer, styrene / acrylic copolymer, straight silicone resin comprising 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 and the like can be used. Among these, silicone resin, fluororesin, and (meth) acrylic resin are particularly excellent in charge stability and coating strength, and can be more preferably used. That is, in the present invention, the magnetic carrier is preferably a resin-coated magnetic carrier coated with at least one resin selected from a silicone resin, a fluororesin, and a (meth) acrylic resin.

The method for coating the surface of the carrier core material with the resin is not particularly limited, but may be any of a dipping method of dipping in a solution of the coating resin, a spray method of spraying the coating resin solution onto the surface of the carrier core material, and a carrier method. Fluidized bed method in which the carrier is sprayed while being floated by flowing air, a kneader coater method in which a carrier core material and a coating resin solution are mixed in a kneader coater, and a solvent is removed.

The solvent used in the coating resin solution is not particularly limited as long as it dissolves the coating resin. For example, toluene, xylene, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane and the like can be used. The thickness of the coating layer on the carrier surface is usually 0.1
〜3.0 μm.

The weight ratio between the toner of the present invention and the magnetic carrier is not particularly limited.
The amount of the toner is 0.5 to 10 parts by weight per 00 parts by weight.

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

The remarkable technical effect of the toner for developing an electrostatic image of the present invention is exhibited in a developing / fixing apparatus which develops at a higher speed and performs heat roll fixing. As the recording medium in the present invention, any known and commonly used 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 films and OHP sheets.

[0077]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. In the following, numerical values in the composition table represent "parts by weight". An example of the synthesis of the binder resin used in preparing the toner first is shown below.

(Synthesis Example 1) Naphthalenedicarboxylic acid 87 parts by weight Terephthalic acid 249 parts by weight Diethylene glycol 26 parts by weight Neopentyl glycol 104 parts by weight Ethylene glycol 50 parts by weight Tetrabutyl titanate 2.5 parts by weight The mixture was placed in a four-necked flask, fitted with a thermometer, a stirring rod, and a nitrogen inlet tube. The reaction was carried out at 240 ° C. for 10 hours in an electric heating mantle heater under a normal pressure of nitrogen gas, and the pressure was sequentially reduced, and the reaction was continued at 10 mmHg. The reaction is ASTM
・ Tracking by softening point according to E28-517, softening point is 101 ℃
When the reaction reached, the reaction was terminated. The obtained polymer was a colorless solid, having an acid value of 7, and a glass transition temperature of 70 as measured by DSC.
° C and softening point was 102 ° C.

(Synthesis Example 2) Terephthalic acid 315 parts by weight Diethylene glycol 21 parts by weight Cyclohexanedimethanol 144 parts by weight Ethylene glycol 50 parts by weight Tetrabutyl titanate 2.5 parts by weight A reaction was carried out in the same manner as in Synthesis Example 1 using the above raw materials. went. The obtained polymer was a colorless solid, having an acid value of 9, a glass transition temperature of 60 ° C by DSC measurement, and a softening point of 97 ° C.

(Synthesis Example 3) Isophthalic acid 116 parts by weight Terephthalic acid 166 parts by weight Trimellitic anhydride 38 parts by weight Diethylene glycol 26 parts by weight Neopentyl glycol 104 parts by weight Ethylene glycol 50 parts by weight Tetrabutyl titanate 2.5 parts by weight or more The raw materials were placed in a glass 2L four-necked flask, fitted with a thermometer, a stirring rod and a nitrogen inlet tube, and reacted in an electric heating mantle heater at 240 ° C. under a normal pressure nitrogen stream for 10 hours. The reaction was continued. The reaction is ASTM
・ Tracking by softening point according to E28-517, softening point is 140 ℃
When the reaction reached, the reaction was terminated. The obtained polymer was a colorless solid, having an acid value of 5, and a glass transition temperature of 72 as determined by DSC.
° C and softening point was 141 ° C.

(Synthesis Example 4) Polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane 1650 parts by weight Isophthalic acid 415 parts by weight Terephthalic acid 415 parts by weight Tetrabutyl titanate 6 parts by weight The above raw materials were placed in a glass 2L four-necked flask, fitted with a thermometer, a stir bar and a nitrogen inlet tube, and reacted at 230 ° C. for 24 hours under a normal pressure nitrogen stream in an electric heating mantle heater. The reaction was continued at 10 mmHg. The reaction is ASTM
・ Tracking by softening point according to E28-517, softening point is 99 ℃
When the reaction reached, the reaction was terminated. The obtained polymer was a colorless solid, having an acid value of 7, and a glass transition temperature of 62 as measured by DSC.
° C and softening point was 103 ° C.

(Synthesis Example 5) Terephthalic acid 283 parts by weight Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 527 parts by weight Trimellitic anhydride 45 parts by weight Tetrabutyl titanate 2.5 Parts by weight

The above-mentioned raw materials were placed in a glass 2-L four-necked flask, fitted with a thermometer, a stirring rod and a nitrogen inlet tube, and heated at 240 ° C. under a normal pressure nitrogen stream in an electric heating mantle heater.
After the reaction for 5 hours, the pressure was sequentially reduced, and the reaction was continued at 10 mmHg.
The reaction was followed by a softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 133 ° C. The obtained polymer was a colorless solid, having an acid value of 5, a glass transition temperature of 64 ° C by DSC measurement, and a softening point of 134 ° C.

(Example 1) <Production of Toner> 93 parts by weight of resin of Synthesis Example 1 4 parts by weight of Fastgen Super Magenta R manufactured by Dainippon Ink and Chemicals 1 part by weight of charge control agent 1 purified carnauba wax No. 12 parts by weight (Acid value: 5, manufactured by Cera Rica NODA)
Are mixed with a Henschel mixer and kneaded with a twin-screw kneader. The kneaded material thus obtained was pulverized and classified to obtain “toner material A” having a volume average particle diameter of 7.5 μm.

100 parts by weight of the above-mentioned “toner raw material A” 1 part by weight of Nippon Aerosil silica “R-812” was mixed with a Henschel mixer, and then sieved.
"Toner A" was obtained.

<Adjustment of Developer> Four parts of toner A and a carrier “Ferrite Carrier F-150” manufactured by Powder Tech Co., Ltd. 9
The developer A was prepared by friction-mixing 6 parts.

Hereinafter, toners were prepared in the same manner as in Example 1 with the composition shown in Table 1, and developer A (Example 1) to developer E using toners using a linear polyester resin as a binder resin
(Example 5) and Developer H (Comparative Example 1) to Developer J
(Comparative Example 3) was produced. In addition, a developer F (Example 6), a developer G (Example 7), and a developer K (Comparative Example 4) to a developer M (Comparative Example 6) using a toner having a branched resin as a binder resin are manufactured. did.

[0088]

[Table 1]

The indications in the table are as follows.・ Magenta R; Fastogen Super Magenta R manufactured by Dainippon Ink and Chemicals ・ TYHG; Toner Yellow HG VP2155 manufactured by Clariant Japan ・ KET B.111; KET Blue 111 “Dainippon Ink and Chemicals” ・ Mogal L; Carbon black "Cabot Specialty Chemicals, Inc." Carnauba wax; 1 (acid value 5) manufactured by Cera Rica NODA Co., Ltd. 1 (acid value 2) manufactured by Cera Rica NODA Co., Ltd. ・ PP WAX; polypropylene wax manufactured by Viscol 550P “Sanyo Kasei” ・ Wax 4; tetrabehenate ester of pentaerythritol ・ E-84; zinc disalicylate complex “Orient Chemical”

<Fixing Offset Test by Heat Roll Fixing> An unfixed image sample of A-4 paper size was prepared using a test machine modified from a commercially available two-component developing type copying machine, and a heat roll fixing unit having the following specifications was prepared. The fixing start temperature and the presence or absence of an offset phenomenon were confirmed under the following test conditions. In order to measure the fixing start temperature, an image density remaining ratio calculated by the following equation was obtained.

Image density remaining ratio = image density after fastness test / image density before left test * Image density was measured by Macbeth image densitometer RD-918. * The image density after fastness test is the image density after rubbing the fixed image using a Gakushin type friction fastness tester (load: 200 g, rubbing operation: 5 strokes). Image density remaining ratio
At 80% or more, there was no practical problem, and the lowest temperature was the fixing start temperature.

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 Tables 2 and 3.

<Print Durability Test> Using a commercially available copying machine, the density of the image area and the density of the background stain in continuous printing of 50,000 sheets were measured, and the charge amount of the developer was measured. Image density and background dirt are measured by Macbeth densitometer RD-918.
Was measured. The background stain was obtained by subtracting the density of the white paper before printing from the density of the white background after printing. When the difference was less than 0.01, it was evaluated as ○, when it was less than 0.01 to 0.03, it was evaluated as Δ, and when it was 0.03 or more, it was evaluated as ×.

The charge amount was measured by using a blow-off charge amount measuring device by collecting toner from the inside of the developing device for each number of printed sheets. The results are shown in Tables 2 and 3.

<Heat Resistance Aggregation Test> Toner 10 before mixing with carrier in 100 cc cylindrical lidless cup
g was put in a thermostat set at 65 ° C. 2
After a lapse of 4 hours, the polycup was taken out, and the toner inside was discharged by slowly tilting the polycup on a horizontal table. At that time, there is no aggregation due to fusion of the toner particles, and the state where the toner powder spreads on the table is ○. The state in which the shape of the polycup as it was in the polycup while being kept almost was evaluated as x. The results are shown in Tables 2 and 3.

<Evaluation of OHP Sharpness> An unfixed image was formed on an OHP sheet using a commercially available copying machine, and the unfixed image was fixed using a separately prepared fixing tester. As a fixing tester, a heat roll fixing machine with a built-in temperature sensor was used at a roll temperature of 140 ° C. The heat roll (upper) is made of Teflon (registered trademark of DuPont), the lower roll is made of HTV silicon, and the load is 7 kg / 350 m.
m, the nip width was 4 mm, and the fixing speed was 50 mm / sec.

The OHP sheet prepared according to the above procedure was projected on a white screen by an overhead projector, and the sharpness was evaluated. The evaluation was performed by visual observation, and a clear and transparent good projected image was evaluated as ○, and a turbid blackish projected image was evaluated as ×. Table-Results
2 is shown.

[0098]

[Table 2]

The indications in the table are as follows. * "Charge amount"; [mu] C / g * "Background dirt evaluation" ○: less than 0.01, Δ: 0.01 to less than 0.03,
La: 0.03 or more

[0100]

[Table 3]

The indications in the table are as follows. * "Charge amount"; [mu] C / g * "Background dirt evaluation" ○: less than 0.01, Δ: 0.01 to less than 0.03,
La: 0.03 or more

From the above results, the toners of Comparative Examples 1 and 6 were inferior in fixability to the toners of Examples using the aliphatic diol. The toner of Comparative Example 2 using the polypropylene wax was inferior in low-temperature fixability and OHP permeability, and in the print durability test, the image density and charge amount at the initial stage of printing and at the time of printing 50,000 sheets were observed, and the background smear increased. confirmed. Further, a binder component or a wax component of the toner adheres to the carrier surface after printing 50KP (50,000 sheets), and generation of spent carrier is recognized. Stain was observed. Further, when the toner particles were sliced and the cross section thereof was observed with a microscope, it was recognized that polypropylene wax was dispersed as large particles in the binder resin.

The same applies to the toner of Comparative Example 4 (using polypropylene wax). The toners of Comparative Examples 3 and 5 using different types of charge control agents also showed variations in the image density and charge amount at the initial printing stage and at the time of printing 50,000 sheets in the print durability test, as in the other comparative examples. An increase in dirt was confirmed.

On the other hand, the toner of the embodiment has OHP transparency,
Excellent low-temperature fixability and anti-offset properties, the charge amount was constant even at 50 KP printing, and printing with a uniform image density could be performed. No toner scattering was observed around the developing device. Further, when the toner particles were sliced and observed with a microscope, it was observed that the wax was finely and uniformly dispersed in the toner particles.

[0105]

According to the present invention, a long-life image having excellent low-temperature fixability and anti-offset properties, exhibiting a stable charging behavior even during continuous printing, and providing good images without fluctuations in image density can be obtained. An electrostatic image developing toner can be obtained.

Further, the toner of the present invention has excellent transparency and exhibits good fixing / offset characteristics in a wide temperature range, so that it exhibits excellent characteristics as a color toner of an oilless heat roll fixing system.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masanobu Nakamura 1-17-30 Chuo Warabi, Saitama Prefecture 1-709 René Warabi 1-709 F term (reference) 2H005 AA01 AA06 CA14 CA25 DA01

Claims (4)

[Claims] 1. A toner comprising a binder resin, a colorant, a release agent, and a charge control agent, wherein the binder resin comprises: (A) a dibasic or higher polybasic acid and / or an acid anhydride; And / or a polybasic acid compound selected from these lower alkyl esters. (B) A polyester resin containing a dihydric or higher aliphatic polyhydric alcohol as a main component, wherein the releasing agent is a higher fatty acid ester compound and / or a fatty acid. A toner mainly composed of a group III alcohol compound, wherein the charge control agent is a zirconium complex or salt represented by the following general formula 1. <General formula 1> Wherein R ₁ is a quaternary carbon, methine, methylene,
N may include a heteroatom of N, S, O, or P; Y represents a cyclic structure connected by a saturated bond or an unsaturated bond;
₂ and R ₃ are each independently an alkyl group, an alkenyl group, an alkoxy group, an aryl group or an aryloxy group which may have a substituent, an aralkyl group or an aralkyloxy group, a halogen group, hydrogen, a hydroxyl group, a substituent Which may have an amino group, a carboxyl group, a carbonyl group, a nitro group,
R ₄ represents hydrogen or an alkyl group; t is an integer of 0 to 1 to 12; m is an integer of 1 to 20; n is an integer of 0 to 1 to 20; Is an integer from 0 to 1 to 4, p is an integer from 0 to 1 to 4, q is an integer from 0 to 1 to 3, r is an integer from 1 to 20, and s is 0 or an integer from 1 to 20. ) 2. The electrostatic charge according to claim 1, wherein 1 mol% or more of naphthalenedicarboxylic acid and / or an acid anhydride and / or a lower alkyl ester thereof is used as the polybasic acid compound. Image developing toner. 3. The release agent is at least one selected from carnauba wax, montan ester wax, rice wax, scale insect wax, lanolin wax, and compounds represented by the following general formulas 2 to 6. The toner for developing an electrostatic image according to claim 1, wherein: <General formula 2> (R1 and R2 are a hydrocarbon group having 1 to 40 carbon atoms,
At least one of them represents a chain hydrocarbon group having 12 or more carbon atoms. <General formula 3> (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 4> (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 5> (R1 is a hydrocarbon group having 12 to 40 carbon atoms. R2 is a hydrocarbon group having 1 to 40 carbon atoms. A + b = 4, a represents an integer of 1 to 4, and b represents an integer of 0 to 3. <General formula 6> (R1, R2 and R3 are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which is a chain hydrocarbon group having 12 or more carbon atoms, and a and c are integers of 0 to 2,
a + c = 2. b is an integer from 1 to 4, and d is 1
Or 2. Furthermore, e = d-1. ) 4. The electrostatic image developing toner according to claim 1, wherein the colorant is a chromatic organic pigment.