JP2003005450A - Electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner showing preferable fixing and offset characteristics in a wide temperature range, having excellent color reproducibility and transparency, showing stable electrification behavior even for continuous printing and forming preferable images with high picture quality. SOLUTION: The toner contains at least a binder resin, a coloring agent and an electrification controlling agent. The binder resin is a polyester resin prepared by the reaction of (A) polybasic acid compounds selected from polybasic acids having two or more valences and/or acid anhydrides and/or lower alkylesters of these and (B) aliphatic polyhydric alcohols of two or more valences as the main components (excluding compounds having a bis-phenol structure). The electrification controlling agent is a complex or salt expressed by formula (1).

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In a two-component developing method in electrophotography, a carrier shares functions such as stirring, carrying, and charging of a developer, and the functional separation of the carrier and the toner is clarified. Therefore, the two-component developing method is widely used because it is relatively easy to control the charging of the toner and can cope with the speedup.

As a method of 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 important characteristics required for the toner. . In recent copying machines or printers, the processing speed has been increased, and the fixing temperature has become lower and the fixing time has become shorter. In addition, in order to simplify the machine structure and facilitate maintenance, an oilless fixing method has been developed in which oil for offset prevention is not applied to the heat roll for fixing, and the demand for black toner suitable for this has increased. There is.

In order to satisfy these required characteristics, various studies have been conducted on the toner used in the two-component developing method. In particular, the selection of the charge control agent and the binder resin is important, and it is necessary to select the molecular design and the material according to the characteristics of the carrier used with the toner. In charge control agents, until now, various salicylic acid metal complexes,
Charge control agents having various skeletons such as a quaternary ammonium salt, a trimethylethane dye, and a metal complex salt azo dye have been studied.

However, the fixing performance and the anti-offset performance in a wide temperature range from the low temperature region to the high temperature region are sufficiently satisfied, the compatibility with the carrier is good, and the desired charge amount is instantly reached after mixing, and the long-term No toner has been found that can maintain the charge level. In particular, recently, a copying machine and a printer for high-speed printing utilizing the characteristics of the two-component developing system have been developed, and a high-speed printing toner suitable for such a machine has not been found.

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

Another object of the present invention is to provide a toner for developing an electrostatic charge image, which exhibits a stable charging behavior even during continuous printing and can obtain a high quality image.

[0007]

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.

In order to solve the above problems, the present invention provides a toner containing at least a binder resin, a colorant and a charge control agent, wherein the binder resin is (A) a divalent or higher polybasic base. A polybasic acid compound (B) selected from an acid and / or an acid anhydride and / or a lower alkyl ester thereof and a divalent or higher aliphatic polyhydric alcohol as a main component (provided that the compound is represented by the following general formula (1): And a charge control agent is a complex or a salt represented by the following general formula (2). It is provided. <General formula (1)>

[Chemical 4] (In the formula, R ¹ and R ² may be the same or different and each represents an ethylene group or a propylene group. Further, m and n
May be the same or different and represent an integer of 0 to 7, and m + n represents an integer of 0 to 7. ) <General formula (2)>

[Chemical 5] [Wherein, X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different, m
And m'represent an integer of 1 to 3, R ₁ and R ₃ are hydrogen atoms, alkyl having 1 to 18 carbons, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxyester,
Hydroxy, alkoxy having 1 to 18 carbon atoms, acetylamino, benzoylamino group or a halogen atom,
R ₁ and R ₃ may be the same or different, n and n ′ represent an integer of 1 to 3, R ₂ and R ₄ represent a hydrogen atom or a nitro group, and A ⁺ represents a cation ion. It has 75 to 98 mol% of ammonium ion, and also has hydrogen ion, sodium ion, potassium ion or a mixed ion thereof. ]

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The toner for developing an electrostatic charge image of the present invention (hereinafter abbreviated as "the toner of the present invention" or "the toner of the present invention") is used for producing the toner.
Examples of the polybasic acid compound (A) selected from divalent or higher polybasic acids and / or acid anhydrides and / or lower alkyl esters thereof include, 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 Acid, azelaic acid, dicarboxylic acid such as sebacic acid or a derivative thereof or an esterified product thereof, and also a trifunctional or higher polycarboxylic acid such as trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride. Alternatively, a derivative thereof or an esterified product thereof can be used.

Examples of the divalent or higher polyhydric aliphatic alcohol (B) include 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
Tetrahydrofuran copolymer diol, diol such as polycaprocactone diol, 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.

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

Further, in the present invention, an aromatic diol or a polyhydric alcohol having a valence of 3 or more can be used in combination within a range that does not affect the performance. Examples of aromatic diols and polyhydric alcohols having 3 or more valences include catechol, resorcinol, hydroquinone, and bisphenol A.
Type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, and the like. However, compounds having the bisphenol A skeleton represented by the above general formula (I) are excluded. Examples of aromatic diols 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
Examples include -bis (4-hydroxyphenyl) propane and derivatives thereof.

In the present invention, by using the aliphatic polyhydric alcohol, the flexibility of the molecular chain in the polyester resin is improved, and when mixed with the carrier and used as a two-component developer, the stress received by the carrier in the developing device is reduced. There is an effect of alleviating, and it is possible to obtain an effect that the resin coating phase on the carrier surface is prevented from peeling off, and as a result, the life of the developer is extended.

Further, the softening of the polyester main chain improves the fixability at low temperatures. Furthermore, for the purpose of improving the fixing / offset performance, adding a wax to the toner is a generally used means, but in the polyester resin using the aliphatic polyhydric alcohol according to the present invention, it is particularly preferable to use waxes. Has good compatibility, and the fixing performance at low temperature and 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 based on the total alcohol component.
It is desirable that the content is mol% or less. More preferably 20
It is not more than mol%.

Further, as the carboxylic acid component used in the present invention, naphthalenedicarboxylic acid, and / or lower alkyl ester thereof such as dimethyl naphthalate, diethyl naphthalate and dibutyl naphthalate are more preferably used. It is necessary to use 1 mol% or more of these compounds for all acid components, and more preferably 5 mol%.
That is all.

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.

The polyester resin used in the present invention can be obtained, for example, by performing a dehydration condensation reaction or a transesterification reaction using the above 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, it is usually 150 to 300 ° C.
It takes 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, paratoluene sulfonic 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 among them, one having a Tg of 55 ° C. or higher is particularly preferable. If the Tg is 50 ° C. or less, a blocking phenomenon (thermal aggregation) is likely to occur when the toner is stored, transported, or exposed to a high temperature inside the developing device of the machine.

The softening point of the polyester resin used in the present invention is 90 ° C. or higher, and particularly 90 ° C. to 1
It is preferably in the range of 80 ° C., more preferably 95
It is in the range of ℃ to 160 ℃. When the softening point is lower than 90 ° C., the toner is apt to cause an agglomeration phenomenon and tends to cause troubles during storage and printing, and when the softening point is higher than 180 ° C., fixability is often deteriorated.

Further, when fixing performance at a lower temperature is required as a black toner used together with a cyan toner, a magenta toner, and a yellow toner for a full-color toner, the softening point of the polyester resin is 90 ° C to
It is preferably in the range of 130 ° C., more preferably 9
It is in the range of 5 ° C to 120 ° C. The acid value of the polyester resin of the present invention is preferably 20 mgKOH / g or less in order to improve the moisture resistance of the toner.

Examples of the colorant that can be used in the present invention include carbon blacks such as furnace black, channel black, acetylene black, thermal black and lamp black, which are classified by the manufacturing method as black colorants. C. I. Pigment B
rack 11 iron oxide pigments, C.I. I. Pigme
nt Black 12 iron-titanium oxide-based pigments, phthalocyanine-based cyanine black BX, and the like. Further, it is also possible to use the chromatic color pigments exemplified below as a chromatic color toner, or use two or more kinds of pigments to adjust the color to black.

As a blue colorant which can be used in the toner of the present invention, a phthalocyanine type C.I. I. Pigment
Blue 1, 2, 15: 1, 15: 2, 15: 3
15: 4,15: 6,15,16,17: 1,27,2
8, 29, 56, 60, 63 and the like. As the bluish colorant, preferably C.I. I. Pigment Bl
ue 15: 3 (generic name Phthalocyanine Blue G), 1
5 (phthalocyanine blue R), 16 (metal-free phthalocyanine blue), 60 (indanthrone blue), and most preferably C.I. I. Pigment Bl
ue 15: 3, 60.

As the 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 etc. are mentioned. Preferably, C.I. I. Pigment Yellow 12 (generic name disazo yellow AAA), 13 (disazo yellow AAMX), 17 (disazo yellow AAO)
A), 97 (Fast Yellow FGL), 110 (Isoindolinone Yellow 3RLT), and 155.
(Sandrin Yellow 4G), 180 (benzimidazolone), most preferably C.I. I. Pigm
ent Yellow 17, 155, 180.

Further, as the red colorant, for example,
C. 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. 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 these colorants is preferably 1 to 20% by weight based on the whole toner. Above all 2
It is more preferably ˜15% by weight, particularly preferably 2 to 10% by weight. These colorants may be used either individually or in combination of two or more.

In the present invention, the compound represented by the following general formula (2) is used as a charge control agent. General formula (2) used in the present invention
Since the above charge control agent can be uniformly dispersed in the resin of the present invention, a desired charge amount can be obtained with a small amount. <General formula (2)>

[0029]

[Chemical 6] [Wherein, X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different, m
And m'represent an integer of 1 to 3, R ₁ and R ₃ are hydrogen atoms, alkyl having 1 to 18 carbons, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxyester,
Hydroxy, alkoxy having 1 to 18 carbon atoms, acetylamino, benzoylamino group or a halogen atom,
R ₁ and R ₃ may be the same or different, n and n ′ represent an integer of 1 to 3, R ₂ and R ₄ represent a hydrogen atom or a nitro group, and A ⁺ represents a cation ion. It has 75 to 98 mol% of ammonium ion, and also has hydrogen ion, sodium ion, potassium ion or a mixed ion thereof. ]

As the charge control agent used in the toner of the present invention, compounds having various structures can be suitably used within a range not deviating from the structure of the general formula (2), but a complex salt or a salt having the following structure is higher. It has charge imparting ability, charge stability, and transparency and can be used particularly preferably. The structural formulas of preferable charge control agents are shown below: <Charge control agent 1> to <Charge control agent 3>
Is. Of these, <charge control agent 1> is particularly preferable.

<Charge Control Agent 1>

[0032]

[Chemical 7] The cations are NH ₄ ⁺ and H ⁺ , Na ⁺ , K ⁺ or mixed ions thereof.

<Charge control agent 2>

[0034]

[Chemical 8] The cations are NH ₄ ⁺ and H ⁺ , Na ⁺ , K ⁺ or mixed ions thereof.

<Charge control agent 3>

[0036]

[Chemical 9] The cations are NH ₄ ⁺ and H ⁺ , Na ⁺ , K ⁺ or mixed ions thereof.

The amount of the charge control agent used is in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. Within this range, sufficient charging performance can be obtained without lowering the toner resistance. . It is more preferably 0.3 to 5 parts by weight, and particularly preferably 0.5 to 3 parts by weight.

As the charge control agent that can be used in combination with the compound of the general formula (2), 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,
Trimethylethane dyes as negative charge control agents, metal complex salts of salicylic acid, metal complex salts of benzyl acid, copper phthalocyanine, perylene, quinacridone, azo pigments, metal complex salt azo dyes, acid dyes containing heavy metals such as azochrome complex, calixarene Type phenolic condensates, cyclic polysaccharides, resins containing carboxyl groups and / or sulfonyl groups, etc. are used as necessary.
Since the charge control agent of the general formula (2) used in the present invention is a negative charge control agent, it is preferably a negative charge control agent when used in combination with other charge control agents.

Further, various known release agents (hereinafter referred to as wax in the present invention) such as polypropylene wax, polyethylene wax, etc.
Polyamide wax, Fischer-Tropsch wax, carnauba wax, ester wax and the like can be appropriately used as a release agent. Of these, waxes containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component are preferably used in the present invention. Such waxes are preferable because they have good dispersibility in the polyester resin of the present invention, and also have good mold releasability 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, the wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component functions as a release agent for preventing an offset phenomenon at the time of heat roll fixing, and also a large number of waxes for a long time. In printing, for example, when used as a toner for two-component developer, it gives a stable charge to the toner without adhering to the surface of the carrier, making it possible to print high-quality and high-definition images without the generation of scattered toner. And

As a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component, carnauba wax, montan ester wax, rice wax, scale wax, lanolin wax or the following general formulas (3) to (7) There are compounds represented. <General formula (3)>

[Chemical 10] (R ₁ and R ₂ are hydrocarbon groups having 1 to 40 carbon atoms,
At least one of them represents a chain hydrocarbon group having 12 or more carbon atoms. )

<General formula (4)>

[Chemical 11] (R ₁ , R ₂ and R ₃ are hydrocarbon groups 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)>

[Chemical 12] (R ₁ , R ₂ and R ₃ are hydrocarbon groups 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 (6)>

[Chemical 13] (R ₁ is a hydrocarbon group having 12 to 40 carbon atoms. R ₂ is a hydrocarbon group having 1 to 40 carbon atoms. Further, a + b = 4, a represents an integer of 1 to 4, b represents 0 to 3). Represents the integer of.)

<General formula (7)>

[Chemical 14] (R ₁ , R ₂ and R ₃ 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. Further, a and c are integers of 0 to 2). And
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 (3)

[Chemical 15]

<Wax 2>: Specific example of general formula (4)

[Chemical 16]

<Wax 3>: Specific example of general formula (5)

[Chemical 17]

<Wax 4>: Specific example of general formula (6)

[Chemical 18]

<Wax 5>: Specific example of general formula (7)

[Chemical 19]

<Wax 6>: Specific example of general formula (7)

[Chemical 20]

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 released 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 minerals, and by refining, it becomes microcrystalline like carnauba wax, and dispersibility in the polyester resin is improved.

The acid value of the montan ester wax is preferably 30 or less. Rice wax is a refined rice bran wax and has an acid value of 13
The following is preferable.

The scale insect wax can be obtained by, for example, dissolving a waxy component secreted by scale insect (also known as rotifer) larvae in hot water, separating the upper layer by cooling and solidifying, or repeating the process. The scale insect wax purified by such means is white in a solid state, has an extremely sharp melting point, and is suitable as a wax for toner in the present invention. The acid value becomes 10 or less by purification, and 5 or less is preferable for toner.

Lanolin wax is a wax-like substance adhering to sheep's hair, which is purified and dehydrated. It is preferable to use an acid value of 8 or less, more preferably 5 or less.

Examples of the releasing agent containing an aliphatic alcohol compound as a main component include those containing a higher alcohol obtained by an oxidation reaction of paraffin, olefin and the like as a main component. The release agent containing an aliphatic alcohol as a main component is, for example, "Unilin 425", "Unilin 550" (above Petrolite Co., Ltd.), "NPS-9210",
Examples include "Paracor 5070" (Nippon Seiwa Co., Ltd.) and the like.

Among the above specific examples, carnauba wax having a acid value of 8 or less, scale wax, and tetrabehenic acid ester of pentaerythritol <wax 4> is the most preferable wax which 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 make a large contribution to the offset resistance and are particularly preferable.

The wax may be used alone or in combination, and if the wax is contained in an amount of 0.3 to 15 parts by weight, preferably 1 to 5 parts by weight, good fixing offset performance can be obtained. If it is less than 0.3 parts by weight, the offset resistance is impaired, and if it is more than 15 parts by weight, the fluidity of the toner is deteriorated. In the case of a two-component developer, the spent carrier is generated by adhering to the carrier surface. However, the charging characteristics of the toner are adversely affected.

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

Various additives (referred to as external additives) can be used in the toner of the present invention in order to improve the fluidity of the toner, improve the charging characteristics, and improve the surface of the toner. Examples of external additives that can be used in the present invention include inorganic fine powders such as silicon dioxide, titanium oxide, aluminum oxide, cerium oxide, zinc oxide, tin oxide and zirconium oxide, and silicone oils, silane coupling agents and the like. Surface-treated with a hydrophobic treatment agent, polystyrene, acrylic, styrene acrylic, polyester, polyolefin, cellulose, polyurethane, benzoguanamine, melamine, nylon, silicone, phenol, vinylidene fluoride, Teflon (registered trademark), and other resin fine powder Etc. are used.

Among these, silicon dioxide (silica) whose surface is hydrophobized with various polyorganosiloxanes or silane coupling agents 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. External additive usage ratio is Toner 1
It is 0.05 to 5% by weight, preferably 0.1 to 3% by weight, based on 00 parts by weight.

The toner of the present invention may contain other additives inside the toner particles. For example, a lubricant such as metal soap and zinc stearate can be used, and a polishing agent such as cerium oxide and silicon carbide can be used.

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

The toner of the present invention can be obtained by a very general production method without depending on a specific production method.
For example, it can be obtained by melt-kneading a resin, a colorant, and a charge control agent at a melting point (softening point) or higher of the resin, then pulverizing and classifying.

Specifically, for example, the above-mentioned resin and colorant are mixed by a kneading means such as a two-roll, three-roll, pressure kneader, or 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 18
It is 30 seconds to 2 hours at 0 ° C. The colorant may be subjected to a flushing treatment in advance so as to be uniformly dispersed in the resin, or a masterbatch melt-kneaded with the resin at a high concentration may be used.

Then, after cooling it, there is a method in which it 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 having a particle size smaller than that of the toner base (hereinafter referred to as an external additive) are mixed with the toner base thus obtained by using a mixer such as a Henschel mixer.

The toner of the present invention can be used as a two-component developer by mixing it with a magnetic carrier. In this case, it is desirable that the surface of the magnetic carrier be coated with a resin. By coating the surface with 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 or a ferrite carrier used in a usual two-component developing system can be used, but among them, the true specific gravity is low, Ferrite or magnetite carrier, which has high resistance, is excellent in environmental stability, and has good fluidity because it is easy to be spherical, is preferably used. The shape of the carrier may be spherical, amorphous or the like, and may be used without any particular problem. Average particle size is generally 10
˜500 μm, but 30 to 80 μm is preferable for printing a high resolution image.

Coating carriers obtained by coating these carriers with a resin can also be suitably used, and examples of the coating resin 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 composed 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 and the like can be used. Among these, silicone resins, fluororesins, and (meth) acrylic resins are particularly excellent in charging stability and coating strength and can be used more preferably. That is, in the present invention, the magnetic carrier is preferably a resin-coated magnetic carrier coated with at least one resin selected from silicone resin, fluororesin, and (meth) acrylic resin.

The method of coating the resin on the surface of the carrier core material is not particularly limited, but a dipping method of immersing the resin in the solution of the coating resin, a spray method of spraying the coating resin solution on the surface of the carrier core material, or a carrier And the like, and a kneader coater method of removing the solvent by mixing the carrier core material and the coating resin solution in a kneader coater.

The solvent used in the coating resin solution is not particularly limited as long as it dissolves the coating resin, and 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.
Is about 3.0 μm.

The weight ratio of the toner of the present invention to the magnetic carrier is not particularly limited, but the carrier 1 is usually used.
The amount of toner is 0.5 to 10 parts by weight per 00 parts by weight.

The electrostatic image developing toner of the present invention thus obtained is developed and fixed on the recording medium by a known and commonly used method. As a fixing method, it is preferable to adopt a heat roll fixing method. . As the heat roll, the surface of the cylinder that can be heated to a temperature at which the toner can be fused and fixed,
For example, those coated with a coating resin having both releasability and heat resistance such as silicone resin or fluororesin are used. 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 particularly remarkable technical effect of the toner for developing an electrostatic charge image of the present invention is exhibited in a developing and fixing device in which development is performed 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.

[0079]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In the following, the numerical values in the composition table represent "parts by weight". An example of synthesizing the binder resin used for preparing the toner 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, equipped with a thermometer, a stir bar and a nitrogen introduction tube, reacted in an electric heating mantle heater at 240 ° C. for 10 hours under a normal pressure nitrogen stream, and then decompressed successively, and the reaction was continued at 10 mmHg. The reaction is ASTM
-Tracked by the softening point according to E28-517, the softening point is 101 ℃
When the reaction reached, the reaction was terminated. The obtained polymer is a colorless solid, having an acid value of 7 and a glass transition temperature of 70 according to the DSC measurement method.
The 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 The same reaction as in Synthesis Example 1 was performed using the above raw materials. went. The obtained polymer was a colorless solid, had an acid value of 9, a glass transition temperature of 60 ° C. by a DSC measurement method, 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 Put the raw material in a glass 2-liter four-necked flask, attach a thermometer, a stir bar and a nitrogen inlet tube, and react in an electric heating mantle heater at 240 ° C for 10 hours under a normal pressure nitrogen stream, and then reduce the pressure in sequence to 10 mmHg. And the reaction continued. The reaction is ASTM
-Tracked by the softening point according to E28-517, the softening point is 140 ℃
When the reaction reached, the reaction was terminated. The obtained polymer is a colorless solid having an acid value of 5 and a glass transition temperature of 72 according to the DSC measurement method.
The 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 or more Was placed in a glass 2 L four-necked flask, equipped with a thermometer, a stir bar and a nitrogen inlet tube, reacted in an electric heating mantle heater under atmospheric pressure nitrogen stream at 230 ° C. for 24 hours, and then sequentially depressurized, The reaction was continued at 10 mmHg. The reaction is ASTM
・ Tracking with the softening point according to E28-517, the softening point is 99 ° C
When the reaction reached, the reaction was terminated. The obtained polymer is a colorless solid having an acid value of 7 and a glass transition temperature of 62 according to the DSC measurement method.
C., softening point was 103.degree.

[0084] (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 raw materials were placed in a glass 2-liter four-necked flask, equipped with a thermometer, a stir bar and a nitrogen inlet tube, and heated at 240 ° C. under normal pressure nitrogen stream in an electric heating mantle heater at 240 ° C.
After reacting for 5 hours, the pressure was sequentially reduced and the reaction was continued at 10 mmHg.
The reaction was followed by the 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, had an acid value of 5, a glass transition temperature of 64 ° C. by a DSC measurement method, 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 Mogul L (carbon black; manufactured by Cabot Specialty Chemicals, Inc.) 1 part by weight of charge control agent 1 Purified carnauba wax No. 12 parts by weight (acid value 5, manufactured by Celarica NODA Co., Ltd.) are mixed with a Henschel mixer and kneaded with a biaxial kneader. The kneaded material thus obtained was crushed and classified to obtain "toner raw material A" having a volume average particle diameter of 7.5 µm.

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

<Preparation of Developer> 4 parts of Toner A and a carrier "Ferrite Carrier F-150" manufactured by Powder Tech Co., Ltd. 9
A developer A was prepared by friction mixing 6 parts.

Thereafter, toners were prepared in the same manner as in Example 1 with the formulations shown in Table 1 and the developer A (Example 1) to the developer E by the toner using the linear polyester resin as the binder resin.
(Example 5), and Developer H (Comparative Example 1) to Developer I.
(Comparative Example 2) was manufactured. In addition, a developer F (Example 6), a developer G (Example 7), and a developer J (Comparative Example 3) to a developer K (Comparative Example 4) are manufactured using a toner having a branched resin as a binder resin. did.

[0090]

[Table 1]

The display in the table is as follows.・ Mogal L ； Carbon black "Cabot
Specialty Chemicals, Inc. ”-Carnauba WAX; Carnauba Wax No. 1 (acid value 5) Ceralica NODA Co., Ltd. scale bug WAX; purified snow wax No. 1 (acid value 2) Ceralica NODA Co., Ltd. wax 4; pentaerythritol tetrabehenate ester S-34; azo dye (chromium complex salt) "Orient Chemical"

<Fixing Offset Test by Heat Roll Fixing> An unfixed image sample of A-4 paper size was prepared with 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 used. The fixing start temperature and the presence or absence of the offset phenomenon were confirmed under the following test conditions. In order to measure the fixing start temperature, the image density residual ratio calculated by the following formula was determined.

Image density residual 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 the 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). When the image density residual ratio was 80% or more, it was set to a level at which there was no practical problem, and the lowest temperature was set as the fixing start temperature.

The offset start temperature was set to a temperature at which the offset phenomenon was visually observed by observing the fixed image sample. The results are shown in Table-2 and Table-3.

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

The charge amount was measured with 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 Table-2 and Table-3.

<Heat Resistant Cohesion Test> Toner 10 before mixing with a carrier in a 100 cc open-ended cylindrical polycup.
Then, the mixture was placed in a constant temperature bath set at 65 ° C. Two
After 4 hours, the poly cup was taken out, and the poly cup was slowly tilted on a horizontal table so that the toner inside was taken out. At that time, there is no agglomeration due to fusion of the toner particles, and the toner powder spreads on the table ○, there is some agglomeration, but it is easy to loosen by poking with a finger △, even if it appears on the table The state in which the shape of the poly cup was almost maintained when it was in the poly cup as it was was marked with x. The results are shown in Table-2 and Table-3.

[0098]

[Table 2]

The display in the table is as follows. "Electrical charge"; μC / g "Soil stain evaluation" ○: Less than 0.01, △: 0.01 to less than 0.03,
×: 0.03 or more

[0100]

[Table 3]

The indications in the table are as follows. "Electrical charge"; μC / g "Soil stain evaluation" ○: Less than 0.01, △: 0.01 to less than 0.03,
×: 0.03 or more

From the above results, the toners of Comparative Example 1 and Comparative Example 4 were inferior in fixability to the toners of Examples using the aliphatic diol. The toners of Comparative Example 2 and Comparative Example 3 using only the charge control agent different from the charge control agent of the present invention showed variations in the image density and the charge amount at the initial stage of printing and after printing 50,000 sheets in the print durability test. It was confirmed that the amount of soiling increased.

On the other hand, the toners of the examples were excellent in low-temperature fixability and anti-offset property, the charge amount was constant even in the printing of 50 KP, and printing with 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.

[0104]

According to the present invention, excellent low-temperature fixability and anti-offset properties are exhibited, stable charging behavior is exhibited even during continuous printing, and good images having no fluctuation in image density can be obtained. A toner for developing an electrostatic image can be obtained.

Further, the toner of the present invention is excellent in transparency and exhibits excellent fixing / offset characteristics in a wide temperature range, and therefore exhibits excellent characteristics also as an oilless heat roll fixing type toner.

Claims (4)

[Claims] 1. A toner containing at least a binder resin, a colorant and a charge control agent, wherein the binder resin comprises (A) a dibasic or higher polybasic acid and / or an acid anhydride and / or these. Of a polybasic acid compound (B) selected from the lower alkyl esters of (1) and a divalent or higher polyhydric aliphatic polyalcohol as main components (excluding compounds having a bisphenol skeleton represented by the following general formula (1)) A toner for developing an electrostatic charge image, which is made of a polyester resin, wherein the charge control agent is a complex or salt represented by the following general formula (2). <General formula (1)> (In the formula, R ¹ and R ² may be the same or different and each represents an ethylene group or a propylene group. Further, m and n
May be the same or different and represent an integer of 0 to 7, and m + n represents an integer of 0 to 7. ) <General formula (2)> [Wherein, X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, and X ₁ and X ₂ may be the same or different, m
And m'represent an integer of 1 to 3, R ₁ and R ₃ are hydrogen atoms, alkyl having 1 to 18 carbons, alkenyl, sulfonamide, mesyl, sulfonic acid, carboxyester,
Hydroxy, alkoxy having 1 to 18 carbon atoms, acetylamino, benzoylamino group or a halogen atom,
R ₁ and R ₃ may be the same or different, n and n ′ represent an integer of 1 to 3, R ₂ and R ₄ represent a hydrogen atom or a nitro group, and A ⁺ represents a cation ion. It has 75 to 98 mol% of ammonium ion, and also has hydrogen ion, sodium ion, potassium ion or a mixed ion thereof. ] 2. The electrostatic charge according to claim 1, wherein 1 mol% or more of naphthalene dicarboxylic acid, and / or its acid anhydride, and / or its lower alkyl ester is used as the polybasic acid compound. Toner for image development. 3. The toner for developing an electrostatic charge image according to claim 1, wherein the charge control agent is a complex or salt represented by <charge control agent 1> having the following structure. <Charge control agent 1> 4. The toner for developing an electrostatic charge image according to claim 1, further comprising a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a release agent.