JP2001296686A - Static charge image-developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner which is superior in fixing property and offset resistance, showing stable electrification be behavior, even when used for continuous printing, and is satisfactory in durability with which is satisfactory image of high image quality can be obtained. SOLUTION: The toner contains wax, which is an ester of a carboxylic acid and alcohol and has a structure having a 12-40C chain hydrocarbon group in a part of the molecule, and the toner has 0.05×1016 Ω.cm to 1.50×1016 Ω.cm for resistivity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art As an electrophotographic method, US Pat.
No. 97,691, JP-B-42-23910 and JP-B-43-24748, various methods are described. Usually, various methods are described on an electrostatic latent image carrier such as a photoconductive photoreceptor. An electrostatic latent image is formed by charging and exposure, and then the electrostatic latent image is developed with a toner composition containing a colorant in a binder resin, and the obtained toner image is transferred to a support such as transfer paper. In general, a visible image is formed by fixing.

[0003] Toners used in electrophotography have been examined in various ways, but in recent years, with the development of the information-oriented society, there has been a demand for higher quality of printed images, higher speed of recording, higher density, and the like. The demand for toners for recording electrostatic latent images as visible images on non-print media has become excessive. In particular, the toner used in the heat roll fixing method requires stable fixing behavior in a wide temperature range and anti-offset properties, and high-quality and high-precision printing is stable without polluting the inside of the machine even during long-term use. It is required that this be done.

[0004] In the heat roll fixing, toner particles electrostatically adhering to the transfer paper are melted and fixed to the transfer paper by passing between pressurized and heated heat rolls. At this time, if the temperature of the roll surface is too high, the viscosity of the melted toner decreases and adheres to the heat roll. This is called a hot offset (hereinafter simply referred to as offset),
The toner adhering to the heat roll is re-transferred to the transfer paper when the roll makes one rotation, and stains the non-image portion, resulting in a decrease in print quality.

[0005] The anti-offset performance means that the toner does not offset. Generally, a substance having a releasing effect such as wax is contained or dispersed in the toner, and the anti-offset performance in a wide range from a low temperature to a high temperature. I have been able to have performance.

Hitherto, synthetic waxes such as polypropylene wax and polyethylene wax have been mainly studied as waxes.
JP-A-3-5764 and JP-A-5-119509 disclose examples using natural waxes such as montan wax, carnauba wax and rice wax.

[0007] Alternatively, in order to further improve the anti-offset performance, Japanese Patent Application Laid-Open No. H11-237759 and Japanese Patent No. 258
No. 5,755, JP-A-11-194543 and the like have proposed using a fatty acid ester as a wax.

Certainly, the fatty acid ester wax has an excellent releasing effect, and exhibits good fixing / offset resistance in a wide temperature range in a heat roll fixing system. However, the above publications using the wax do not disclose an invention satisfying all the characteristics required for the heat roll toner described above. In particular, there has been obtained a toner which does not generate stain on the non-image portion, can print a high-density, high-quality, and high-precision printed matter for a long time, and which does not generate scattered toner even when used for a long time. Absent.

[0009]

SUMMARY OF THE INVENTION The present invention has good fixing / offset resistance in a wide temperature range in a heat roll fixing system, and generates scattered toner which contaminates the inside of the machine even after long use. It is an object of the present invention to provide a toner which exhibits stable charging behavior without causing a high density, high quality and high precision printing.

[0010]

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 and a wax, wherein the toner has a resistance value of 0.05 × 10 16 Ω ·
cm to 1.50 × 10 16 Ω · cm, wherein the wax is an ester of a carboxylic acid and an alcohol, and has a structure having a chain hydrocarbon group having 12 to 40 carbon atoms in a part of the molecule. And a toner for developing an electrostatic image.

The binder resin used in the present invention includes:
For example, polystyrene, styrene- (meth) acrylate copolymer, styrene-conjugated diene copolymer, polyester, epoxy resin, polybutyral resin, xylene resin, coumarone indene resin and the like can be used. -It is preferable to use an acrylate copolymer, a styrene-conjugated diene copolymer, or a polyester resin.

The styrene- (meth) acrylate copolymer preferably used in the present invention can be obtained, for example, by copolymerizing the following monomers.

(A) Styrene and its derivatives; alkylstyrenes such as styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene and octylstyrene Fluorostyrene, chlorostyrene, bromostyrene, dibromostyrene, halogenated styrene such as iodostyrene, further nitrostyrene,
Examples include acetylstyrene and methoxystyrene.

(B) (meth) acrylate monomers; for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl Alkyl (meth) acrylates such as (meth) acrylate, tertiary butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) Alicyclic (meth) acrylates such as acrylates, aromatic (meth) acrylates such as benzyl (meth) acrylate, hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, and (meth) acryloxy Phosphoric acid group-containing (meth) acrylates such as ciethyl phosphate, 2-chloroethyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, and halogen atoms such as 2,3-dibromopropyl (meth) acrylate ( (Meth) acrylates, epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and ether group-containing (meth) acrylates such as 2-ethoxyethyl (meth) acrylate;
Examples thereof include a basic nitrogen atom or amide group-containing (meth) acrylate such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

(C) Unsaturated compounds copolymerizable therewith can be used if necessary. For example,
(Meth) acrylic acid, α-ethylacrylic acid, crotonic acid, α-methylcrotonic acid, α-ethylcrotonic acid, isocrotonic acid, addition-polymerizable unsaturated aliphatic monocarboxylic acid such as tiglic acid, ungeric acid, or maleic acid Examples include addition-polymerizable unsaturated aliphatic dicarboxylic acids such as acids, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, and dihydromuconic acid.

(D) Still other copolymerizable unsaturated compounds include vinyl monomers containing a sulfo group such as sulfoethylacrylamide, vinyl monomers containing a nitrile group such as (meth) acrylonitrile, vinyl methyl ketone,
Ketone group-containing vinyl monomers such as vinyl isopropenyl ketone, N-vinylimidazole, 1-vinylpyrrole,
A vinyl monomer containing a basic nitrogen atom or an amide group, such as 2-vinylquinoline, 4-vinylpyridine, N-vinyl-2-pyrrolidone, and N-vinylpiperidone, can be used.

(E) A crosslinking agent may be used together with the vinyl monomer. As a crosslinking agent, for example, divinylbenzene, divinylnaphthalene, divinylether,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexane glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetra Methylolmethane tetra (meth) acrylate and the like can be mentioned.

As a method for producing the styrene- (meth) acrylic acid ester copolymer, a usual polymerization method can be adopted, and the polymerization reaction is carried out in the presence of a polymerization catalyst such as solution polymerization, suspension polymerization and bulk polymerization. Is performed.

Examples of the polymerization catalyst include 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 1,1'-azobis (cyclohexane-1-yl).
(Carbonitrile), benzoyl peroxide, dibutyl peroxide, butyl peroxybenzoate, and the like, and the amount used is 0.1 to 10.
0% by mass is preferred.

The styrene- (meth) acrylate copolymer most preferably used in the present invention is (c)
And a resin (hereinafter, referred to as polymer B) obtained by crosslinking a styrene- (meth) acrylate copolymer (hereinafter, referred to as polymer A) to which a carboxyl group-containing vinyl monomer exemplified as above is added as an essential component with a metal salt.

Such a resin is a thermoplastic resin, also called an ionomer, and has a crosslinked structure by ionic bonds or coordinate bonds. At room temperature, this kind of resin has toughness and excellent abrasion resistance due to the presence of the cross-linked structure, and under heat, the cross-linked structure is broken and becomes a molten state. Suitable for toners.

The metal salts used for crosslinking the resin include Al and B
a, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Ni, Pb, S
Examples include halides such as n, Sr, and Zn, hydroxides, oxides, carbonates, carboxylate salts, alkoxylates, and chelate compounds.

In order to bond these metals to the polymer A to form a salt, the polymer A is required to have a halide, hydroxide, oxide, carbonate, carboxylate, alkoxylate, chelate, or the like. Compounds and the like may be appropriately reacted. This reaction can be sufficiently achieved either by heating and stirring the required components in the presence of a solvent or by melt-kneading in the absence of a solvent.

The polymer A and the polymer B are represented by the following formula (1):
It is desirable to satisfy the relationship represented by the expression (2). 10-5 ≦ N ≦ 2 × 10-3 (1) T1-TS ≧ 20 ° C. (2) [In the above formula, N is the number of moles of carboxyl ions converted into metal contained in 1 g of the polymer B, and T1 is The softening point and TS of the polymer B according to the ring and ball method (JIS K2531, K2548) are those of the polymer A
And Tg represent the glass transition temperature of the polymer B measured by a DSC method, respectively. ]

In the formula (1), when N is 10-5 or less, there is no viscosity effect due to metal chloride, and N is 2 × 10-3.
If it is above, there is a possibility that the charging characteristics of the toner may be hindered, and the fixing start temperature is increased. A more specific preferred viscoelastic range is described by equation (2). That is, the ring-and-ball method softening point temperature, which measures the temperature at the time of constant deformation under a constant load, is a kind of viscosity index, but the softening point of the polymer B according to the present invention is T1, Where T1 is the softening point of the polymer B, that is, the softening point of the polymer B is TS.
A toner using a polymer exhibiting a value of at least 20 ° C. or more is preferable in the heat roll fixing system.

The polyester resin suitably used in the present invention is obtained by dehydrating and condensing a dicarboxylic acid and a diol by an ordinary method. Examples of the dicarboxylic acid include phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, adipic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, and cyclohexanedicarboxylic acid. Examples thereof include acids, succinic acid, malonic acid, glutaric acid, azelaic acid, dicarboxylic acids such as sebacic acid and derivatives thereof.

Examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, bisphenol A, 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 derivatives thereof.

Further, for example, polyethylene glycol,
Diols such as polypropylene glycol, ethylene oxide-propylene oxide random copolymer diol, ethylene oxide-propylene oxide block copolymer diol, ethylene oxide-tetrahydrofuran copolymer diol, and polycaprolactone diol can also be used.

If necessary, a trifunctional or higher functional aromatic carboxylic acid such as trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic anhydride or a derivative thereof, or sorbitol, 1,2,3 , 6-hexanetetraol, 1,4-sorbitan, pentaerythritol, 1,2,4-butanetriol,
Trifunctional or higher alcohols such as 5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trimethylolbenzene Or bisphenol A epoxy resin, bisphenol F epoxy resin, ethylene glycol diglycidyl ether, hydroquinone diglycidyl ether, N, N-diglycidylaniline, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane Triglycidyl ether, pentaerythritol tetraglycidyl ether, neopentyl glycol diglycidyl ether, cresol novolak epoxy resin, phenol novolak Trifunctional or more, such as a type epoxy resin, a polymer or copolymer of a vinyl compound having an epoxy group, an epoxidized resorcinol-acetone condensate, a partially epoxidized polybutadiene, and a semi-dry or dry fatty acid ester epoxy compound. Can be used in combination.

As the polyester resin used in the present invention, a polyester resin cross-linked with an epoxy compound having two or more epoxy groups in one molecule is particularly preferred because of its excellent fixability and offset resistance. One epoxy group reacts with a carboxyl group or a hydroxyl group to generate a secondary hydroxyl group, and this hydroxyl group further reacts with another carboxyl group. That is, since one epoxy group acts as a divalent group, an epoxy compound having two or more epoxy groups in one molecule is a crosslinker having four or more valences, and gives the resin an offset resistance. Very effective for.

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

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

Further, in the present invention, a styrene-conjugated diene copolymer can be suitably used. The styrene-conjugated diene copolymer can be obtained by a known and commonly used technique, but can be easily obtained by charging monomers at once or by an in-situ method such as multi-step charging, for example, by emulsion polymerization. Can be done.

As the monomer used in the styrene-conjugated diene copolymer, styrene or its derivative exemplified in the above (a) can be used. As the conjugated diene, for example, butadiene, isoprene and the like can be mentioned. Butadiene is preferred among the conjugated dienes.

The styrene-conjugated diene copolymer may be a multi-component copolymer with other copolymerizable monomers as long as the properties of the copolymer of styrene and conjugated diene are not impaired. .

Examples of such copolymerizable monomers include:
For example, in addition to vinyl chloride and vinyl acetate, the monomers exemplified in the above (b) to (e) can be mentioned.

The weight average molecular weight (Mw) of the copolymer of styrene and conjugated diene is preferably from 40,000 to 200,000. If it is less than 40,000, the toner layer strength in the image area is not sufficiently obtained, and the anti-offset performance (the effect of preventing the toner from being adhered to the heat roll) is extremely reduced. If it exceeds 200,000, the softening point is increased. Therefore, the fixing performance is greatly increased under ordinary fixing conditions, which is not preferable.

The ratio of the monomer components constituting the styrene-butadiene copolymer is preferably such that the ratio of the butadiene monomer is 5 to 20% by mass. If the amount is less than 5% by mass, the effect of imparting rubber elasticity is small, so that it is not preferable.

The styrene-acrylate copolymer, styrene-conjugated diene copolymer, and polyester resin used in the present invention need only have a proper glass transition point and softening point as a toner. The point (ring and ball method; JIS K2531, K2548) is preferably from 120 to 180 ° C, more preferably from 140 to 170 ° C. 12
If the temperature is lower than 0 ° C., offset at a high temperature tends to occur. If the temperature is higher than 180 ° C., the fixability at a low temperature deteriorates. Further T
Preferably, g is in the range of 35-75C.

The acid value is desirably 30 or less, particularly desirably 15 or less. If the acid value is too high, the charge amount will decrease, and the desired charge amount cannot be obtained.

As the coloring agent that can be used in the present invention, well-known coloring agents can be mentioned. Carbon blacks such as furnace black, channel black, acetylene black, thermal black, and lamp black classified according to the production method are used as black colorants, and phthalocyanine C.I. I. PigmentBl
ue 15-3, an indanthrone C.I. I. Pigm
ent Blue 60 and the like, and quinacridone C.I. I. Pigment Red 122,
Azo-based C.I. I. Pigment Red 22, C.I.
I. Pigment Red 48: 1, C.I. I. Pig
Ment Red 48: 3, C.I. I. Pigment
Red 57: 1, etc., and an azo-based C.I. I. Pigment Yellow 12, C.I. I.
Pigment Yellow 13, C.I. I. Pigm
ent Yellow 14, C.I. I. Pigment
Yellow 17, C.I. I. Pigment Yellow
ow 97, C.I. I. Pigment Yellow 1
55, isoindolinone-based C.I. I. Pigment
Yellow 110, a benzimidazolone C.I.
I. Pigment Yellow 151, C.I. I. P
pigment yellow 154, C.I. I. Pigm
ent Yellow 180, and the like. The content of the colorant is preferably in the range of 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the binder resin. These colorants are 1
Species or a combination of two or more can be used.

The wax used in the present invention is an ester compound of a carboxylic acid having a chain hydrocarbon group having 12 to 40 carbon atoms in a part of the molecule and an alcohol. Examples of the wax having such a structure are as follows. Is a compound represented by the following general formulas 1 to 5, and in the present invention, a compound containing at least one selected from these is preferable.

[0044]

Embedded image <General formula 1> (R1 and R2 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.)

[0045]

Embedded image <General formula 2> (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them is a hydrocarbon group having 1 carbon atom.
Shows two or more chain hydrocarbon groups. )

[0046]

Embedded image <General formula 3> (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them is a hydrocarbon group having 1 carbon atom.
Shows two or more chain hydrocarbon groups. )

[0047]

Embedded image <General formula 4> (R1 is a hydrocarbon group having 12 to 40 carbon atoms.
R2 is a hydrocarbon group having 1 to 40 carbon atoms. Also, a + b = 4
And a represents an integer of 1 to 4, and b represents an integer of 0 to 3. )

[0048]

Embedded image <General Formula 5> (R1, R2, and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them has 1 carbon atom.
2 or more chain hydrocarbon groups. A and c are integers of 0 to 2, and a + c = 2. b is an integer of 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.

[0050]

Embedded image <Wax 1>: Specific example of general formula 1

[0051]

Embedded image <Wax 2>: Specific example of general formula 2

[0052]

Embedded image <Wax 3>: Specific example of general formula 3

[0053]

Embedded image <Wax 4>: Specific example of general formula 4

[0054]

Embedded image <Wax 5>: Specific example of general formula 5

[0055]

Embedded image <Wax 6>: Specific example of general formula 5

Of the above specific examples, wax 1 and wax 4 can be suitably used, and wax 4 is the most preferred wax which can be used in the present invention.

In the present invention, the wax comprising an ester of a unit price or a polyvalent carboxylic acid having a chain hydrocarbon group having 12 to 40 carbon atoms and a unit price or a polyhydric alcohol can be used in a wide temperature range at the time of heat roll fixing. In addition to its function as a release agent to prevent the offset phenomenon, it does not adhere to the carrier surface even when printing a large number of sheets for a long time, gives stable charge to the toner, and does not generate scattered toner. In addition, it is possible to print a high-definition image.

It is desirable that the wax is contained in an amount of 0.3 to 15 parts by weight, preferably 1 to 5 parts by weight, based on the binder resin. If the amount is less than 0.3 part by mass, the offset resistance is poor. If the amount is more than 15 parts by mass, the fluidity of the toner is deteriorated, and the development stability is adversely affected.

In the present invention, various waxes known so far, for example, polypropylene wax, polyethylene wax, polyamide wax, Fischer-Tropsch wax, synthetic ester wax, as long as the effects of the wax used in the present invention are not impaired. A montan ester wax, carnauba wax, rice wax and / or scale insect wax can be used in combination.

In general, electrophotographic toners must have appropriate triboelectric charging properties and charge leakage properties. If the charge leakage characteristic is small and the frictional charging characteristic is superior, the charge amount of the toner becomes too high.For example, in the case of a two-component developer, the toner does not separate from the carrier, and the electrostatic latent image on the photoreceptor is formed. The amount of attracted toner decreases and the image density decreases. On the other hand, if the leakage characteristic is large, the charge amount of the toner is reduced, and the toner is easily separated from the carrier.

The toner using the specific wax specified in the present invention has an electric resistance of 0.05 × 10 16 Ω · cm or more.
It must be 1.50 × 10 16 Ω · cm. More preferably, 0.10 × 10 16 Ω · cm to 1.00 × 10
It is 16 Ω · cm. In the toner of the present invention, by adjusting the resistance value to fall within this range, high-image-density printing is possible, and a good toner is obtained in which non-image areas are free from contamination and scattering toner. Can be

When the electric resistance of the toner of the present invention is 1.50 × 10 16 Ω · cm or more, the image density is reduced as described above. In addition, 0.05 × 1016Ω
cm or less, the charge amount of the toner is remarkably reduced, resulting in a developer with a large amount of stain fog and scattered toner in the non-image area.

Although the reason is not clear, the wax having a specific structure used in the present invention has a tendency to increase the resistance value of the toner as compared with other polypropylene waxes and the like. This is a unique value found by the present inventors when using a wax having a specific structure. Therefore, for example, it is necessary to take the following means in order to make the resistance value of the toner of the present invention within the above range.

The means for controlling the resistance value of the toner of the present invention to the above-mentioned range is not particularly limited, such as using various resistance adjusting agents such as magnetic powders and metal salt compounds. In this method, a colorant having an appropriate resistance value is selected and the toner resistance value is adjusted in consideration of the balance between the image density after printing and the toner resistance value.

The preferred resistance value of the coloring agent used in the present invention is in the range of 0.05 Ω · cm to 0.80 Ω · cm. Particularly preferably, 0.10 Ω · cm to 0.50 Ω ·
cm. Commercial products of such carbon black include, for example, VULCAN P, VULCAN
N, VULCAN XC-72, REGAL 400,
BLACK PEARLS 1300 (manufactured by Cabot Specialty Chemicals, Inc.), MC
F-88, # 50, # 55, # 45 (manufactured by Mitsubishi Chemical), CONDUCTEX 975 (manufactured by Columbia Carbon), and the like.

By using these carbon blacks, the resistance value of the toner can be set within the above range. If the resistance value of carbon black is 0.80 Ω · cm or more, it is necessary to include a considerable amount of carbon black in the toner in order to make the resistance value of the toner fall within the above range. The ratio becomes small, and the fixing performance is lowered. Conversely, if the resistance value of the carbon black is 0.05 Ω · cm or less, it becomes necessary to reduce the content of the carbon black in the toner, and as a result, it becomes difficult to obtain a desired image density.

As described above, in the present invention, a high density, high quality and high precision printed image can be obtained using the wax according to the present invention having excellent offset resistance without causing stains and toner scattering of the non-image area. In order to obtain a stable print in long-time printing, the resistance value of carbon black is 0.05Ω
cm to 0.80 Ω · cm, particularly preferably 0.1
By using a material in the range of 0 Ω · cm to 0.50 Ω · cm, the resistance value of the toner can be set in the above range.

The resistance value of the toner was measured at a pressure of 2.5 t / cm 2 with a pellet formed into a thickness of 5.0 ± 0.5 mm and a diameter of 50 mm using an R8340A electric resistance meter manufactured by Advantest Corporation. The temperature at the time of measurement is 22-28
C., humidity were measured at 50 to 70% RH, and the electrode diameter was measured at 35 mm.

The resistance of the colorant is 1.6 cm in diameter.
Is a value obtained by adding a colorant to the cell (1), applying a pressure to 1.0 g / cc, and applying a voltage of +50 V.

The charge control of the toner may be performed by the binder resin and the colorant itself, but a charge control agent may be used if necessary. Examples of the negative charge control agent that can be used in the present invention include a trimethylethane dye, a metal complex salt of salicylic acid, a metal complex salt of benzyl acid, copper phthalocyanine, perylene, quinacridone, an azo pigment, a metal complex salt azo dye,
Examples include heavy metal-containing acid dyes such as azochrome complexes, calixarene-type phenol-based condensates, cyclic polysaccharides, and resins containing a carboxyl group and / or a sulfonyl group.

More specifically, "Bontron S-34" manufactured by Orient Chemical Co., Ltd. and "Aizen Spiron Black TR" manufactured by Hodogaya Chemical Co., Ltd. as metal complex salt azo dyes.
H "and the like are preferably used.

In particular, it is desirable to use a colorless charge control agent in a color toner, and "Bontron E-84" manufactured by Orient Chemical Company as a metal complex compound of salicylic acid.
However, as the metal complex compound of benzylic acid, "LR-147" and "LR-297" manufactured by Nippon Carlit are preferably used.

Although the structure is not clear, "TN-105" manufactured by Hodogaya Chemical can also be suitably used as a colorless negative charge control agent.

As the positive charge control agent, a triphenylmethane dye, a nigrosine dye, a quaternary ammonium salt compound, a resin containing an amino group, or the like can be used. The quaternary ammonium salt compound is particularly preferably at least one selected from the following general formulas 6 to 8. Bontron P-51; a compound having the structure of general formula 6;
However, TP-302, TP-
415, TP-610; (made by Hodogaya Chemical).

[0075]

Embedded image <General formula 6> [wherein, R1 to R3 represent a CnH2n + 1 group. However, n shows the integer of 1-10. Also, R1
R3 may be the same or different. ]

[0076]

Embedded image Wherein R 4, R 5, R 6 and R 7 are each independently a hydrogen atom, an alkyl or alkenyl group having 1 to 22 carbon atoms, an unsubstituted or substituted aromatic group having 1 to 20 carbon atoms Represents an aralkyl group having 7 to 20 carbon atoms, and A- represents a molybdate anion or a tungstate anion, or a heteropolyacid anion containing molybdenum or a tungsten atom. ]

[0077]

Embedded image <General formula 8> [wherein, m represents 1, 2 or 3, n represents 0, 1 or 2, M represents a hydrogen atom or 1
Is a multivalent metal ion. X and Z each represent 1 or 2,
Y represents 0 or 1. Further, when X = 1, Y = 1,
When Z = 1 and X = 2, Y = 0 and Z = 2. R8
To R12 are hydrogen, a linear or branched saturated or unsaturated alkyl group having 1 to 30 carbon atoms,
An alkylene group of the general formula (-C2-5 alkylene-O) nR (where R is hydrogen or an alkyl or acyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10) ) Represents a polyalkyloxylene group represented by
1, R2, R3, and R4 are hydrogen, a linear or branched saturated or unsaturated alkyl group having 1 to 30 carbon atoms, or a general formula (-CH2-CH2-O) n-R
(Where R is hydrogen or an alkyl or acyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10), and a mononuclear or polynuclear group having 5 to 12 carbon atoms. Represents an alicyclic residue, a mononuclear or polynuclear aromatic residue or an araliphatic residue. More specifically, there are the following compounds.

[0078]

Embedded image <6-1>

[0079]

Embedded image <7-1>

[0080]

Embedded image <7-2>

[0081]

Embedded image <7-3>

[0082]

Embedded image <7-4>

[0083]

Embedded image <7-5>

[0084]

Embedded image <7-6>

[0085]

Embedded image <7-7>

[0086]

Embedded image <7-8>

[0087]

Embedded image <7-9>

[0088]

Embedded image <7-10>

[0089]

Embedded image <7-11>

[0090]

Embedded image <8-1>

[0091]

Embedded image <8-2>

The charge control agents exemplified above may be used in combination of two or more. For example, when a nigrosine dye and a quaternary ammonium salt compound are used in combination, 1/9 to 9/1
Is preferably used, and more preferably 2/8 to 8/2.

Nigrosine dyes have a high positive charge-imparting ability, and quaternary ammonium salt compounds have excellent charge uniformity and stability. By using both of them, a clear printed image without fog can be stably obtained during continuous printing.

The content of the charge control agent is determined by the binder resin 10
It is preferably used in an amount of 0.3 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 0 parts by mass.

The toner of the present invention can be obtained by an extremely general manufacturing method without depending on a specific manufacturing method.
For example, it can be obtained by melt-kneading a resin and a colorant at a temperature equal to or higher than the melting point (softening point) of the resin, followed by pulverization and classification.

Specifically, for example, the above-mentioned resin and colorant are mixed as essential components by a kneading means such as a two-roll, three-roll, pressure kneader or a twin-screw extruder. At this time, the colorant may be uniformly dispersed in the resin, and the conditions for the melt-kneading are not particularly limited, but are usually from 80 to 180 ° C. for from 30 seconds to 2 hours. 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.

Next, 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 diameter of the particles constituting the toner base is:
Although not particularly limited, it is usually adjusted to be 5 to 15 μm.

Usually, an external additive is mixed with the thus obtained toner base using a mixer such as a Henschel mixer.

The external additives are used for modifying the surface of the toner matrix such as improving the fluidity of the toner and improving the charging characteristics, and include inorganic fine powders such as silicon dioxide, titanium oxide and alumina and silicone oils. What has been subjected to a surface treatment with a hydrophobizing agent such as, or a fine resin powder is used.

Examples of the silica include those having hydrophobicity and the like among silicon dioxides, and examples thereof include those obtained by subjecting silicon dioxide to a surface treatment with various polyorganosiloxanes or silane coupling agents. For example, there is one that is commercially available under the following trade names.

AEROSIL R972, R974, R
202, R805, R812, RX200, RY20
0, R809, RX50, RA200HS, RA20
0H [Nippon Aerosil Co., Ltd.] WORKER 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, TS-530, TS-
720 [Cabot Specialty Chemicals
ink〕

These silicas have different average particle sizes.
More than one species may be used in combination. Further, the usage ratio of silica is usually 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner base.

In the present invention, the toner is a binder resin,
Although a colorant and a wax are used as main components, other additives may be included. For example, as a lubricant, metal soap, zinc stearate or the like can be used, and as an abrasive, for example, cerium oxide or 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 a powder of an alloy or a compound 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 1 to the total mass of the toner.
5 to 70% by mass is good.

In order to use the toner of the present invention as a two-component developer, known carriers such as iron oxide powder can be used as a carrier for the two-component developer. In the present invention, a magnetic carrier whose surface is coated with a resin is particularly used. Is desirable.

As the core agent of the carrier which can be used in combination with the toner of the present invention, iron powder, magnetite, ferrite and the like used in a usual two-component developing system can be used. Among them, the true specific gravity is low and the resistance is high. Ferrite with excellent fluidity due to excellent environmental stability and easy to be spherical,
Alternatively, magnetite is preferably used. The shape of the core agent can be used without any particular problem, such as spherical or amorphous. As the material of the core agent, manganese ferrite, copper-zinc ferrite, or the like is preferably used. The average particle size is generally from 10 to 500 µ, but is preferably from 30 to 80 µ for printing a high-resolution image.

Examples of coating resins for coating these core agents include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether polyvinyl ketone, and 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, phenolic 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, the resin-coated carrier used in the present invention is a resin-coated magnetic carrier coated with at least one resin selected from silicone resin, fluororesin, and (meth) acrylic resin using ferrite or magnetite as a core agent. Is preferred.

The method of coating the surface of the carrier core material with the resin is not particularly limited, but 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, or 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
~ 3.0μ.

The mass ratio between the toner containing the colored resin particles and the resin-coated magnetic carrier is not particularly limited, but usually 0.5 to 0.5 parts per 100 parts by mass of the carrier.
5 parts by mass.

[0112]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, "parts" represents "parts by mass" unless otherwise specified.

(Resin Synthesis Example 1) Styrene ... 368.5 parts Butyl methacrylate ... 119.5 parts Acrylic acid ... 12.0 parts Benzoyl peroxide ... 5.0 parts

Into a two-volume, four-necked round bottom flask equipped with a thermometer, a glass air flow inlet tube, a stirrer equipped with a vacuum-sealing device, and a water-cooled Dimroth condenser, were charged 500 parts of xylene and the total amount of the above monomers and initiator. did. After the inside of the reactor was replaced with an inert atmosphere by introducing nitrogen gas from a glass air flow inlet tube, the content was gradually heated to 75 ° C. by a mantle heater with a slider box. The reaction was carried out while maintaining the temperature at 65 ° C. to 80 ° C., and after 10 to 12 hours, the temperature was increased to 130 ° C. to complete the reaction, and the polymerization was completed. Next, the water-cooled condenser and the glass air flow introducing tube were removed from the flask, and a capillary for vacuum distillation and a Claisen fractionating tube were attached instead. A thermometer and a water-cooled Liebig condenser are connected to the Klaisen distilling tube,
The outlet of the condenser is connected to an eggplant-shaped flask via a suction adapter. The suction adapter and the vacuum pump are connected by a rubber tube for decompression via a manometer and a trap, and the preparation for decompression distillation is completed. Turn on the vacuum pump while heating the mantle heater and stirring the contents thoroughly.
When the pressure is reduced to mmHg, xylene or, if necessary, unreacted monomer starts to distill at a liquid temperature of 75 ° C and a distilling temperature of 38 ° C. Finally, the pressure was reduced to 0.5 mmHg at a liquid temperature of 180 ° C. to completely remove the solvent. The obtained polymer (hereinafter referred to as polymer (a)) was poured into a stainless steel pan in a high-temperature molten state, cooled to room temperature, and crushed.

The obtained polymer (a) was of a ring and ball type (JIS K2531,
K2548) GPC (gel permeation chromatography), a calibration curve obtained at 119 ° C using monodisperse polystyrene as a standard substance by measurement, was about 12 in number average molecular weight.
000 and a weight average molecular weight of about 30,000.

The polymer (a) was crushed into small pieces each having a side of 5 mm or less, and 300 parts thereof were weighed and charged into a one-volume, four-necked round bottom flask. The flask was equipped with a high-speed stirrer, a thermometer, and a drying tube filled with silica gel, and heating was started with a mantle heater. The charged resin gradually melted, and when the temperature was further increased, a completely mucous state was obtained. When the high-speed stirrer is slowly rotated and the temperature reaches 160 ° C, while increasing the stirring, 3.7 parts of calcium hydroxide (equivalent to about 0.5 equivalents of the total free carboxyl groups contained in the polymer (a)) is added to 20 parts.
The mixture was gradually added over a period of minutes, and reacted at a liquid temperature of 150 to 195 ° C. for 10 hours. After the reaction, the hot melt was spread on a stainless steel pan, cooled to room temperature, and then crushed to obtain a calcium metal chloride polymer (hereinafter, referred to as polymer (b)).

The obtained polymer (b) was quantified by FTIR (Fourier transform infrared spectrometer, “FTS-10” manufactured by Digilab, USA). As a result, the reaction rate of calcium hydroxide was about 25%.
≒ 8.3 × 10-5. The softening point of the polymer (b) is
At 148 ° C., T1-TS = 29 ° C. and Tg = 63 ° C.

(Resin Synthesis Example 2) Styrene: 570 parts Diethyl fumarate: 42 parts Butyl acrylate: 75 parts α-ethylcrotonic acid: 16 parts Benzoyl peroxide: 4 parts

Polymerization was carried out in the above-mentioned composition by substantially the same operation as in Resin Synthesis Example 1. The resulting polymer has a softening point of 115 ° C,
The number average molecular weight was about 7,500 and the weight average molecular weight was about 20,500. To 300 parts of this polymer, 4.4 parts of aluminum isopropoxide (corresponding to about 1 equivalent of all free carboxylic acids contained in the polymer) was reacted in the same manner as in Example 1.

The obtained aluminum metal chloride polymer (hereinafter referred to as polymer (c)) had a softening point of 166 ° C., and the conversion of aluminum isopropoxide by FTIR was about 95%. Therefore, N ≒ 2.1 × 10-4, and T1-TS = 51
° C and Tg = 55 ° C.

(Resin Synthesis Example 3) Styrene: 805 parts Lauryl methacrylate: 124 parts Vinylpyridine: 25 parts Methacrylic acid: 46 parts Azobisisobutyronitrile: 10 parts

Polymerization was carried out with the above composition by the same procedure as in Resin Synthesis Example 1. The obtained polymer had a softening point of 120 ° C. 500 parts of this polymer is melted in a kneader, and 17.2 parts of magnesium acetate tetrahydrate (corresponding to 1 equivalent of the total free carboxylic acid contained in the polymer) is added and melt-kneaded for 30 minutes or more. The obtained magnesium metal chloride polymer (hereinafter referred to as polymer (d)) has a softening point of 155 ° C and a reaction rate of about 30 by FTIR.
%, T1-TS = 35 ° C., Tg = 50 ° C.

(Resin Synthesis Example 4) Using 300 parts of the polymer (a) obtained in Resin Synthesis Example 1 and performing the same operation as in Resin Synthesis Example 1, 0.37 parts of calcium hydroxide (contained in Polymer (a)) (Equivalent to about 0.1 equivalent of the total free carboxyl group).

The calcium metal chloride polymer (hereinafter referred to as polymer (e)) was determined by FTIR. As a result, the conversion of calcium hydroxide was about 27.5%, the softening point was 134 ° C., and the T1
-TS = 15 ° C., N = 9.1 × 10−6.

(Resin Synthesis Example 5) Styrene: 380 parts Butyl methacrylate: 120 parts Divinylbenzene: 10 parts Benzoyl peroxide: 5 parts

Polymerization was carried out in the above-mentioned composition by the substantially same operation as in Resin Synthesis Example 1. The obtained polymer (hereinafter referred to as polymer (f)
Has a softening point of 155 ° C and a Tg of 55 ° C.

(Resin Synthesis Example 6) Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane ... 527 parts Terephthalic acid ... 301 parts Epicron N-695 (*) ... 78 parts Tetra Butyl titanate: 3 parts (*); a multifunctional cresol novolak type epoxy resin having more than two epoxy groups in one molecule, and a pentafunctional cresol novolak type epoxy resin having five epoxy groups in one molecule Epoxy compound containing (manufactured by Dainippon Ink and Chemicals, Inc.)

The above mixture was placed in a glass 2L 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 0 hour, the pressure was sequentially reduced, and the reaction was continued at 10 mmHg.
The reaction was followed by a softening point, and the reaction was terminated when the softening point reached 139 ° C.

The obtained polymer (hereinafter referred to as polymer (g))
Was a colorless solid, had an acid value of 3 KOH mg, a glass transition temperature of 65 ° C by DSC measurement and a softening point of 142 ° C.

(Resin Synthesis Example 7) Terephthalic acid ... 332 parts Isophthalic acid ... 332 parts Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane ... 700 parts Trimethylolpropane ... 80 Part Ethylene glycol ... 130 parts Tetrabutyl titanate ... 3 parts

The above composition was placed in a four-necked flask equipped with a stirrer, a condenser and a thermometer, and 4 parts by weight of tetrabutyl titanate was added under a nitrogen gas stream to remove water generated by dehydration condensation. While reacting at 240 ° C. for 10 hours under normal pressure. Thereafter, the pressure was sequentially reduced, and the reaction was continued at 10 mmHg. Reaction is tracked by softening point, softening point is 151 ℃
When the reaction reached, the reaction was terminated. The softening point of the obtained cross-linked polyester (hereinafter referred to as polymer (h)) is 153 ° C., the acid value is 4,
Tg measured by DSC was 65 ° C.

Example 1 <Production of Toner> 100 parts of polymer (b) 5 parts of carbon black VULCAN XC-72 (manufactured by Cabot Specialty Chemicals Inc.) * Electric resistance value; 0.15 Ω · cm Control agent (positive charge control agent) Bontron N-01 (manufactured by Orient Chemical Industry Co., Ltd.) 3 parts ・ Wax Wax 4 2 parts 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 α before external addition” having a volume average particle diameter of 10.1 μm.

100 parts of the above-mentioned “Before External Addition Toner α” • 1 part of Silica TG820F (manufactured by Cabot Specialty Chemicals, Inc.) using a Henschel mixer, followed by sieving.
“Toner α” was obtained.

<Adjustment of Developer> 5 parts of the above “toner α” 95 parts of a carrier (silicone resin-coated ferrite carrier) were mixed and stirred to adjust the developer α.

In the same manner, toners were manufactured in the same manner as in Tables 1-1 to 1-3, and developer α (Example 1) to developer κ (Example 10) and developer λ (Comparative Example 1). To ν (Comparative Example 3). The developer κ uses 40 parts of magnetic powder BL-200 (manufactured by Titanium Industry) as a coloring agent. Also,
A magnetic one-component developer was used without mixing with a carrier (silicone resin-coated ferrite carrier). In Example 9, a commercially available styrene-butadiene copolymer (softening point 145 ° C., T
g 50 ° C, Mw: 71,000, Mn: 11,000, styrene / butadiene mass ratio = 90/10).

[0136]

[Table 1] Table 1-1. Recipe

Polymer (I); styrene-butadiene copolymer (softening point: 145 ° C., Tg: 50 ° C., Mw: 71,000, Mn: 11,00
0, styrene / butadiene weight ratio = 90/10) ・ VULCAN XC-72 (Cabot Specialty Chemicals, Inc.); resistance value 0.15Ω ・ cm ・ REAGAL 400 (Cabot Specialty Chemicals, Inc.); resistance value 0.50Ω ・ cm・ BLACK PEARLS 1300 (Cabot Specialty Chemicals, Inc.); resistance 0.71Ω ・ cm ・ BLACK PEARLS L (Cabot Specialty
Chemicals Inc.); Resistance value 1.00Ω · cm ・ Viscol 550P; Polypropylene wax nigrosine N-01 manufactured by Sanyo Chemical Co., Ltd .; Bontron N-01 (manufactured by Orient Chemical Industry Co., Ltd.)

[0138]

[Table 2] Table 1-2. Recipe

Polymer (I); styrene-butadiene copolymer (softening point: 145 ° C., Tg: 50 ° C., Mw: 71,000, Mn: 11,00
0, styrene / butadiene weight ratio = 90/10) ・ VULCAN XC-72 (Cabot Specialty Chemicals, Inc.); resistance value 0.15Ω ・ cm ・ REAGAL 400 (Cabot Specialty Chemicals, Inc.); resistance value 0.50Ω ・ cm・ BLACK PEARLS 1300 (Cabot Specialty Chemicals, Inc.); resistance 0.71Ω ・ cm ・ BLACK PEARLS L (Cabot Specialty
Chemicals Inc.); Resistance value 1.00 Ω · cm ・ Viscol 550P; Polypropylene wax Nigrosin N-01 manufactured by Sanyo Chemical Co., Ltd .; Bontron N-01 (manufactured by Orient Chemical Industry Co., Ltd.)

[0140]

[Table 3] Table 1-3. Recipe

Polymer (I); styrene-butadiene copolymer (softening point: 145 ° C., Tg: 50 ° C., Mw: 71,000, Mn: 11,00
0, styrene / butadiene weight ratio = 90/10) ・ VULCAN XC-72 (Cabot Specialty Chemicals, Inc.); resistance value 0.15Ω ・ cm ・ REAGAL 400 (Cabot Specialty Chemicals, Inc.); resistance value 0.50Ω ・ cm・ BLACK PEARLS 1300 (Cabot Specialty Chemicals, Inc.); resistance 0.71Ω ・ cm ・ BLACK PEARLS L (Cabot Specialty
Chemicals Inc.); Resistance value 1.00 Ω · cm ・ Viscol 550P; Polypropylene wax Nigrosin N-01 manufactured by Sanyo Chemical Co., Ltd .; Bontron N-01 (manufactured by Orient Chemical Industry Co., Ltd.)

<Fixing Offset Test and Printing Test>
With respect to the developers obtained in the above Examples and Comparative Examples, a fixing start temperature, a hot offset start temperature, and a printing test were performed as follows.

(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 copier, and a heat roll fixing unit having the following specifications was mounted. The fixing start temperature and the presence or absence of an offset phenomenon were confirmed under the following test conditions.

With respect to the toner of Example 10, an unfixed image sample was prepared by modifying a commercially available magnetic one-component developing type printer.

[0145]

To measure the fixing start temperature, the image density residual ratio calculated by the following equation was obtained.

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 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).

An image density remaining ratio of 80% or more was set to a level that would cause no practical problem, and the lowest temperature was used as 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.

(Printing test) The printing quality of continuous printing was evaluated using a commercially available laser beam printer (with a selenium photosensitive member), and the charge amount of the developer was measured. Replenishment of toner during continuous printing was performed automatically by filling the toner after silica addition into a replenishment toner hopper of the machine.

The charge amount was measured by a blow-off charge amount measuring device. The image density was measured with a Macbeth densitometer RD-918, and the background stain (stain in the non-image area) was obtained by subtracting the white paper density before printing from the white area density.

The toner of Example 10 was tested by modifying a commercially available magnetic one-component developing printer. Regarding the charge amount, a toner is sampled from the inside of the developing device for each number of printed sheets, a developer is prepared with toner / carrier (silicone resin-coated ferrite carrier) = 5/95 (mass ratio), and another two-component developer It measured similarly to.

(Toner Scattering Amount) Observing the inside of the machine after printing 50KP (50,000 sheets), ○ indicates that there is almost no dirt due to the scattering toner around the photosensitive member and the peripheral portion of the developing device, and Δ indicates that slight dirt has occurred. And the case where severe stains occurred was evaluated as x.

The results of the above evaluation are shown in Tables 2-1 to 2-2.

[0155]

[Table 4] Table 2-1. Evaluation results

The indications in the table are as follows.

* “Charge amount”; μC / g * “Background dirt evaluation” ○: less than 0.01, Δ: 0.01 to less than 0.03,
×: 0.03 or more * “Toner scattering”; visual observation after printing 50 KP (50,000 sheets) ○: almost no scattering △: slight scattering caused by contamination ×: severe scattering occurred

[0158]

[Table 5] Table 2-2. Evaluation results

The indications in the table are as follows.

* "Charge amount"; μC / g * "Stain evaluation" ○: less than 0.01, Δ: 0.01 to less than 0.03,
×: 0.03 or more * “Toner scattering”; visual observation after printing 50 KP (50,000 sheets) ○: almost no scattering △: slight scattering caused by contamination ×: severe scattering occurred

[0161]

[Table 6] Table 2-3. Evaluation results

The indications in the table are as follows.

* “Charge amount”; μC / g * “Background dirt evaluation” ○: less than 0.01, Δ: 0.01 to less than 0.03,
×: 0.03 or more * “Toner scattering”; visual observation after printing 50 KP (50,000 sheets) ○: almost no scattering △: slight scattering caused by contamination ×: severe scattering occurred

As is clear from Table 2, the toner of the present invention shows a sufficient image density in continuous printing, does not cause background stain on the white background of the printed matter, and does not cause toner scattering inside the machine, and has a stable charging performance. Has become a developer.

On the other hand, the toners of Comparative Examples 1 and 2 had too high a resistance value of the toner, an increase in the charge amount was observed, and the printed matter had a low image density.

The toner using the polypropylene wax of Comparative Example 3 has a narrow fixing / offset temperature range.
Further, with the increase in the number of printed sheets, background soiling occurred, and toner scattering was also observed.

In order to confirm the difference between the wax according to the present invention and the polypropylene wax, the dispersion state of the polypropylene wax in the toner used in Comparative Example 1 was observed with a microscope. It was found that the dispersion particles were very large in comparison. In addition, since the carrier surface after 50KP printing had attached polypropylene and generation of spent carrier was recognized, the difference in the dispersibility of the wax appeared as background contamination, toner scattering, and the difference in developer life. It is inferred. In Examples according to the present invention, generation of spent carrier was not recognized.

[0168]

As described in the above embodiment, the resistance value of the toner is 0.05 × 10 16 Ω · cm to 1.50 × 101.
According to the toner of the present invention using an ester wax having a structure of having a chain hydrocarbon group having 12 to 40 carbon atoms in a part of the molecule, good fixing properties can be obtained in a wider temperature range. Thus, a developer exhibiting offset resistance is obtained. In addition, since it has a stable charging behavior at the same time, it is possible to stably obtain a high-density and high-quality printed image free of stain on the non-image area without causing spent carrier and toner scattering in the developing device. An agent can be provided.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 16, 2001 (2001.2.1)
6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Embedded image <General Formula 1> ( R ₁ and R _{2 each} represent 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.)

Embedded image <General Formula 2> ( R ₁ , R ₂ and R ₃ are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them is a hydrocarbon group having 12 carbon atoms.
The above-mentioned chain hydrocarbon groups are shown. )

Embedded image <General Formula 3> ( R ₁ , R ₂ and R ₃ are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them is a hydrocarbon group having 12 carbon atoms.
The above-mentioned chain hydrocarbon groups are shown. )

Embedded image <General formula 4> ( R ₁ is a hydrocarbon group having 12 to 40 carbon atoms.
R ₂ is a hydrocarbon group having 1 to 40 carbon atoms. Also, a + b = 4
And a represents an integer of 1 to 4, and b represents an integer of 0 to 3. )

Embedded image <General Formula 5> ( R ₁ , R ₂ and R ₃ are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them is a hydrocarbon group having 12 carbon atoms.
The above chain hydrocarbon group. A and c are integers of 0 to 2, and a + c = 2. b is an integer of 1 to 4, and d is 1 or 2. Furthermore, e = d-1. )

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

That is, the present invention provides a toner comprising a binder resin, a colorant, and a wax, wherein the toner has a resistance value of 0.05 × 10 ¹⁶ Ω · c.
m to 1.50 × 10 ¹⁶ Ω · cm, wherein the wax is an ester of a carboxylic acid and an alcohol, and has a structure in which a part of a molecule has a chain hydrocarbon group having 12 to 40 carbon atoms. And a toner for developing an electrostatic image.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0025

[Correction method] Change

[Correction contents]

The polymer A and the polymer B are represented by the following formula (1):
It is desirable to satisfy the relationship represented by the expression (2). 10 ⁻⁵ ≦ N ≦ 2 × 10 ⁻³ (1) T1−TS ≧ 20 ° C. (2) [In the above formula, N is the number of moles of the carboxyl ion converted into metal contained in 1 g of the polymer B, and T1 is The softening point and TS of the polymer B according to the ring and ball method (JIS K2531, K2548) are those of the polymer A
And Tg represent the glass transition temperature of the polymer B measured by a DSC method, respectively. ]

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

In the formula (1), when N is 10 ^-5 or less, there is no viscosity effect due to metal chloride, and when N is 2 × 10 ^-3 or more, the charging characteristics of the toner may be impaired. Also, the fixing start temperature is increased. A more specific preferred viscoelastic range is described by equation (2). That is, the ring-and-ball method softening point temperature, which measures the temperature at the time of constant deformation under a constant load, is a kind of viscosity index, but the softening point of the polymer B according to the present invention is T1, The toner using a polymer having a T1-TS value of at least 20 ° C. or more when the softening point of the polymer B, ie, the softening point of the polymer B, is represented by TS is preferable in the heat roll fixing system.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction contents]

[0044]

Embedded image <General Formula 1> ( R ₁ and R _{2 each} represent 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.)

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0045

[Correction method] Change

[Correction contents]

[0045]

Embedded image <General Formula 2> ( R ₁ , R ₂ and R ₃ are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them is a hydrocarbon group having 12 carbon atoms.
The above-mentioned chain hydrocarbon groups are shown. )

[Procedure amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction contents]

[0046]

Embedded image <General Formula 3> ( R ₁ , R ₂ and R ₃ are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them is a hydrocarbon group having 12 carbon atoms.
The above-mentioned chain hydrocarbon groups are shown. )

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0047

[Correction method] Change

[Correction contents]

[0047]

Embedded image <General formula 4> ( R ₁ is a hydrocarbon group having 12 to 40 carbon atoms.
R ₂ is a hydrocarbon group having 1 to 40 carbon atoms. Also, a + b = 4
And a represents an integer of 1 to 4, and b represents an integer of 0 to 3. )

[Procedure amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction contents]

[0048]

Embedded image <General Formula 5> ( R ₁ , R ₂ and R ₃ are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them is a hydrocarbon group having 12 carbon atoms.
The above chain hydrocarbon group. A and c are integers of 0 to 2, and a + c = 2. b is an integer of 1 to 4, and d is 1 or 2. Furthermore, e = d-1. )

[Procedure amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction contents]

The electric resistance value of the toner using the specific wax specified in the present invention is 0.05 × 10 ¹⁶ Ω · cm to 1.
It needs to be 50 × 10 ¹⁶ Ω · cm. More preferably, 0.10 × 10 ¹⁶ Ω · cm to 1.00 × 10 ¹⁶ Ω · c
m. In the toner of the present invention, by adjusting the resistance value to fall within this range, high-image-density printing is possible, and a good toner is obtained in which non-image areas are free from contamination and scattering toner. Can be

[Procedure amendment 11]

[Document name to be amended] Statement

[Correction target item name] 0062

[Correction method] Change

[Correction contents]

When the electric resistance of the toner of the present invention is 1.50 × 10 ¹⁶ Ω · cm or more, the image density is reduced as described above. 0.05 × 10 ¹⁶ Ω · cm
If it is less than the above range, the charge amount of the toner will be significantly reduced, and the developer will be a lot of stain fogging and scattered toner in the non-image area.

[Procedure amendment 12]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

The resistance value of the toner was measured at a pressure of 2.5 t / cm ² with a pellet formed into a thickness of 5.0 ± 0.5 mm and a diameter of 50 mm using an R8340A type electric resistance meter manufactured by Advantest Corporation. . The temperature at the time of measurement is 22-28
C., humidity were measured at 50 to 70% RH, and the electrode diameter was measured at 35 mm.

[Procedure amendment 13]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction contents]

[0075]

Embedded image <General formula 6> [wherein, R _{1 to} R ₃ represent a CnH2n + 1 group. However, n shows the integer of 1-10. Also, R _{1 to} R ₃
May be the same or different. ]

[Procedure amendment 14]

[Document name to be amended] Statement

[Correction target item name] 0076

[Correction method] Change

[Correction contents]

[0076]

Embedded image Wherein R ₄ , R ₅ , R ₆ and R ₇ are each independently a hydrogen atom, an alkyl or alkenyl group having 1 to 22 carbon atoms, an unsubstituted or 1 to 20 carbon atoms, substituted aromatic group, a 7-20 amino aralkyl group having a carbon, a ^- represents a heteropolyacid anion containing molybdenum anion or tungstic acid anion, molybdenum or tungsten atoms. ]

[Procedure amendment 15]

[Document name to be amended] Statement

[Correction target item name] 0077

[Correction method] Change

[Correction contents]

[0077]

Embedded image<General formula 8> [wherein m represents 1, 2 or 3;
And n represents 0, 1 or 2, and M represents a hydrogen atom or 1
Is a multivalent metal ion. X and Z each represent 1 or 2,
Y represents 0 or 1. Further, when X = 1, Y = 1,
When Z = 1 and X = 2, Y = 0 and Z = 2.R ₈
~ R ₁₂ Is hydrogen, C1-C30 linear or branched
Saturated or unsaturated alkyl group having 1 to 4 carbon atoms
Alkoxylen group, general formula (-C2-5 alkylene-
O) n-R (where R is hydrogen or an alkyl having 1 to 4 carbon atoms)
And n is an integer of 1 to 10.
Represents a polyalkyloxylene group represented by
R ₁ , R ₂ , R ₃ , R ₄ Is hydrogen or a straight chain having 1 to 30 carbon atoms.
Linear or branched saturated or unsaturated alkyl
Or a general formula (-CH2-CH2-O) n-R
(Where R is hydrogen or an alkyl group having 1 to 4 carbon atoms or
Is an acyl group, and n is an integer of 1 to 10.)
Oxyethyl group, further mononuclear having 5 to 12 carbon atoms or
Polynuclear alicyclic residue, mononuclear or polynuclear aromatic residue or aromatic
Represents an araliphatic residue. More specifically, there are the following compounds.

[Procedure amendment 16]

[Document name to be amended] Statement

[Correction target item name] 0117

[Correction method] Change

[Correction contents]

The obtained polymer (b) was quantified by FTIR (Fourier transform infrared spectrometer, “FTS-10” manufactured by Digilab, USA). As a result, the reaction rate of calcium hydroxide was about 25%.
≒ 8.3 × 10 ^-5 The softening point of the polymer (b) is 14
At 8 ° C, T1-TS = 29 ° C and Tg = 63 ° C.

[Procedure amendment 17]

[Document name to be amended] Statement

[Correction target item name] 0120

[Correction method] Change

[Correction contents]

The obtained aluminum metal chloride polymer (hereinafter referred to as polymer (c)) had a softening point of 166 ° C., and the conversion of aluminum isopropoxide by FTIR was about 95%. Therefore, N ≒ 2.1 × 10 ^-4 and T1-TS = 51
° C and Tg = 55 ° C.

[Procedure amendment 18]

[Document name to be amended] Statement

[Correction target item name] 0124

[Correction method] Change

[Correction contents]

The calcium metal chloride polymer (hereinafter referred to as polymer (e)) was determined by FTIR. As a result, the conversion of calcium hydroxide was about 27.5%, the softening point was 134 ° C., and the T1
-TS = 15 ° C., N = 9.1 × 10 ⁻⁶ .

[Procedure amendment 19]

[Document name to be amended] Statement

[Correction target item name] 0168

[Correction method] Change

[Correction contents]

[0168]

As described in the above embodiment, the toner has a resistance value of 0.05 × 10 ¹⁶ Ω · cm to 1.50 × 10 ¹⁶ Ω.
According to the toner of the present invention using an ester wax having a structure in which a part of a molecule has a chain hydrocarbon group having 12 to 40 carbon atoms, good fixing properties can be obtained in a wider temperature range. A developer exhibiting offset resistance is obtained. In addition, since it has a stable charging behavior at the same time, it is possible to stably obtain a high-density and high-quality printed image free of stain on the non-image area without causing spent carrier and toner scattering in the developing device. An agent can be provided.

Continued on the front page (72) Inventor Masamichi Asai 4-119 Tobe-cho, Nishi-ku, Yokohama-shi, Kanagawa F-term (reference) 2H005 AA06 CA14 CB18 EA01

Claims (4)

[Claims] 1. A toner comprising a binder resin, a colorant and a wax, wherein the toner has a resistance value of 0.05 × 10
16 Ω · cm to 1.50 × 10 16 Ω · cm, wherein the wax is an ester of a carboxylic acid and an alcohol, and has a structure having a chain hydrocarbon group having 12 to 40 carbon atoms in a part of the molecule. A toner for developing electrostatic images, characterized by the following. 2. The electrostatic image developing toner according to claim 1, wherein the wax contains at least one selected from compounds represented by the following general formulas 1 to 5. Embedded image <General formula 1> (R1 and R2 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 2> (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them is a hydrocarbon group having 1 carbon atom.
Shows two or more chain hydrocarbon groups. ) <General formula 3> (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them is a hydrocarbon group having 1 carbon atom.
Shows two or more chain hydrocarbon groups. ) <General formula 4> (R1 is a hydrocarbon group having 12 to 40 carbon atoms.
R2 is a hydrocarbon group having 1 to 40 carbon atoms. Also, a + b = 4
And a represents an integer of 1 to 4, and b represents an integer of 0 to 3. ) <General Formula 5> (R1, R2, and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them has 1 carbon atom.
2 or more chain hydrocarbon groups. A and c are integers of 0 to 2, and a + c = 2. b is an integer of 1 to 4, and d is 1 or 2. Furthermore, e = d-1. ) 3. The toner according to claim 1, wherein the colorant is carbon black. 4. The carbon black having a resistance value of 0.05.
4. The toner for an electrostatic developer according to claim 3, wherein the toner has an Ω · cm to 0.80 Ω · cm.