JP2003255575A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner exhibiting good developing performance even in long-term use and even at high temperature and high humidity. <P>SOLUTION: In the toner comprising at least a bonding resin and a colorant, 0.1 to 100 ppm sulfonic acid-containing monomer is contained, wherein the sulfonic acid is 2-acrylamide, 2-methylpropane sulfonic acid. A copolymerized resin obtained by copolymerizing a styrene/acrylic monomer and 2-acrylamide, 2-methylpropane sulfonic acid is incorporated into the toner as an electrostatic charge controlling agent. The copolymerization ratio of the styrene/acrylic monomer to the 2-acrylamide, 2-methylpropane sulfonic acid is 98:2 to 80:20. The copolymerized resin has a weight average molecular weight of 2,000 to 20,000 and a glass transition temperature of 50 to 90°C. The bonding resin is a hybrid resin having a polyester unit and a vinyl copolymer unit. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, a toner used for developing an electrostatic latent image in electrophotography is required to have an appropriate amount of charge in order to obtain a clear developed image without fog. . Furthermore, it is required that stable chargeability be maintained even during long-term durability, and that the charge amount does not change due to environmental changes such as humidity changes.

In order to meet the above demands, a method of internally or externally adding a charge control agent to the toner is known. Conventionally, as the charge control agent, chromium-containing, iron- or cobalt-complex azo dyes and metal dyes such as chromium-containing salicylic acid and alkylsalicylic acid compounds have been used. However, these compounds have poor stability due to their structural complexity. Further, it is decomposed and deteriorated due to thermal and mechanical influences such as melt-kneading and pulverization in the toner manufacturing process, deteriorating dispersibility in the toner, and sufficient charge imparting ability cannot be exhibited.

With respect to such a problem, Japanese Patent Laid-Open No. 3-56
974, JP-A-7-77839, JP-A-1
No. 0-133421 discloses a toner in which a sulfonic acid-containing resin control agent (CCR) is added to a vinyl resin. The charge control agent having such a structure is stable in the toner because the main component is resin, and the chargeability is also stable.

However, with the recent progress in speeding up of copying machines, energy saving, and reduction in particle size of toner due to higher image quality, the reality is that there is no toner capable of maintaining sufficient charging characteristics.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which solves the above problems.

An object of the present invention is to provide a toner which maintains good developability even in long-term durability.

An object of the present invention is to provide a toner exhibiting good developability even under high temperature and high humidity.

[0009]

The present invention is a toner containing at least a binder resin and a colorant, wherein the toner contains 0.1 to 100 ppm of a sulfonic acid-containing monomer. Regarding

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below.

The toner of the present invention contains 0.1 to 100 pp.
It is characterized by containing m sulfonic acid-containing monomer. Since this sulfonic acid-containing monomer is excellent in negative chargeability, it can impart stable negative chargeability to the binder resin and maintain good chargeability even in long-term durability.
Further, the dispersibility in the binder resin is good, and even when the toner has a small particle size, the toner is uniformly charged, so that selective development or the like does not occur and the environmental stability is excellent. Further, since this sulfonic acid-containing monomer has a small molecular weight, it is likely to exist on the toner surface, and the toner charge amount control is excellent. However, when the content of the sulfonic acid-containing monomer is more than 100 ppm, not only the dispersibility in the binder resin is deteriorated but also the moisture resistance is deteriorated, so that the charge amount of the toner is reduced. If it is less than 0.1 ppm, the desired charging performance cannot be obtained, which is not preferable.

The sulfonic acid-containing monomer used in the present invention is particularly preferably a sulfonic acid-containing acrylamide monomer, such as 2-acrylamidopropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid,
2-acrylamido-n-hexanesulfonic acid, 2-acrylamido-n-octanesulfonic acid, 2-acrylamido-n-dodecanesulfonic acid, 2-acrylamido-n-tetradecanesulfonic acid, 2-acrylamido-
2-methylpropanesulfonic acid, 2-acrylamide-
2-phenylpropanesulfonic acid, 2-acrylamido-2,2,4-trimethylpentanesulfonic acid, 2-acrylamido-2-methylphenylethanesulfonic acid,
2-acrylamido-2- (4-chlorophenyl) propanesulfonic acid, 2-acrylamido-2-carboxymethylpropanesulfonic acid, 2-acrylamido-2-
(2-pyridyl) propanesulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid, 2-methacrylamido-n-decanesulfonic acid, 2-methacrylamido-
Examples thereof include n-tetradecane sulfonic acid. Preferred is 2-acrylamido-2-methylpropanesulfonic acid.

The method of adding these sulfonic acid-containing monomers is not particularly limited, and the method of adding the monomers themselves in the toner manufacturing process, and the general monomer used in binder resins and the like. Any known method can be used, such as a method of incorporating it as a copolymer with a monomer. Among them, from the viewpoint of dispersibility in the toner, a method in which a copolymer is previously produced and then added is preferable as in the latter case.

The other monomer used in the copolymer is preferably a styrene / acrylic monomer from the viewpoint of improving the compatibility with the binder resin. The styrene / acryl-based monomer used is appropriately selected from the vinyl-based monomers for producing the vinyl-based copolymer described below. Preferably, a combination of styrene and acrylic acid ester or methacrylic acid ester is used.

The polymerization initiator used when synthesizing the copolymer is appropriately selected from the initiators used when forming the vinyl copolymer described below. Peroxide initiators are preferably used.

The method for synthesizing the copolymer is not particularly limited, and any method such as solution polymerization, suspension polymerization and bulk polymerization can be used, but the copolymerization is carried out in an organic solvent containing a lower alcohol. Solution polymerization is preferred.

The copolymerization ratio of the styrene / acrylic monomer and the sulfonic acid-containing acrylamide monomer is 98 /
2 to 80/20, preferably 95 /
It is preferably 5 to 85/15. When the amount of the sulfonic acid-containing acrylamide monomer is less than 2%, the chargeability of the copolymer decreases, and the amount of the copolymer to be mixed with the toner particles must be increased, resulting in poor fixability. It is not preferable because it may happen. When it is more than 20%, sufficient chargeability cannot be obtained, and the moisture resistance of the toner particles themselves deteriorates, which is not preferable.

The weight average molecular weight of the copolymer is 20.
It is preferably from 00 to 200,000, preferably 1
It is preferably 0000 to 150,000, and more preferably 15,000 to 120,000.
When the weight average molecular weight is less than 2,000, it is likely to be affected by the environment, and the chargeability is deteriorated especially under high temperature and high humidity. On the other hand, if it exceeds 200,000, the dispersion in the binder resin is deteriorated and the image characteristics such as fog are deteriorated, which is not preferable.

The glass transition temperature (Tg) of the copolymer is 5
It is preferably 0 to 90 ° C., preferably 70 to 8
It is preferably 5 ° C. When Tg is less than 50 ° C,
If the temperature is higher than 90 ° C, the dispersion state of the copolymer in the binder resin is deteriorated, which is not preferable.

Examples of the binder resin for the toner of the present invention include polyester resins, styrene / acrylic resins, epoxy resins, styrene / butadiene resins, polyurethane resins and the like, but the known resins are not particularly limited. You can Of these, polyester resin and styrene / acrylic resin are particularly preferable.

Two or more of the above resins may be used in combination. In the present invention, a polyester resin and a vinyl resin such as styrene / acrylic resin, and a polyester unit and a vinyl copolymer unit are particularly used. Those containing the hybrid resin component they have are preferable.

The following are examples of the monomers of the polyester resin used in the present invention.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol,
1,5-Pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl 1,3-hexanediol, hydrogenated bisphenol A, a bisphenol derivative represented by the formula (a) and the following (a) ) The diols represented by the formula.

[0024]

[Chemical 1]

As the divalent carboxylic acid containing 50 mol% or more in all the acid components, benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or their anhydrides; succinic acid, adipic acid, sebacine acid,
Alkyl dicarboxylic acids such as azelaic acid or anhydrides thereof, and succinic acid substituted with an alkyl group having 6 to 18 carbon atoms or anhydrides thereof: unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid Or the anhydride etc. are mentioned.

Further, glycerin, pentaerythritol, sorbit, sorbitan, and further polyhydric alcohols such as oxyalkylene ether of novolac type phenol resin; trimellitic acid, pyromellitic acid,
Examples thereof include polyvalent carboxylic acids such as benzophenone tetracarboxylic acid and its anhydride.

Further, those having a crosslinked structure crosslinked with a trivalent or higher polyvalent carboxylic acid or an anhydride thereof, or a trivalent or higher polyhydric alcohol are preferable. Examples of trivalent or higher polycarboxylic acids or anhydrides thereof include 1,2,4
-Benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid and acid anhydrides or lower alkyl esters thereof, and the like, and trivalent or higher polyhydric alcohols. For example, 1,2,3-propanetriol,
Trimethylolpropane, hexanetriol, pentaerythritol and the like are mentioned, but preferably 1,2,
4-benzenetricarboxylic acid and its anhydride.

The vinyl-based monomers for producing the styrene / acrylic resin include the following.

Styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p -Methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene,
Styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride, Vinyl halides such as vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate. , Isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate. Α-methylene aliphatic monocarboxylic acid esters such as: methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate Acrylic acid esters such as stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether: vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone Vinyl ketones such as; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl compounds such as N-vinyl pyrrolidone; vinyl naphthalene; acrylonitrile, methacrylonitrile And acrylic acid or methacrylic acid derivatives such as acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenylsuccinic anhydride. Unsaturated dibasic acid anhydrides such as: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, cytofuconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl ester Half ester of unsaturated basic acid such as half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; unsaturated basic acid ester such as dimethyl maleic acid, dimethyl fumaric acid; acrylic Α, β-unsaturated acid anhydrides such as methacrylic acid, crotonic acid and cinnamic acid; anhydrides of the α, β-unsaturated acids and lower fatty acids; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, etc. Monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyl ethyl acrylate, 2-hydroxyl ethyl methacrylate and 2-hydroxyl propyl methacrylate, 4- (1-hydroxy-)
1-methylbutyl) styrene, 4- (1-hydroxy-)
Mention may be made of monomers having a hydroxyl group such as 1-methylhexyl) styrene.

Further, it may be a polymer which is cross-linked with a cross-linking monomer as exemplified below, if necessary.

Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include:
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and the above. Compounds in which acrylate is replaced with methacrylate include: diacrylate compounds linked by an alkyl chain containing an ether bond, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # Methacrylate of 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds. Include those instead; eg as diacrylate compounds linked with a chain containing an aromatic group and e one ether bond, polyoxyethylene (2) -
2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate,
And those in which the acrylates of the above compounds are replaced by methacrylates; examples of the polyester type diacreille include trade name MANDA (Nippon Kayaku Co., Ltd.).

As the polyfunctional cross-linking agent, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and the above compounds in which acrylate is replaced with methacrylate Triallyl cyanurate, triallyl trimellitate;

These cross-linking agents are based on other monomer components 10
0.01 to 10 parts by mass (more preferably 0.03 to 5 parts by mass) can be used with respect to 0 parts by mass.

Among these crosslinkable monomers, those which are preferably used in the resin for toner from the viewpoints of fixing property and anti-offset property, are aromatic divinyl compounds (particularly divinylbenzene), chains containing an aromatic group and an ether bond. Examples of the diacrylate compounds bound by

The polymerization initiator used when producing the vinyl copolymer of the present invention is, for example, 2,2′-
Azobisisobutyronitrile, 2,2'-azobis (4
-Methoxy-2,4 dimethylvaleronitrile), 2,
2'-azobis (-2,4-dimethylvaleronitrile), 2,2'-azobis (-2 methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate,
1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4- Dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane), methyl ethyl ketone peroxide,
Acetoneacetone peroxide, ketone peroxides such as cyclohexanone peroxide, 2,2 ′
-Bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butyl Cumyl peroxide, di-cumyl peroxide,
α, α'-bis (t-butylperoxypropyl)
Benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate , Di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate,
Di-methoxyisopropyl peroxydicarbonate,
Di (3-methyl-3-methoxybutyl) peroxycar
Carbonate, acetylcyclohexylsulfonylperoxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t -Butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropylcarbonate, di-t-butylperoxyisophthalate, t-butylperoxyallylcarbonate, t-amylperoxy-2 -Ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, and di-t-butylperoxyazelate.

The binder resin of the present invention preferably contains a monomer component capable of reacting with both resin components in the vinyl copolymer component and / or the polyester resin component. Among the monomers that constitute the polyester resin component, examples of monomers that can react with the vinyl copolymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl-based copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

As a method for obtaining a reaction product of a vinyl-based copolymer and a polyester resin, a polymer containing a monomer component capable of reacting with each of the above-mentioned vinyl-based copolymer and polyester resin is present. The method obtained by polymerizing one or both of the resins is preferable.

The binder resin as described above may be used alone, or two or more kinds of binder resins having different softening points may be mixed and used. Such a system is preferable because the melt viscosity of the toner can be designed relatively easily.

If desired, the toner of the present invention may contain one or more waxes as a release agent, and the wax is measured by a differential scanning calorimeter (DSC). The melting point defined by the endothermic peak temperature at the time of temperature increase is preferably 60 to 130 ° C. Melting point 6
If the temperature is lower than 0 ° C., the viscosity of the toner is lowered and the toner is apt to adhere to the photoconductor, and if the melting point is higher than 130 ° C., the low temperature fixability is deteriorated.

The wax is preferably added in an amount of 1 to 30 parts by mass with respect to 100 parts by mass of the binder resin. 1
If it is less than 30 parts by mass, the desired releasing effect cannot be sufficiently obtained, and if it exceeds 30 parts by mass, the dispersion in the toner is poor.
Adhesion of toner to the photoconductor or surface contamination of a toner carrier such as a carrier or a sleeve may occur, resulting in deterioration of a toner image and a practical problem.

Examples of the wax include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; Block copolymers of hydrocarbon wax; waxes having fatty acid ester as a main component such as carnauba wax, sazol wax and montanic acid ester wax; deoxidation of fatty acid ester such as deoxidized carnauba wax The ones that have been done are listed. Furthermore, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkylcarboxylic acids having a longer-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and vinalinaric acid; Stearin alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, melysyl alcohol,
Alternatively, saturated alcohols such as long-chain alkyl alcohols having a long-chain alkyl group; polyhydric alcohols such as sorbitol: fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (generally metal soaps). Waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; partial esterification products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; vegetable matter A methyl ester compound having a hydroxyl group obtained by hydrogenation of fats and oils is mentioned. In the present invention, hydrocarbon waxes are particularly preferable in terms of high releasability and ease of dispersion in the toner.

The wax may be added at the time of melt-kneading during the production of toner, or may be added during the production of resin.

The toner of the present invention may be a magnetic toner or a non-magnetic toner. In the case of a magnetic toner, the following magnetic materials are used for charging property,
It is preferable for reasons such as fluidity and uniformity of copy density.

As the magnetic material which is also used as the coloring agent,
Iron oxides such as magnetite, maghemite, and ferrite, and magnetic iron oxides containing other metal oxides; Fe, C
o, metals such as Ni, or these metals and A
l, Co, Pb, Mg, Ni, Sn, Zn, Sb, B
Examples thereof include alloys with metals such as e, Bf, Cd, Ca, Mn, Se, Ti, W and V, and mixtures thereof. Conventionally, triiron tetraoxide (Fe ₃ O _4), iron sesquioxide (.gamma.
Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe ₅ O ₁₂ ), cadmium iron oxide (Cd ₃
Fe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ O ₁₂ ),
Iron oxide copper (CuFe ₂ O ₄ ), iron oxide lead (PbFe)
₁₂ O ₁₉ ), iron nickel oxide (NiFe ₂ O ₄ ), iron neodymium oxide (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂
O ₁₉ ), magnesium iron oxide (MgFe ₂ O ₄ ), manganese iron oxide (MnFe ₂ O ₄ ), lanthanum iron oxide (LaFe
O ₃ ), iron powder (Fe), cobalt powder (Co), nickel powder (Ni) and the like are known. The above magnetic materials are used alone or in combination of two or more. A particularly preferred magnetic material is a fine powder of ferric tetroxide or gamma ferric oxide.

These ferromagnetic materials have an average particle size of 0.05 to
At 2 μm, the magnetic properties under application of 795.8 kA / m show coercive force of 1.6 to 12.0 kA / m, saturation magnetization of 50 to 200 A.
m ² / kg (preferably 50 to 100 Am ² / kg) and residual magnetization of ^{2 to 20} Am ² / kg are preferable.

The magnetic material is preferably added in an amount of 10 to 200 parts by mass with respect to 100 parts by mass of the binder resin.

When the toner of the present invention is used as a non-magnetic toner, any suitable pigment or dye can be used as a colorant.

As the dye, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Mordant Red 30, C.I. I. Direct Blue 1, C.I.
I. Direct Blue 2, C.I. I. Acid Blue 9,
C. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant To Blue 7, C.I. I. Direct Green 6, C.I.
I. Basic Green 4, C.I. I. There are Basic Green 6 etc. Examples of pigments include yellow lead, cadmium yellow, mineral fast yellow, navel yellow, naphthol yellow S, Hansa yellow G, permanent yellow NCG, tartrazine lake, red lead yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, benzidine orange G. , Cadmium red, Permanent red 4R, Watching red calcium salt, Eosin lake, Brilliant carmine 3
B, manganese purple, fast violet B, methyl violet lake, navy blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, fast sky blue, indanthrene blue BC, chrome green, chromium oxide, pigment green B, malachite. Green Rake, Final Yellow Green G, etc.

When the toner of the present invention is used as a toner for forming a full-color image, the following colorants may be mentioned. Examples of magenta color pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,
11, 12, 13, 14, 15, 16, 17, 18, 1
9, 21, 22, 23, 30, 31, 32, 37, 3
8, 39, 40, 41, 48, 49, 50, 51, 5
2,53,54,55,57,58,60,63,6
4,68,81,83,87,88,89,90,11
2,114,122,123,163,202,20
6,207,209, C.I. I. Pigment violet 19, C.I. I. Butt Red 1, 2, 10, 13, 1
5,23,29,35 and the like.

The above magenta pigment may be used alone, but it is more preferable to use a dye and a pigment together to improve the sharpness from the viewpoint of the image quality of a full color image. Examples of magenta dyes include C.I. I. Solvent Red 1,
3,8,23,24,25,27,30,49,81,
82, 83, 84, 100, 109, 121, C.I. I.
Disperse Red 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil soluble dyes such as Disperse Violet 1, C.I. I. Basic Red 1,2,9,12,13,14,15,17,1
8, 22, 23, 24, 27, 29, 32, 34, 3
5,36,37,38,39,40, C.I. I. Basic Violet 1,3,7,10,14,15,21,
Basic dyes such as 25, 26, 27 and 28 are mentioned.

As the color pigment for cyan, C.I. I. Pigment Blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted in the phthalocyanine skeleton having the following structure, and the like.

[0054]

[Chemical 2]

As the coloring pigment for yellow, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10,
11, 12, 13, 14, 15, 16, 17, 23, 3
5, 73, 83, C.I. I. Bat yellow 1,3,20
And so on.

The coloring agent is based on 100 parts by mass of the resin component.
0.1 to 60 parts by mass is preferable, and more preferably 0.5.
˜50 parts by mass.

The chargeability of the toner of the present invention may be either positive or negative, but since the binder resin itself has a high negative chargeability,
It is preferably a negatively chargeable toner.

The toner of the present invention may further contain a charge control agent, if necessary, in order to further stabilize the charge amount. As the negatively chargeable one, for example, an organometallic complex or a chelate compound is effective, and examples thereof include:
Monoazo metal complexes; acetylacetone metal complexes; metal complexes of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acids and their metal salts, anhydrides, esters and phenol derivatives such as bisphenol.

For controlling the positive charging property, a modified product with nigrosine and a fatty acid metal salt; a quaternary ammonium salt such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate. , And onium salts such as phosphonium salts, which are analogs thereof, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdate acid, phosphotungsten molybdate acid, Tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanine compounds, etc.); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide;
Organo tin borates such as dibutyl tin borate, dioctyl tin borate, dicyclohexyl tin borate are included. These may be used alone or in combination of two or more.

The content of the charge control agent is 100% by weight of the binder resin 100.
About 0.5 to 10 parts by mass is preferable with respect to parts by mass. If the content is low, the desired effect cannot be obtained,
When the amount is large, the fluidity of the toner is deteriorated.

Inorganic fine powder may be used as a fluidity improver in the toner of the present invention. As the fluidity improver, any fluidity improver can be used as long as the fluidity can be increased by externally adding the toner particles before and after the addition. For example, fine powder silica such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder and the like, fine powder silica such as wet process silica and dry process silica, and silane coupling agent, titanium coupling agent, silicone oil, etc. There is a treated silica which has been subjected to a surface treatment by. A preferred fluidity improver is a fine powder produced by vapor phase oxidation of a silicon halogen compound, which is so-called dry process silica or fumed silica, and is produced by a conventionally known technique. . For example,
It utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen, and the basic reaction formula is as follows. SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this production process, it is also possible to obtain a fine composite powder of silica and another metal oxide by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound. Also included as silica. The average particle diameter of the particles is preferably in the range of 0.001 to 2 μm, and particularly preferably 0.002 to 0.2.
It is preferable to use silica fine powder in the range of μm.

Examples of commercially available silica fine powders produced by vapor phase oxidation of a silicon halogen compound include those commercially available under the following trade names. AEROSiL (Nippon Aerosil Forest) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N 20H (WACKER-CHE) ) V15 N20E T30 T40 D-C Fine Silica (Dow Corning Co.) Francol (Francil)

Furthermore, it is preferable to use a treated silica fine powder obtained by subjecting the silica fine powder produced by vapor-phase oxidation of the silicon halogen compound to a hydrophobic treatment. The treated silica fine powder is particularly preferably one obtained by treating the silica fine powder so that the hydrophobicity titrated by the methanol titration test shows a value in the range of 30 to 80.

As a method of hydrophobizing, it is imparted by chemically treating with an organic silicon compound or the like which reacts with or physically adsorbs on silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound. Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, and benzyldimethylchlorosilane. , Bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyl Dimethoxysilane, diphenyldiethoxysilane, 1
-Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and having 2 to 12 siloxane units per molecule, one for each terminally located unit S
Examples thereof include dimethylpolysiloxane containing a hydroxyl group bonded to i. These are used alone or as a mixture of two or more.

The inorganic fine powder may be treated with silicone oil, or may be treated in combination with the above hydrophobic treatment.

A preferred silicone oil is 25
Those having a viscosity at 30 ° C. of 30 to 1000 mm ² / s are used, and for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil and the like are particularly preferable.

The method for treating silicone oil is, for example, a method in which silica fine powder treated with a silane coupling agent and silicone oil are directly mixed using a mixer such as a Henschel mixer; Method of spraying silicone oil on the surface; or after dissolving or dispersing silicone oil in a suitable solvent,
It is possible to use a method in which fine silica powder is added and mixed to remove the solvent. Silicone oil treated silica
Silica in inert gas after treatment with silicone oil 2
It is more preferable to heat to 00 ° C or higher (more preferably 250 ° C or higher) to stabilize the surface coating.

Aminopropyltrimethoxysilane having a nitrogen atom, aminopropyltriethoxycine, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane, monobutylamino Propyltrimethoxysilane, dioctylaminopropyldimethoxysilane,
A silane coupling agent such as dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ-propylbenzylamine may be used alone or in combination. Used. As a preferable silane coupling agent, hexamethyldisilazane (HMDS)
Is mentioned.

In the present invention, silica is previously added to
Those treated by a method of treating with a coupling agent and then a silicone oil, or a method of treating silica with a coupling agent and a silicone oil at the same time are preferable.

The fluidity improver has a specific surface area by nitrogen adsorption of 30 m ² / g or more, preferably 5 or more, as measured by the BET method.
Those of 0 m ² / g or more give good results. The fluidity improver may be used in an amount of 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass based on 100 parts by mass of the toner particles.

If necessary, an external additive other than the chargeability improving agent may be added to the toner of the present invention.

For example, resin fine particles or inorganic fine particles that act as a charging aid, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent, a lubricant, an abrasive, etc. As such, for example, polyfluorinated ethylene,
Lubricants such as zinc stearate, polyvinylidene fluoride,
Of these, polyvinylidene fluoride is preferable. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate are preferable, and strontium titanate is particularly preferable. Alternatively, fluidity-imparting agents such as titanium oxide and aluminum oxide, among which hydrophobic ones are particularly preferable. Alternatively, a small amount of anti-caking agent, conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, tin oxide, etc., or fine particles of opposite polarity can be used as a developing property improver.

The resin fine particles, the inorganic fine powder or the hydrophobic inorganic fine powder mixed with the toner is preferably used in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the toner.

The toner of the present invention can be mixed with a carrier and used as a two-component toner. The current value of the carrier is preferably 20 to 200 μA by adjusting the degree of unevenness of the carrier surface and the amount of resin to be coated.

As the resin for coating the surface of the carrier, a styrene-acrylic acid ester copolymer, a styrene-methacrylic acid ester copolymer, an acrylic acid ester copolymer, a methacrylic acid ester copolymer, a silicone resin,
Fluorine-containing resin, polyamide resin, ionomer resin,
A polyphenylene sulfide resin or the like or a mixture thereof can be used.

As the magnetic material for the carrier core, oxides such as ferrite, iron-excessive ferrite, magnetite and γ-iron monoxide, metals such as iron, cobalt and nickel, or alloys thereof can be used. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin,
Examples thereof include zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium.

The toner of the present invention preferably has a weight average particle diameter of 3 to 9 μm from the viewpoint of image density and resolution.

To prepare the toner of the present invention, first, a binder resin, a colorant and / or a magnetic material, a release agent, a charge control agent or other additives are mixed with a mixer such as a Henschel mixer or a ball mill. Mix well. The mixture is melted and kneaded using a kneader such as a kneader or an extruder to make the resins compatible with each other, and the solidified product is crushed after cooling and solidification of the melt-kneaded product, and the crushed product is classified according to the invention. Toner can be obtained. Further, a toner having a fluidity improver and / or other external additive on the surface of toner particles is obtained by thoroughly mixing the fluidity improver and / or other external additive with a toner by a mixer such as a Henschel mixer. You can

The following are commonly used toner manufacturing devices, but the present invention is not limited to these.

Crushing device for toner manufacturing Example: Device name Manufacturer Counter jet mill Hosokawa Micron Micron jet Hosokawa Micron IDS type mill Japan Pneumatic Industrial PJM jet crusher Japan Pneumatic industrial cross jet mill Kurimoto Tekkosho Ulmax Nisso Engineering SK jet Oh-Mill Seishin Enterprise Kryptron Kawasaki Heavy Industries Turbo-Mill Turbo Industrial Inomazer Hosokawa Micron

Example of classification device for toner production: Device name Manufacturer Clasir Seisin Company Micron Classifier Seisin Company Spedic Classifier Seisin Company Turbo Classifier Nisshin Engineering Micron Separator Hosokawa Micron Turboplex (ATP) Hosokawa Micron TSP Separator Hosokawa Micron Elbow Jet Nichi Iron Mining Dispersion Separator Nippon Pneumatic Mfg. YM Micro Cut Yasukawa

Sieve device for toner production Example: Device name Manufacturer Ultrasonic Koei Sangyo Rezona Sheep Tokuju Seisakusho Vibrasonic System Dalton Soniclein Shinto Kogyo Gyro Shifter Dekuju Seisakusho Circular Vibrating Sieve Manufacturer Many Turbo Screener Turbo Industrial Micro Shifter Makino industry

Mixing device for toner production: Device name Manufacturer Henschel Mixer Mitsui Mine Super Mixer Kawata Ribocon Okawara Seisakusho Nauta Mixer Hosokawa Micron Spiral Pin Mixer Pacific Kiko Redige Mixer Matsuboter Bulizer Hosokawa Micron Cyclomix Hosokawa Micron

Kneading apparatus for toner production: Equipment name Manufacturer KRC Kneader Kurimoto Iron Works Buss Co-Kneader Buss TEM type extruder Toshiba Machine TEX twin-screw kneader Japan Steel Works PCM kneader Ikegai Ironworks 3-roll mill Inoue mill mixing Roll mill Inoue mill Kneader Inoue mill Needex Mitsui Mine MS type pressure kneader Moriyama mill Nider Ruder Moriyama mill Banbury mixer Kobe Steel

The methods for measuring the physical properties of the toner and raw materials of the present invention are shown below.

(1) Quantitative measurement device for sulfonic acid-containing monomer and copolymer in toner: HP3D capillary electrophoresis system (manufactured by HEWLETT PACK ARD) Measurement conditions: Capillary: 75 μm × 56 cm Buffer: 20 mM phosphoric acid or Borate buffer pH 8 to 10 Applied voltage: positive 20 to 30 kV Capillary temperature: 20 to 30 ° C. Injection: Pressurization method 50 mbr, 2-3 s Detection: 200 nm 0.1 to 0.5 g of measurement sample and 5 to 10 ml of methanol in a centrifuge tube. After putting in and ultrasonically dispersing for 1 hour, 600
Extract AMPS by centrifugation at 0 rpm for 30 minutes. After centrifugation, the supernatant is filtered with a 0.2 μm filter, and diluted with pure water for electrophoresis (CE) by a factor of 2 to put 50 μl in a vial to obtain a measurement sample. When this sample was measured under the above measurement conditions, a UV absorption spectrum specific to the sulfonic acid-containing monomer and copolymer as shown in FIG. 1 (here, UV absorption of 2-acrylamido-2-methylpropanesulfonic acid (AMPS)) A peak with a spectrum) appears. From the area of this peak, the contents of the sulfonic acid-containing monomer and the copolymer are measured.

In measuring the sample, the content of the sulfonic acid-containing monomer and copolymer contained in the sample was measured by using a calibration curve prepared with a methanol standard solution of the sulfonic acid-containing monomer and copolymer adjusted in advance. It is calculated from the relationship between the logarithmic value and the peak area.

(2) Measurement of glass transition temperature (Tg) and melting point of wax Measuring device: differential scanning calorimeter (DSC), DSC-7
(Manufactured by Perkin-Elmer) Measured according to ASTM D3418-82.

The measurement sample is 2 to 10 mg, preferably 5 m
Weigh g accurately. This is placed in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at room temperature and normal humidity at a temperature rising rate of 10 ° C./min in a measurement temperature range of 30 to 200 ° C. The analysis is performed using the DSC curve in the temperature range of 30 to 200 ° C. obtained in the second heating process.

Regarding the glass transition temperature (Tg), the value analyzed by the midpoint method from the obtained DSC curve is used.
For the melting point of the wax, the temperature value of the endothermic main peak of the obtained DSC curve is used.

(3) Measurement of molecular weight Measuring apparatus: HLC-8120GPC (manufactured by Tosoh Corporation) The molecular weight of the chromatogram by GPC is measured under the following conditions.

The column is stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent is flown through the column at this temperature at a flow rate of 1 ml / min.
When the sample is a binder resin raw material, the binder resin raw material is passed through a roll mill (130 ° C., 15 minutes). If the sample is toner, 0.2μ after dissolving the toner in THF
m-filter and use the filtrate as a sample.
The measurement is performed by injecting 50 to 200 μl of a THF sample solution of a resin adjusted to a sample concentration of 0.05 to 0.6% by mass. When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for creating a calibration curve,
For example, Pressure Chemical Co.
Made or manufactured by Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 1
0 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ ,
5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.
It is suitable to use those of 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

As the column, a plurality of commercially available polystyrene gel columns may be combined in order to accurately measure the molecular weight region of 10 ³ to 2 × 10 ⁶ , for example, Water.
s Co., Ltd. of μ-styragel 500,10 ^3, 1
Combination of 0 ⁴ , 10 ⁵ and shodex manufactured by Showa Denko KK
KA801, 802, 803, 804, 805, 80
A combination of 6,807 is preferred.

(4) Measurement of particle size distribution Measuring device: Coulter Multisizer IIe (manufactured by Beckman Coulter, Inc.) As the electrolytic solution, primary sodium chloride was used and 1% N
Prepare an aCl aqueous solution. For example, ISOTON R-
II (manufactured by Beckman Coulter) can be used. The measuring method is 100 to 150 ml of the electrolytic aqueous solution.
0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles having a particle size of 2 μm or more are measured by the measuring device using a 100 μm aperture as an aperture. The volume distribution and number distribution were calculated. Then, the weight average particle diameter (D4) and the number average particle diameter (D1) according to the present invention (the median value of each channel is used as a representative value for each channel) were determined.

[0096]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

(1) Production Example of Sulfonic Acid-Containing Monomer and Copolymer) (Production of Compound 1) -Water: 200 g-Isopropanol (IPA): 200 g-Methylethylketone (MEK): 100 g-Styrene: 586 g-2 -Ethylhexyl acrylate: 112 g-Acrylamido-2-methylpropanesulfonic acid: 53 g-Lauroyl peroxide: 7 g The above raw materials were placed in a flask and equipped with a stirrer, a temperature measuring device and a nitrogen introducing device, and under a nitrogen atmosphere 65. The solution was polymerized at 0 ° C. and kept for 10 hours to complete the polymerization reaction.
The resulting polymer was dried under reduced pressure and then pulverized with a jet mill to obtain Compound 1 having a polymerization average molecular weight of 33,000 and a Tg of 78 ° C.
Got

(Production of Compounds 2 to 6 and 8 to 10) In the above production method of Compound 1, the raw materials shown in Table 1 were used,
Compounds 2 to 6 and 8 to 10 shown in Table 1 were obtained in the same manner except that the polymerization reaction was carried out while changing the temperature, time and the like.

(Production of Compound 7) In the production process of Compound 1, 0.3% of 2-acrylamido-2-methylpropanesulfonic acid was added to the mass of Compound 1 after termination of the polymerization reaction, and thereafter, In the same manner, Compound 7 as shown in Table 1 was obtained.

[0100]

[Table 1]

(2) Production Example of Binder Resin (Production of Binder Resin 1) -Trimellitic acid: 365 g-Fumaric acid: 336 g-Propoxylated bisphenol A: 1060 g-Epoxidized bisphenol A: 966 g Esterification of the above monomers A 4-necked flask was charged with the catalyst and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, under a nitrogen atmosphere at 23
The temperature was raised to 0 ° C. to carry out the reaction. After completion of the reaction, the resin was taken out from the container, cooled and pulverized to obtain Binder Resin 1.

(Production of Binder Resin 2) 1060 g of xylene
Was charged into a reaction vessel equipped with a reflux pipe, a stirrer, a nitrogen introduction pipe, a thermometer, a dropping device and a decompression device, and then styrene 1394 g, butyl acrylate 436 g, monobutyl maleate 550 g and di-t as a polymerization initiator. -Butyl peroxide (158 g) was added, and the mixture was heated to the reflux temperature with nitrogen bubbling and held for 12 hours. Next, xylene was distilled off under reduced pressure to obtain a binder resin 2.

(Production of Binder Resin 3) -Terephthalic acid: 400 g-Trimellitic acid: 400 g-Dodecenylsuccinic acid: 500 g-Propoxylated bisphenol A: 700 g-Ethoxylated bisphenol A: 300 g The above polyester monomer and the waxes shown in Table 2 One to one
44 g, charged into a 4-neck flask together with an esterification catalyst, equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirring device, and under a nitrogen atmosphere, 130
While stirring at a temperature of ℃, vinyl polymerization monomer (styrene 472g, 2-ethylhexyl acrylate 103
and a mixture of 0.1 g of divinylbenzene) were added dropwise from the dropping funnel over 4 hours. While maintaining the temperature at 130 ° C, the mixture was aged for 3 hours, heated to 230 ° C and reacted.
After completion of the reaction, the resin was taken out from the container, cooled and pulverized to obtain a binder resin 3.

[0104]

[Table 2]

(3) Example (Production of Toner 1) Binder resin 3: 105 parts by mass Magnetic iron oxide: 90 parts by mass (average particle size 0.2 μm, HC 9.5 kA / m, σs = 81 Am ² / kg, σr = 11 Am ² / kg) -Salicylic acid-based Al complex: 0.5 parts by mass-Compound 1: 2 parts by mass The above mixture was melt-kneaded in a twin-screw extruder heated to 130 ° C, and the mixture was cooled. Was roughly crushed with a hammer mill. The coarsely pulverized material is finely pulverized with a jet mill, and the obtained fine powder is classified with an air classifier to obtain a weight average particle diameter of 7 μm.
Magnetic toner of

To 100 parts by mass of this magnetic toner, 1.0 part by mass of hydrophobic oil silica (BET140 m ² / g) was externally added by a Henschel mixer to obtain a toner 1.

The content of the sulfonic acid-containing monomer in Toner 1 thus obtained was measured by the above-mentioned method and found to be 5 ppm.

Next, this toner 1 was used in a normal environment (temperature: 23 ° C., using a Canon digital copying machine GP405).
Humidity: 60%) and high temperature and high humidity (temperature: 30 ° C, humidity:
The paper passing test of 100,000 sheets was performed at 80%), and the following points were evaluated.

Image Density As a result of comparing the image densities before and after 100,000 sheets of durability, the following good results were obtained. Under normal environment: Initial image density 1.41 → 1.4 after 200,000 sheets
1 High temperature and high humidity: Initial image density 1.40 → 1.3 after 200,000 sheets
8

As a result of measuring the image fog after running 100,000 sheets of fog, good results were obtained under normal environment: 0.2% and under high temperature and high humidity: 0.2%.

Tribo on sleeve Measurement of tribo on sleeve before and after 100,000 sheets durability,
The following good results were obtained. Under normal environment: initial −9.1 μC / g → −8.2 μC / g High temperature and high humidity: initial −8.0 μC / g → −6.4 μC / g

High-temperature high-humidity storage test After the 100,000-sheet endurance developer was left as it was for 1 week under high temperature and high humidity, 1000 sheets were passed, and the image density was evaluated. Results were obtained. Image density: 1.32 for the first sheet → 1.37 for the 1000th sheet

(Production of Toners 2 to 13) Toners 2 to 13 were obtained in the same manner as in the production method of Toner 1, except that the raw materials shown in Table 3 were changed. Further, as a result of performing evaluation in the same manner as in Example 1, good results as shown in Table 4 were obtained.

(Production of Comparative Toners 1 to 3) Comparative Toners 1 to 3 were obtained in the same manner as in the production method of Toner 1, except that the raw materials shown in Table 3 were changed. Example 1
As a result of evaluation in the same manner as above, the results shown in Table 4 were obtained.

[0115]

[Table 3]

[0116]

[Table 4]

[0117]

As described above, according to the present invention, there is provided a toner capable of maintaining good developability without image density reduction and fog generation not only in a normal environment but also in long-term durability under high temperature and high humidity. be able to.

[Brief description of drawings]

FIG. 1 is a graph showing a UV absorption spectrum of 2-acrylamido-2-methylpropanesulfonic acid.

Continued front page    (72) Inventor Yuichi Mizoo             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Yusuke Hasegawa             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F term (reference) 2H068 AA19 AA20 BA13 BA38 BA39                       BA40

Claims (17)

[Claims] 1. A toner containing at least a binder resin and a colorant, wherein the toner contains 0.1 to 100 ppm of a sulfonic acid-containing monomer. 2. The toner according to claim 1, wherein the sulfonic acid-containing monomer is a sulfonic acid-containing acrylamide monomer. 3. The toner according to claim 1, wherein the sulfonic acid-containing monomer is 2-acrylamido-2-methylpropanesulfonic acid. 4. The toner according to any one of claims 1 to 3, wherein the toner further contains a copolymer of a styrene / acrylic monomer and a sulfonic acid-containing monomer. 5. The copolymerization ratio of the copolymer is 98/2 to 8
The toner according to claim 4, which is 0/20. 6. The copolymerization ratio of the copolymer is 95/5 to 8
The toner according to claim 4, which is 5/15. 7. The weight average molecular weight of the copolymer is 2000.
7 to 200,000. 7.
The toner according to any one of 1. 8. The weight average molecular weight of the copolymer is 1,000.
7. The toner according to claim 4, which is 0 to 150,000. 9. The weight average molecular weight of the copolymer is 1500.
The toner according to any one of claims 4 to 6, which is 0 to 120,000. 10. The glass transition temperature (Tg) of the copolymer.
10. The toner according to claim 4, wherein the temperature is 50 to 90 ° C. 11. A glass transition temperature (Tg) of the copolymer.
Is 70 to 85 ° C. 10. The toner according to claim 4, wherein the toner is 70 to 85 ° C. 12. The toner has a weight average particle diameter of 3 to 9.
The toner according to claim 1, wherein the toner has a thickness of μm. 13. The toner according to claim 1, wherein the binder resin is a polyester resin. 14. The toner according to claim 1, wherein the binder resin is a vinyl-based copolymer. 15. The binder resin contains a hybrid resin component having a polyester unit and a vinyl-based copolymer unit.
2. The toner according to any one of 2. 16. The toner according to claim 1, wherein the toner contains magnetic powder as a colorant. 17. The toner according to any one of claims 1 to 16, wherein the toner is externally added with a hydrophobized silica fine powder.